В.П. Федин

ВП Федин

Пористые координационные полимеры от синтеза

и структуры к функциональным свойствам

wwwniicnscruclusterniicnscru

1

ПЛАН ЛЕКЦИИ

1)Ведение

2)MOFs для сорбции и разделения

3)MOFs как сенсоры

4)MOFs для энантиоселективного разделения

5)Материалы с высокой протонной

проводимостью

6)Заключение

Координационные полимеры

AgCN

hellip rarrAg‒CequivNrarr Ag‒CequivN rarrAg‒CequivN rarr

Pd(CN)2KFe[Fe(CN)6]

Питер ван дер Верфф Погребение Христа (1709)

Соединения с координационными связями металл-лиганд в которых атомы

металлов связаны мостиковыми лигандами с образованием регулярной

структуры

Zeolites Metal-Organic

Frameworks MOFs

Nanocarbons

Примеры пористых материалов

4

История MOF

[CuI(tpc)]BF4

tpc

Hoskins BF Robson R

J Am Chem Soc 1989

S Noro S Kitagawa et al

Angew Chem Int Ed 2000

bpy

[CuI(SiF6)(bpy)]

[Zn4O(bdc)3] (MOF-5)

OM Yaghi et al

Science 2003

bdc2-

Porous coordination polymers (PCPs)

Metal-organic frameworks (MOFs)

Web of Science

May 1 2017

Search titlemetal-

organic framework

h-index = 253 ()

6

Metal-organic frameworks

+Inorganic BU Organic BU

7

Building units

Linear

Triangular

Tetrahedral

Square

Octahedral

Inorganic BU Organic BU

М2(СОО)3

М2(СОО)4

М2(СОО)4L2М4O(СОО)6

O

O

O

O

O

O

COO

OOC

COO

COO

N

N

N

N

NN

coo

coo

coo

ooc

O

O O

O

O

OO

O

N NOH

HO

O

O

8

Примеры дизайна 3D пористых структур

[Zn4O(OOC-R)6]

ВСБ

O

O O

O

O

O

O

O

O

O O

O

O

O O

O

OM Yaghi et al Science 2002 295 469 Nature 2003 423 705

++

Natura abhorret vacuum

10

H Furukawa et al Science 2010 329 424

Void volume = 89 Crystal density = 025 gcm2

S(BET) = 6240 m2g S(Lang) = 10400 m2g

Рекорды в науке

11

Основные особенности MOFs

Framework

magnetic

electric

optical

dynamic (breathing) behavior

Pores and channels

storage

separation

ion exchange

mediation of unique chemical reactions

Surface

catalysis

adsorption

selective recognition

post-synthetic modifications

12

MOFs for sorption and separation

13

MOF

[Zn4(dmf)(ndc)4(ur)2]middot5DMF∙Н2О

Zn(NO3)2middot6H2O + H2ndc + urDMF

100degС 12 hYield 42

[Zn4(dmf)(ndc)4(ur)2]middot5DMFmiddotH2O

α channels 9times11 Aring

β channels 6times9 Aring ur =

Zn

Zn

Zn Zn

N

N

N

N

HOOC

COOH

H2ndc =

β

β

β β

α

α

α

α

α

14


[Zn4(dmf)(ndc)4(ur)2]

1 CH2Cl2 3 days

2 50 ordmC vacuum

1 day

SA Sapchenko et al Dalton Trans 2011 40 2196

[Zn4(dmf)(ndc)4(ur)2] guest-free α channels

Channels 9x11 Aring

Monoclinic Cc

15

[Zn4(dmf)(ndc)4(ur)2] N2 and H2 adsorption

00 25 50 75 100 125 150

00

01

02

03

04

05

06

07

(d

Vd

D)

Диаметр нм

S (BET) = 820 m2 g-109 nm

15 nm

36 nm

77 K 092 Н2

ΔHads = 47 ndash 52 kJmol

Hydrogen sorption isotherms at 77 and 87 K

Nitrogen sorption isotherm at 77 K

16

[Zn4(dmf)(ndc)4(ur)2] C2H2 CO2 and CO adsorption

C2H

2 adsorption

C2H

2 desorption

CO2 adsorption

CO2 desorption

CO adsorption

CO desorption

0 20 40 60 80 100

0

10

20

30

40

50

60

V m

lg

pp0

0 20 40 60 80 100

0

5

10

15

20

25

30

35

V m

lg

C2H

2 adsorption

C2H

2 desorption

CO2 adsorption

CO2 desorption

CO adsorption

CO desorption

pp0

273 K

298 K

C2H2

CO2

CO

C2H2

CO2

CO

SA Sapchenko et al Chem Commun 2015 51 13918

17

DFT calculations


View of charge density isosurfaces for the interactions of (a) C2H2 (b) CO2 and (c)

CO with the urotropine linker for the most favorable intermolecular interactions Red

represents the accumulation of electron density and blue the depletion of electron

density

18

[Zn2(dmf)(ur)2(ndc)4] + S4N4 + xMe2C=O rarr [Zn2(S4N4)(ur)2(ndc)4]middotxMe2C=O +DMF

ZnmiddotmiddotmiddotN 2885 Aring

ZNU inclusion of S4N4

[Zn2(S4N4)(ur)2(ndc)4] ]middotxMe2C=O + Me2C=Orarr[Zn2(Me2C=O)(ur)2(ndc)4]middotxMe2C=O + S4N4

[Zn2(Me2C=O)(ur)2(ndc)4]middotxMe2C=O rarr [Zn2(ur)2(ndc)4] + (x+1)Me2C=O (in vacuum)19

Step-by-step activation of biporous ZNU

β

β

β β

α

α

α

α

α

[Zn2(dmf)(ur)2(ndc)4] S(BET) = 820 m2 g-1

[Zn2(ur)2(ndc)4] S(BET) = 1113 m2 g-1


β channels 6times9 Aring

00 02 04 06 08 1050

100

150

200

250

300

[Zn4(dmf)(ur)

2(ndc)

4]

[Zn4(ur)

2(ndc)

4]

V млг

pp0

SA Sapchenko et al Inorg Chem 2013 52 970220

ZNU selective separation

21


Zn2+ + H2tdc + dabco [Zn2(tdc)2dabco]solv∆

SHOOC COOH

N

N

H2tdc dabco

Channels (75 x 75 Aring) S-decorated windows (3times4 Aring)

Porous zinc(II) thiophenedicarboxylate

Very similar to the structure of [Zn2(bdc)2dabco] (DN Dybtsev et al

ACIE 2004 43 5033)

VA Bolotov et al 2017 MS in preparation 22

[Zn2(tdc)2dabco] Guest-dependent

framework dynamics

vacuum

solvent

Fully reversible

V = -3

AGAIN Very similar to [Zn2(bdc)2dabco] (DN Dybtsev et al ACIE 2004 43 5033)

TDC ligands are linearTDC ligands are bent

23

0

50

100

150

200

250

300

350

400

450

500

0 01 02 03 04 05 06 07 08 09 1

Am

ount adsorb

ed m

Lg

Relative pressure PP0

Adsorption

Desorption

[Zn2(tdc)2dabco] nitrogen adsorption

N2 adsorption isotherm at 77K Pore-size distribution plot

Porous properties

BET surface area = 1800 m2g

Langmuir = 2000 m2g

Pore volume = 07 mlg

AGAIN Very similar to the properties

of [Zn2(bdc)2dabco]24

0

20

40

60

80

100

120

140

160

180

0 01 02 03 04 05 06 07 08 09 1

Am

ou

nt

ad

so

rbe

d

mL

g


Adsorption

Desorption

[Zn2(tdc)2dabco] CO2 adsorption at 273 K

CO2 sorption summary

-- Highly unsaturated adsorption curve

-- At 1 bar (273 K) = 162 mlg = 32

mass

-- formula [Zn2(tdc)dabco]4СО2

-- This number is higher than for any

other porous MOF at this conditions

except for SNU-5 (385 mass)

Suh M P et al ACIE 2008 47 7741

See also J Long et al Chem Rev

2012 112 724

Twice as higher than for [Zn2(bdc)2dabco] 25

VA Bolotov et al 2017 MS in preparation

Snapshot from GCMC simulation at low pressure in which the majority of CO2

molecules were found to be located near to the thiophene ring (a) The DFT-optimised

lowest-energy binding site for CO2 viewed from above (b) and alongside the TDC

fragment (c)

Calculated binding energies ranging from ndash157 to ndash183 kJmolndash1 ca 3-10 kJmolndash1

stronger than reported binding energies for CO2 with benzene-based moieties

GCMC and DFT calculations


MOFs for sensor materials

28

Cryptand-like MOF(H3O)2[Zn4(ur)(Hfdc)2(fdc)4]middotG

SA Sapchenko et al Chem Eur J 2017 23 2286

OmiddotmiddotmiddotO = 3076(2) and 2908(2) Aring

K+ 1 + Cs+K+ +

2 3

Cs+

Cations exchange

KmiddotmiddotmiddotO(fdc) = 286 Aring KmiddotmiddotmiddotO(COO) = 302 Aring

CsmiddotmiddotmiddotO(fdc) = 310 Aring CsmiddotmiddotmiddotO(COO) = 314 Aring

a) Molar fraction of alkali metal cation in the

supramolecular adducts of compound 1 after

immersion in 001 M MNO3 solution (M=Li NaK

Rb Cs) in NMP

b) Molar fraction of alkali metal cation in a 0001 M

solution of alkali metals nitrates (blue) versus the

molar fraction obtained within the supramolecular

adduct of 1 (red)


Solid-state photoluminescence spectra

of compound 1 and its adducts with alkali

metal cations

Extraction and detection of alkali metal cations

Chiral MOFs for

enainioselective separation

0 10 20 30 40

R

S

32

Metal or cluster

cation

Chiral rigid bridging

ligand (spacer)

Chiral porous MOF

Cl

Cl

N

N

OH

OH

O

O

O

OO

O

N

N

O O

O O

HO NH

N

O

O

P

P

O

O

OH

OH

OH

OH

Synthesis of chiral porous MOFs

some examples of ligands used for the synthesis33

Катион

металла

Хиральный

лиганд

хиральность

Хиральный комплекс

(Вторичный СБ)Хиральный пористый

МОКП

Жесткий

мостик

пористость

bull Позволяет использовать простые доступные хиральные лиганды

природного происхождения

bull Позволяет контролировать размер пор за счет изменения длины

мостиковых лигандов

ДВА ЛИГАНДА ЛУЧШЕ ОДНОГО

Новый подход к синтезу хиральных

пористых МОКП

DN Dybtsev et al Angew Chem Int Ed 2006 45 91634

Zn(NO3)2

(+)-camphoric acid

+

Layered zinc(II) camphorate

DMF + Py

Structure of Zn2 paddle-wheel

[Zn2camph2py2]middotDMF

Zn(II) Camphorates

35DN Dybtsev et al Inorg Chem 2007 46 6843

N

N

N

N

N

Ndabcobipy

bpe

Chiral

layers

Homochiral

porous

frameworkLinear pillars

From chiral 2D layer to chiral 3D framework

36

[Zn2camph2dabco] [Zn2camph2bipy] [Zn2camph2bpe]

Vfree = 31

channel

3 35 Aring

Sarea = 520 m2g

Vfree = 51

channel

5 7 Aring

Sarea = 1040 m2g

Vfree = 56

channel

5 10 Aring

Isoreticular chiral porous MOFs

DN Dybtsev et al Inorg Chem 2007 46 6843 37

38

Porous Zn(II) lactate-terephtalate

Zn(NO3)2

(S)-H2lac

OH

HO

O

O

H2bdc

DMF

100 degC[Zn2(S-lac)(bdc)(dmf)]middotDMF

Chiral chain

OO

OO

Linear

spacer

4 x 5 Aring 5 x 5 Aring

COOH

HO H

CH3

Chiral chain

(SBU) [Zn2(ndc)(R-man)] [Zn2(bpdc)(R-man)]

Zn(NO3)2 +H

COOH

OH

CH3

H

COOH

OH

+

H2lac

H2man

H2ndc

H2bpdc

HO

O

OH

O

HO

O OH

O

DMF

Chiral porous MOFs

39

[Zn2(bdc)(S-lac)] [Zn2(ndc)(R-man)] [Zn2(bpdc)(R-man)]

channel 4 x 5 Aring

window 5 x 5 Aring

channel 5 x 9 Aring

window 4 x 5 Aring

channel 4 x 14 Aring

window 6 x 7 Aring


40

Enantioselective sorption

(R + S)

Racemic

mixture

Stereoselective sorptionS

CH3

O

HO 20 (S)

Sulforaphane

Zn(NO3)2 + +CH3

H

COOH

OH

OH

HO

O

O

[Zn2(S-lac)(bdc)]

SCH3

O

S

O

CH3

OH

HO

Enantiomeric excess (ee)

ee= ([R]-[S])([R]+[S])

Substrate ee()

60 (S)

55 (S)

21 (S)

25 (+)

no sorptionS

CH3

OChiral sorbent

[Zn2(S-lac)(bdc)]

Angew Chem Int Ed 2006 45 916 Chem Eur J 2010 16 10348

41

Racemic

mixture

Separated

optical

isomers

Chiral

stationary

phase

[Zn2(bdc)(lac)]

0 10 20 30 40

R

S

Con

c (

ru

)

0 20 40 60 80

SR

Con

c (

ru

)

SCH3

O

S

O

Enantioselective separation

DN Dybtsev et al J Am Chem Soc 2007 129 1295842

Chiral guest in chiral host [Zn2(bdc)(S-lac)(dmf)]

1) Эксперимент более высокое сродство каркаса к S-PhEtOH (ee = 21)

2) TG-DSC измерения разложение S-PhEtOHMOF происходит труднее чем

R-PhEtOHMOF (∆H asymp 20 kJmol)

R-PhEtOHMOF S-PhEtOHMOF

d(OhellipO) = 325 Aring d(OhellipC) = 333 Aring

K Suh MP Yutkin et al Chem Commun 2012 48 51343

Materials with high proton-

conductivity

VG Ponomareva et al J Am Chem Soc 2012 134 15640

DN Dybtsev et al ACS Appl Mater Interfaces 2014 6 5161

VG Ponomareva et al RCS Anvances 2017 7 403

MIL-101

Cr3OF(H2O)2 [O2CC6H4CO2]3ca25H2O

45

FOH

H2O H2O

Mesoporous MOF with MTN

zeolytic topology

G Ferey et al Science 309 (2005)

2040

Imparting high proton conductivity to a MOF material

by controlled acid impregnation

(Proton conductivity) (H+ mobility) times (H+ concentration)

Strong (mineral) acids = ideal proton conductors

Inclusion of strong andor non-volatile acids into

mesoporous (and stable) MIL-101

1) Liquids can not be used for membranes

2) Operating temperature of the fuel cell can must be 110 ndash 140 C

H2SO4 H3PO4 TfOH TsOH

MIL-101 acidMIL-101

VG Ponomareva et al J Am Chem Soc 2012 134 15640 DN Dybtsev et al ACS Appl Mater Interfaces 2014 6 5161

How to make acidMIL-101

H2SO4MIL MILmiddot45H2SO4middot10H2O

H3PO4MIL MILmiddot37H3PO4middot5H2O

The molar concentration of the

acid in acidMIL-101

corresponds to concentration

of the initial aqueous solution

(3 - 4 M)

1) Soaking crystalline MIL-101 in an aqueous acid solution (2 - 4

M) for 30 min at room temperature

2) Filtration

3) drying at 60deg C or in vacuo

H-conductivity of acid-impregnated MIL-101

H2SO4

H3PO4

1) Linear vs T plot as soon as the sample hydration is stabilized

2) AcidMIL-101 materials are stable no acid leeching no framework

deterioration after several measurements 48

Inclusion of strong acids does not destroy MIL-101 framework

Deviations in the values of proton conductivity in the heating and

cooling regimes due to different moisture content in the sample The

amount of acid is not changed

Samples at a constant humidity give reproducible proton

conductivity

Maximum proton conductivity = 006 Scm for H2SO4MIL-101 at

80 degC and RH 10

The proton conductivities of the H2SO4MIL-101 and H3PO4MIL-

101 at T = 150 ordmC and low humidity outperform any other MOF-

based materials and could be compared with the best proton

conductors such as Nafion

Nafion = 9middot10minus3 Scm at 80 degC and RH = 3449

Storage and delivery

volatile gases (H2 CH4 C2H2 CO2)

drugs

Selective sorption

gas molecules

enantioseparation

Heterogeneous catalysis

Chiral catalysis

Applications for porous MOFs

laquoВЫВОДЫraquo

1) Химия пористых МОКП (MOFs) чрезвычайно интенсивноразвивается в последние годы но по-прежнему остается laquoновойraquoобластью междисциплинарных исследований

2) Многие исследовательские группы со всего мира сообщают ополучении новых MOF с сенсорными свойствами протонной ионнойэлектронной проводимостью нелинейными оптическим свойствамимагнитными свойствами и тд

3) Очевидно много новых структур с интересными новыми свойствами и применениями будут открыты в ближайшее время

4) ПОСМОТРИТЕ БОЛЕЕ ВНИМАТЕЛЬНО НА ЭТИ СОЕДИНЕНИЯ ВОЗМОЖНО ОНИ МОГУТ ОКАЗАТЬСЯ ПОЛЕЗНЫМИ ДЛЯ ВАШИХ ИССЛЕДОВАНИЙ

51

52

Лаборатория химии кластерных и

супрамолекулярных соединений ИНХ СО РАН

Acknowledgments

Prof K Brilyakov and Prof E Talsi

Prof OA Kholdeeva

Prof V Ponomareva

Prof K Kim

Prof M Schoumlder

Russian Science Foundation

Ministry of Science and Education

Russian Foundation for Basic Research

Институт неорганической химии

им АВ Николаева СО РАН

АСПИРАНТУРА ИНХ СО РАН

актуальные и амбициозные научные задачи публикации в высокорейтинговых журналах навыки работ на современном научном оборудовании международное сотрудничество и зарубежные стажировки стипендии им АВ Николаева гранты и стипендии

Президента РФ другие престижные награды

ИНХ СО РАН является лидирующим научным центром России в области химии

Аспирантура ИНХ СО РАН аккредитована по направлению laquoХимические наукиraquo по специальностям неорганическая химия физическая химия аналитическая химия

Вступительные экзаменыlaquoобщая химияraquolaquoиностранный языкraquo

По всем вопросам обращаться Ирина Валентиновна Андриенко 8-383-330-92-56

Этот е-мэйл может изменить твою жизнь

ПЛАН ЛЕКЦИИ

1)Ведение

2)MOFs для сорбции и разделения

3)MOFs как сенсоры

4)MOFs для энантиоселективного разделения

5)Материалы с высокой протонной

проводимостью

6)Заключение


AgCN


Pd(CN)2KFe[Fe(CN)6]




структуры


Frameworks MOFs

Nanocarbons


4

История MOF

[CuI(tpc)]BF4

tpc

Hoskins BF Robson R

J Am Chem Soc 1989



bpy

[CuI(SiF6)(bpy)]


OM Yaghi et al

Science 2003

bdc2-



Web of Science

May 1 2017

Search titlemetal-

organic framework

h-index = 253 ()

6



7

Building units

Linear

Triangular

Tetrahedral

Square

Octahedral


М2(СОО)3

М2(СОО)4


O

O

O

O

O

O

COO

OOC

COO

COO

N

N

N

N

NN

coo

coo

coo

ooc

O

O O

O

O

OO

O

N NOH

HO

O

O

8


[Zn4O(OOC-R)6]

ВСБ

O

O O

O

O

O

O

O

O

O O

O

O

O O

O


++


10



S(BET) = 6240 m2g S(Lang) = 10400 m2g


11


Framework

magnetic

electric

optical


Pores and channels

storage

separation

ion exchange


Surface

catalysis

adsorption



12


13

MOF







Zn

Zn

Zn Zn

N

N

N

N

HOOC

COOH

H2ndc =

β

β

β β

α

α

α

α

α

14



1 CH2Cl2 3 days

2 50 ordmC vacuum

1 day



Channels 9x11 Aring

Monoclinic Cc

15


00 25 50 75 100 125 150

00

01

02

03

04

05

06

07

(d

Vd

D)

Диаметр нм

S (BET) = 820 m2 g-109 nm

15 nm

36 nm

77 K 092 Н2




16


C2H

2 adsorption

C2H

2 desorption

CO2 adsorption

CO2 desorption

CO adsorption

CO desorption

0 20 40 60 80 100

0

10

20

30

40

50

60

V m

lg

pp0

0 20 40 60 80 100

0

5

10

15

20

25

30

35

V m

lg

C2H

2 adsorption

C2H

2 desorption

CO2 adsorption

CO2 desorption

CO adsorption

CO desorption

pp0

273 K

298 K

C2H2

CO2

CO

C2H2

CO2

CO


17

DFT calculations





density

18







β

β

β β

α

α

α

α

α


[Zn2(ur)2(ndc)4] S(BET) = 1113 m2 g-1



00 02 04 06 08 1050

100

150

200

250

300

[Zn4(dmf)(ur)

2(ndc)

4]

[Zn4(ur)

2(ndc)

4]

V млг

pp0



21



SHOOC COOH

N

N

H2tdc dabco




ACIE 2004 43 5033)



framework dynamics

vacuum

solvent

Fully reversible

V = -3



23

0

50

100

150

200

250

300

350

400

450

500

0 01 02 03 04 05 06 07 08 09 1

Am

ount adsorb

ed m

Lg


Adsorption

Desorption



Porous properties


Langmuir = 2000 m2g




0

20

40

60

80

100

120

140

160

180

0 01 02 03 04 05 06 07 08 09 1

Am

ou

nt

ad

so

rbe

d

mL

g


Adsorption

Desorption




-- At 1 bar (273 K) = 162 mlg = 32

mass







2012 112 724






fragment (c)






28




K+ 1 + Cs+K+ +

2 3

Cs+

Cations exchange






Rb Cs) in NMP




adduct of 1 (red)




metal cations


Chiral MOFs for


0 10 20 30 40

R

S

32

Metal or cluster

cation


ligand (spacer)

Chiral porous MOF

Cl

Cl

N

N

OH

OH

O

O

O

OO

O

N

N

O O

O O

HO NH

N

O

O

P

P

O

O

OH

OH

OH

OH



Катион

металла

Хиральный

лиганд




МОКП

Жесткий

мостик










Zn(NO3)2

(+)-camphoric acid

+


DMF + Py



Zn(II) Camphorates


N

N

N

N

N

Ndabcobipy

bpe

Chiral

layers

Homochiral

porous



36


Vfree = 31

channel

3 35 Aring

Sarea = 520 m2g

Vfree = 51

channel

5 7 Aring

Sarea = 1040 m2g

Vfree = 56

channel

5 10 Aring



38


Zn(NO3)2

(S)-H2lac

OH

HO

O

O

H2bdc

DMF


Chiral chain

OO

OO

Linear

spacer


COOH

HO H

CH3

Chiral chain


Zn(NO3)2 +H

COOH

OH

CH3

H

COOH

OH

+

H2lac

H2man

H2ndc

H2bpdc

HO

O

OH

O

HO

O OH

O

DMF

Chiral porous MOFs

39


channel 4 x 5 Aring

window 5 x 5 Aring

channel 5 x 9 Aring

window 4 x 5 Aring


window 6 x 7 Aring


40


(R + S)

Racemic

mixture


CH3

O

HO 20 (S)

Sulforaphane

Zn(NO3)2 + +CH3

H

COOH

OH

OH

HO

O

O

[Zn2(S-lac)(bdc)]

SCH3

O

S

O

CH3

OH

HO


ee= ([R]-[S])([R]+[S])

Substrate ee()

60 (S)

55 (S)

21 (S)

25 (+)

no sorptionS

CH3

OChiral sorbent

[Zn2(S-lac)(bdc)]


41

Racemic

mixture

Separated

optical

isomers

Chiral

stationary

phase

[Zn2(bdc)(lac)]

0 10 20 30 40

R

S

Con

c (

ru

)

0 20 40 60 80

SR

Con

c (

ru

)

SCH3

O

S

O











conductivity




MIL-101


45

FOH

H2O H2O


zeolytic topology


2040










MIL-101 acidMIL-101






acid in acidMIL-101



(3 - 4 M)



2) Filtration



H2SO4

H3PO4









conductivity


80 degC and RH 10








drugs

Selective sorption

gas molecules

enantioseparation


Chiral catalysis







51

52



Acknowledgments


Prof OA Kholdeeva

Prof V Ponomareva

Prof K Kim

Prof M Schoumlder















AgCN


Pd(CN)2KFe[Fe(CN)6]




структуры


Frameworks MOFs

Nanocarbons


4

История MOF

[CuI(tpc)]BF4

tpc

Hoskins BF Robson R

J Am Chem Soc 1989



bpy

[CuI(SiF6)(bpy)]


OM Yaghi et al

Science 2003

bdc2-



Web of Science

May 1 2017

Search titlemetal-

organic framework

h-index = 253 ()

6



7

Building units

Linear

Triangular

Tetrahedral

Square

Octahedral


М2(СОО)3

М2(СОО)4


O

O

O

O

O

O

COO

OOC

COO

COO

N

N

N

N

NN

coo

coo

coo

ooc

O

O O

O

O

OO

O

N NOH

HO

O

O

8


[Zn4O(OOC-R)6]

ВСБ

O

O O

O

O

O

O

O

O

O O

O

O

O O

O


++


10



S(BET) = 6240 m2g S(Lang) = 10400 m2g


11


Framework

magnetic

electric

optical


Pores and channels

storage

separation

ion exchange


Surface

catalysis

adsorption



12


13

MOF







Zn

Zn

Zn Zn

N

N

N

N

HOOC

COOH

H2ndc =

β

β

β β

α

α

α

α

α

14



1 CH2Cl2 3 days

2 50 ordmC vacuum

1 day



Channels 9x11 Aring

Monoclinic Cc

15


00 25 50 75 100 125 150

00

01

02

03

04

05

06

07

(d

Vd

D)

Диаметр нм

S (BET) = 820 m2 g-109 nm

15 nm

36 nm

77 K 092 Н2




16


C2H

2 adsorption

C2H

2 desorption

CO2 adsorption

CO2 desorption

CO adsorption

CO desorption

0 20 40 60 80 100

0

10

20

30

40

50

60

V m

lg

pp0

0 20 40 60 80 100

0

5

10

15

20

25

30

35

V m

lg

C2H

2 adsorption

C2H

2 desorption

CO2 adsorption

CO2 desorption

CO adsorption

CO desorption

pp0

273 K

298 K

C2H2

CO2

CO

C2H2

CO2

CO


17

DFT calculations





density

18







β

β

β β

α

α

α

α

α


[Zn2(ur)2(ndc)4] S(BET) = 1113 m2 g-1



00 02 04 06 08 1050

100

150

200

250

300

[Zn4(dmf)(ur)

2(ndc)

4]

[Zn4(ur)

2(ndc)

4]

V млг

pp0



21



SHOOC COOH

N

N

H2tdc dabco




ACIE 2004 43 5033)



framework dynamics

vacuum

solvent

Fully reversible

V = -3



23

0

50

100

150

200

250

300

350

400

450

500

0 01 02 03 04 05 06 07 08 09 1

Am

ount adsorb

ed m

Lg


Adsorption

Desorption



Porous properties


Langmuir = 2000 m2g




0

20

40

60

80

100

120

140

160

180

0 01 02 03 04 05 06 07 08 09 1

Am

ou

nt

ad

so

rbe

d

mL

g


Adsorption

Desorption




-- At 1 bar (273 K) = 162 mlg = 32

mass







2012 112 724






fragment (c)






28




K+ 1 + Cs+K+ +

2 3

Cs+

Cations exchange






Rb Cs) in NMP




adduct of 1 (red)




metal cations


Chiral MOFs for


0 10 20 30 40

R

S

32

Metal or cluster

cation


ligand (spacer)

Chiral porous MOF

Cl

Cl

N

N

OH

OH

O

O

O

OO

O

N

N

O O

O O

HO NH

N

O

O

P

P

O

O

OH

OH

OH

OH



Катион

металла

Хиральный

лиганд




МОКП

Жесткий

мостик










Zn(NO3)2

(+)-camphoric acid

+


DMF + Py



Zn(II) Camphorates


N

N

N

N

N

Ndabcobipy

bpe

Chiral

layers

Homochiral

porous



36


Vfree = 31

channel

3 35 Aring

Sarea = 520 m2g

Vfree = 51

channel

5 7 Aring

Sarea = 1040 m2g

Vfree = 56

channel

5 10 Aring



38


Zn(NO3)2

(S)-H2lac

OH

HO

O

O

H2bdc

DMF


Chiral chain

OO

OO

Linear

spacer


COOH

HO H

CH3

Chiral chain


Zn(NO3)2 +H

COOH

OH

CH3

H

COOH

OH

+

H2lac

H2man

H2ndc

H2bpdc

HO

O

OH

O

HO

O OH

O

DMF

Chiral porous MOFs

39


channel 4 x 5 Aring

window 5 x 5 Aring

channel 5 x 9 Aring

window 4 x 5 Aring


window 6 x 7 Aring


40


(R + S)

Racemic

mixture


CH3

O

HO 20 (S)

Sulforaphane

Zn(NO3)2 + +CH3

H

COOH

OH

OH

HO

O

O

[Zn2(S-lac)(bdc)]

SCH3

O

S

O

CH3

OH

HO


ee= ([R]-[S])([R]+[S])

Substrate ee()

60 (S)

55 (S)

21 (S)

25 (+)

no sorptionS

CH3

OChiral sorbent

[Zn2(S-lac)(bdc)]


41

Racemic

mixture

Separated

optical

isomers

Chiral

stationary

phase

[Zn2(bdc)(lac)]

0 10 20 30 40

R

S

Con

c (

ru

)

0 20 40 60 80

SR

Con

c (

ru

)

SCH3

O

S

O











conductivity




MIL-101


45

FOH

H2O H2O


zeolytic topology


2040










MIL-101 acidMIL-101






acid in acidMIL-101



(3 - 4 M)



2) Filtration



H2SO4

H3PO4









conductivity


80 degC and RH 10








drugs

Selective sorption

gas molecules

enantioseparation


Chiral catalysis







51

52



Acknowledgments


Prof OA Kholdeeva

Prof V Ponomareva

Prof K Kim

Prof M Schoumlder















Frameworks MOFs

Nanocarbons


4

История MOF

[CuI(tpc)]BF4

tpc

Hoskins BF Robson R

J Am Chem Soc 1989



bpy

[CuI(SiF6)(bpy)]


OM Yaghi et al

Science 2003

bdc2-



Web of Science

May 1 2017

Search titlemetal-

organic framework

h-index = 253 ()

6



7

Building units

Linear

Triangular

Tetrahedral

Square

Octahedral


М2(СОО)3

М2(СОО)4


O

O

O

O

O

O

COO

OOC

COO

COO

N

N

N

N

NN

coo

coo

coo

ooc

O

O O

O

O

OO

O

N NOH

HO

O

O

8


[Zn4O(OOC-R)6]

ВСБ

O

O O

O

O

O

O

O

O

O O

O

O

O O

O


++


10



S(BET) = 6240 m2g S(Lang) = 10400 m2g


11


Framework

magnetic

electric

optical


Pores and channels

storage

separation

ion exchange


Surface

catalysis

adsorption



12


13

MOF







Zn

Zn

Zn Zn

N

N

N

N

HOOC

COOH

H2ndc =

β

β

β β

α

α

α

α

α

14



1 CH2Cl2 3 days

2 50 ordmC vacuum

1 day



Channels 9x11 Aring

Monoclinic Cc

15


00 25 50 75 100 125 150

00

01

02

03

04

05

06

07

(d

Vd

D)

Диаметр нм

S (BET) = 820 m2 g-109 nm

15 nm

36 nm

77 K 092 Н2




16


C2H

2 adsorption

C2H

2 desorption

CO2 adsorption

CO2 desorption

CO adsorption

CO desorption

0 20 40 60 80 100

0

10

20

30

40

50

60

V m

lg

pp0

0 20 40 60 80 100

0

5

10

15

20

25

30

35

V m

lg

C2H

2 adsorption

C2H

2 desorption

CO2 adsorption

CO2 desorption

CO adsorption

CO desorption

pp0

273 K

298 K

C2H2

CO2

CO

C2H2

CO2

CO


17

DFT calculations





density

18







β

β

β β

α

α

α

α

α


[Zn2(ur)2(ndc)4] S(BET) = 1113 m2 g-1



00 02 04 06 08 1050

100

150

200

250

300

[Zn4(dmf)(ur)

2(ndc)

4]

[Zn4(ur)

2(ndc)

4]

V млг

pp0



21



SHOOC COOH

N

N

H2tdc dabco




ACIE 2004 43 5033)



framework dynamics

vacuum

solvent

Fully reversible

V = -3



23

0

50

100

150

200

250

300

350

400

450

500

0 01 02 03 04 05 06 07 08 09 1

Am

ount adsorb

ed m

Lg


Adsorption

Desorption



Porous properties


Langmuir = 2000 m2g




0

20

40

60

80

100

120

140

160

180

0 01 02 03 04 05 06 07 08 09 1

Am

ou

nt

ad

so

rbe

d

mL

g


Adsorption

Desorption




-- At 1 bar (273 K) = 162 mlg = 32

mass







2012 112 724






fragment (c)






28




K+ 1 + Cs+K+ +

2 3

Cs+

Cations exchange






Rb Cs) in NMP




adduct of 1 (red)




metal cations


Chiral MOFs for


0 10 20 30 40

R

S

32

Metal or cluster

cation


ligand (spacer)

Chiral porous MOF

Cl

Cl

N

N

OH

OH

O

O

O

OO

O

N

N

O O

O O

HO NH

N

O

O

P

P

O

O

OH

OH

OH

OH



Катион

металла

Хиральный

лиганд




МОКП

Жесткий

мостик










Zn(NO3)2

(+)-camphoric acid

+


DMF + Py



Zn(II) Camphorates


N

N

N

N

N

Ndabcobipy

bpe

Chiral

layers

Homochiral

porous



36


Vfree = 31

channel

3 35 Aring

Sarea = 520 m2g

Vfree = 51

channel

5 7 Aring

Sarea = 1040 m2g

Vfree = 56

channel

5 10 Aring



38


Zn(NO3)2

(S)-H2lac

OH

HO

O

O

H2bdc

DMF


Chiral chain

OO

OO

Linear

spacer


COOH

HO H

CH3

Chiral chain


Zn(NO3)2 +H

COOH

OH

CH3

H

COOH

OH

+

H2lac

H2man

H2ndc

H2bpdc

HO

O

OH

O

HO

O OH

O

DMF

Chiral porous MOFs

39


channel 4 x 5 Aring

window 5 x 5 Aring

channel 5 x 9 Aring

window 4 x 5 Aring


window 6 x 7 Aring


40


(R + S)

Racemic

mixture


CH3

O

HO 20 (S)

Sulforaphane

Zn(NO3)2 + +CH3

H

COOH

OH

OH

HO

O

O

[Zn2(S-lac)(bdc)]

SCH3

O

S

O

CH3

OH

HO


ee= ([R]-[S])([R]+[S])

Substrate ee()

60 (S)

55 (S)

21 (S)

25 (+)

no sorptionS

CH3

OChiral sorbent

[Zn2(S-lac)(bdc)]


41

Racemic

mixture

Separated

optical

isomers

Chiral

stationary

phase

[Zn2(bdc)(lac)]

0 10 20 30 40

R

S

Con

c (

ru

)

0 20 40 60 80

SR

Con

c (

ru

)

SCH3

O

S

O











conductivity




MIL-101


45

FOH

H2O H2O


zeolytic topology


2040










MIL-101 acidMIL-101






acid in acidMIL-101



(3 - 4 M)



2) Filtration



H2SO4

H3PO4









conductivity


80 degC and RH 10








drugs

Selective sorption

gas molecules

enantioseparation


Chiral catalysis







51

52



Acknowledgments


Prof OA Kholdeeva

Prof V Ponomareva

Prof K Kim

Prof M Schoumlder














История MOF

[CuI(tpc)]BF4

tpc

Hoskins BF Robson R

J Am Chem Soc 1989



bpy

[CuI(SiF6)(bpy)]


OM Yaghi et al

Science 2003

bdc2-



Web of Science

May 1 2017

Search titlemetal-

organic framework

h-index = 253 ()

6



7

Building units

Linear

Triangular

Tetrahedral

Square

Octahedral


М2(СОО)3

М2(СОО)4


O

O

O

O

O

O

COO

OOC

COO

COO

N

N

N

N

NN

coo

coo

coo

ooc

O

O O

O

O

OO

O

N NOH

HO

O

O

8


[Zn4O(OOC-R)6]

ВСБ

O

O O

O

O

O

O

O

O

O O

O

O

O O

O


++


10



S(BET) = 6240 m2g S(Lang) = 10400 m2g


11


Framework

magnetic

electric

optical


Pores and channels

storage

separation

ion exchange


Surface

catalysis

adsorption



12


13

MOF







Zn

Zn

Zn Zn

N

N

N

N

HOOC

COOH

H2ndc =

β

β

β β

α

α

α

α

α

14



1 CH2Cl2 3 days

2 50 ordmC vacuum

1 day



Channels 9x11 Aring

Monoclinic Cc

15


00 25 50 75 100 125 150

00

01

02

03

04

05

06

07

(d

Vd

D)

Диаметр нм

S (BET) = 820 m2 g-109 nm

15 nm

36 nm

77 K 092 Н2




16


C2H

2 adsorption

C2H

2 desorption

CO2 adsorption

CO2 desorption

CO adsorption

CO desorption

0 20 40 60 80 100

0

10

20

30

40

50

60

V m

lg

pp0

0 20 40 60 80 100

0

5

10

15

20

25

30

35

V m

lg

C2H

2 adsorption

C2H

2 desorption

CO2 adsorption

CO2 desorption

CO adsorption

CO desorption

pp0

273 K

298 K

C2H2

CO2

CO

C2H2

CO2

CO


17

DFT calculations





density

18







β

β

β β

α

α

α

α

α


[Zn2(ur)2(ndc)4] S(BET) = 1113 m2 g-1



00 02 04 06 08 1050

100

150

200

250

300

[Zn4(dmf)(ur)

2(ndc)

4]

[Zn4(ur)

2(ndc)

4]

V млг

pp0



21



SHOOC COOH

N

N

H2tdc dabco




ACIE 2004 43 5033)



framework dynamics

vacuum

solvent

Fully reversible

V = -3



23

0

50

100

150

200

250

300

350

400

450

500

0 01 02 03 04 05 06 07 08 09 1

Am

ount adsorb

ed m

Lg


Adsorption

Desorption



Porous properties


Langmuir = 2000 m2g




0

20

40

60

80

100

120

140

160

180

0 01 02 03 04 05 06 07 08 09 1

Am

ou

nt

ad

so

rbe

d

mL

g


Adsorption

Desorption




-- At 1 bar (273 K) = 162 mlg = 32

mass







2012 112 724






fragment (c)






28




K+ 1 + Cs+K+ +

2 3

Cs+

Cations exchange






Rb Cs) in NMP




adduct of 1 (red)




metal cations


Chiral MOFs for


0 10 20 30 40

R

S

32

Metal or cluster

cation


ligand (spacer)

Chiral porous MOF

Cl

Cl

N

N

OH

OH

O

O

O

OO

O

N

N

O O

O O

HO NH

N

O

O

P

P

O

O

OH

OH

OH

OH



Катион

металла

Хиральный

лиганд




МОКП

Жесткий

мостик










Zn(NO3)2

(+)-camphoric acid

+


DMF + Py



Zn(II) Camphorates


N

N

N

N

N

Ndabcobipy

bpe

Chiral

layers

Homochiral

porous



36


Vfree = 31

channel

3 35 Aring

Sarea = 520 m2g

Vfree = 51

channel

5 7 Aring

Sarea = 1040 m2g

Vfree = 56

channel

5 10 Aring



38


Zn(NO3)2

(S)-H2lac

OH

HO

O

O

H2bdc

DMF


Chiral chain

OO

OO

Linear

spacer


COOH

HO H

CH3

Chiral chain


Zn(NO3)2 +H

COOH

OH

CH3

H

COOH

OH

+

H2lac

H2man

H2ndc

H2bpdc

HO

O

OH

O

HO

O OH

O

DMF

Chiral porous MOFs

39


channel 4 x 5 Aring

window 5 x 5 Aring

channel 5 x 9 Aring

window 4 x 5 Aring


window 6 x 7 Aring


40


(R + S)

Racemic

mixture


CH3

O

HO 20 (S)

Sulforaphane

Zn(NO3)2 + +CH3

H

COOH

OH

OH

HO

O

O

[Zn2(S-lac)(bdc)]

SCH3

O

S

O

CH3

OH

HO


ee= ([R]-[S])([R]+[S])

Substrate ee()

60 (S)

55 (S)

21 (S)

25 (+)

no sorptionS

CH3

OChiral sorbent

[Zn2(S-lac)(bdc)]


41

Racemic

mixture

Separated

optical

isomers

Chiral

stationary

phase

[Zn2(bdc)(lac)]

0 10 20 30 40

R

S

Con

c (

ru

)

0 20 40 60 80

SR

Con

c (

ru

)

SCH3

O

S

O











conductivity




MIL-101


45

FOH

H2O H2O


zeolytic topology


2040










MIL-101 acidMIL-101






acid in acidMIL-101



(3 - 4 M)



2) Filtration



H2SO4

H3PO4









conductivity


80 degC and RH 10








drugs

Selective sorption

gas molecules

enantioseparation


Chiral catalysis







51

52



Acknowledgments


Prof OA Kholdeeva

Prof V Ponomareva

Prof K Kim

Prof M Schoumlder
















Web of Science

May 1 2017

Search titlemetal-

organic framework

h-index = 253 ()

6



7

Building units

Linear

Triangular

Tetrahedral

Square

Octahedral


М2(СОО)3

М2(СОО)4


O

O

O

O

O

O

COO

OOC

COO

COO

N

N

N

N

NN

coo

coo

coo

ooc

O

O O

O

O

OO

O

N NOH

HO

O

O

8


[Zn4O(OOC-R)6]

ВСБ

O

O O

O

O

O

O

O

O

O O

O

O

O O

O


++


10



S(BET) = 6240 m2g S(Lang) = 10400 m2g


11


Framework

magnetic

electric

optical


Pores and channels

storage

separation

ion exchange


Surface

catalysis

adsorption



12


13

MOF







Zn

Zn

Zn Zn

N

N

N

N

HOOC

COOH

H2ndc =

β

β

β β

α

α

α

α

α

14



1 CH2Cl2 3 days

2 50 ordmC vacuum

1 day



Channels 9x11 Aring

Monoclinic Cc

15


00 25 50 75 100 125 150

00

01

02

03

04

05

06

07

(d

Vd

D)

Диаметр нм

S (BET) = 820 m2 g-109 nm

15 nm

36 nm

77 K 092 Н2




16


C2H

2 adsorption

C2H

2 desorption

CO2 adsorption

CO2 desorption

CO adsorption

CO desorption

0 20 40 60 80 100

0

10

20

30

40

50

60

V m

lg

pp0

0 20 40 60 80 100

0

5

10

15

20

25

30

35

V m

lg

C2H

2 adsorption

C2H

2 desorption

CO2 adsorption

CO2 desorption

CO adsorption

CO desorption

pp0

273 K

298 K

C2H2

CO2

CO

C2H2

CO2

CO


17

DFT calculations





density

18







β

β

β β

α

α

α

α

α


[Zn2(ur)2(ndc)4] S(BET) = 1113 m2 g-1



00 02 04 06 08 1050

100

150

200

250

300

[Zn4(dmf)(ur)

2(ndc)

4]

[Zn4(ur)

2(ndc)

4]

V млг

pp0



21



SHOOC COOH

N

N

H2tdc dabco




ACIE 2004 43 5033)



framework dynamics

vacuum

solvent

Fully reversible

V = -3



23

0

50

100

150

200

250

300

350

400

450

500

0 01 02 03 04 05 06 07 08 09 1

Am

ount adsorb

ed m

Lg


Adsorption

Desorption



Porous properties


Langmuir = 2000 m2g




0

20

40

60

80

100

120

140

160

180

0 01 02 03 04 05 06 07 08 09 1

Am

ou

nt

ad

so

rbe

d

mL

g


Adsorption

Desorption




-- At 1 bar (273 K) = 162 mlg = 32

mass







2012 112 724






fragment (c)






28




K+ 1 + Cs+K+ +

2 3

Cs+

Cations exchange






Rb Cs) in NMP




adduct of 1 (red)




metal cations


Chiral MOFs for


0 10 20 30 40

R

S

32

Metal or cluster

cation


ligand (spacer)

Chiral porous MOF

Cl

Cl

N

N

OH

OH

O

O

O

OO

O

N

N

O O

O O

HO NH

N

O

O

P

P

O

O

OH

OH

OH

OH



Катион

металла

Хиральный

лиганд




МОКП

Жесткий

мостик










Zn(NO3)2

(+)-camphoric acid

+


DMF + Py



Zn(II) Camphorates


N

N

N

N

N

Ndabcobipy

bpe

Chiral

layers

Homochiral

porous



36


Vfree = 31

channel

3 35 Aring

Sarea = 520 m2g

Vfree = 51

channel

5 7 Aring

Sarea = 1040 m2g

Vfree = 56

channel

5 10 Aring



38


Zn(NO3)2

(S)-H2lac

OH

HO

O

O

H2bdc

DMF


Chiral chain

OO

OO

Linear

spacer


COOH

HO H

CH3

Chiral chain


Zn(NO3)2 +H

COOH

OH

CH3

H

COOH

OH

+

H2lac

H2man

H2ndc

H2bpdc

HO

O

OH

O

HO

O OH

O

DMF

Chiral porous MOFs

39


channel 4 x 5 Aring

window 5 x 5 Aring

channel 5 x 9 Aring

window 4 x 5 Aring


window 6 x 7 Aring


40


(R + S)

Racemic

mixture


CH3

O

HO 20 (S)

Sulforaphane

Zn(NO3)2 + +CH3

H

COOH

OH

OH

HO

O

O

[Zn2(S-lac)(bdc)]

SCH3

O

S

O

CH3

OH

HO


ee= ([R]-[S])([R]+[S])

Substrate ee()

60 (S)

55 (S)

21 (S)

25 (+)

no sorptionS

CH3

OChiral sorbent

[Zn2(S-lac)(bdc)]


41

Racemic

mixture

Separated

optical

isomers

Chiral

stationary

phase

[Zn2(bdc)(lac)]

0 10 20 30 40

R

S

Con

c (

ru

)

0 20 40 60 80

SR

Con

c (

ru

)

SCH3

O

S

O











conductivity




MIL-101


45

FOH

H2O H2O


zeolytic topology


2040










MIL-101 acidMIL-101






acid in acidMIL-101



(3 - 4 M)



2) Filtration



H2SO4

H3PO4









conductivity


80 degC and RH 10








drugs

Selective sorption

gas molecules

enantioseparation


Chiral catalysis







51

52



Acknowledgments


Prof OA Kholdeeva

Prof V Ponomareva

Prof K Kim

Prof M Schoumlder
















7

Building units

Linear

Triangular

Tetrahedral

Square

Octahedral


М2(СОО)3

М2(СОО)4


O

O

O

O

O

O

COO

OOC

COO

COO

N

N

N

N

NN

coo

coo

coo

ooc

O

O O

O

O

OO

O

N NOH

HO

O

O

8


[Zn4O(OOC-R)6]

ВСБ

O

O O

O

O

O

O

O

O

O O

O

O

O O

O


++


10



S(BET) = 6240 m2g S(Lang) = 10400 m2g


11


Framework

magnetic

electric

optical


Pores and channels

storage

separation

ion exchange


Surface

catalysis

adsorption



12


13

MOF







Zn

Zn

Zn Zn

N

N

N

N

HOOC

COOH

H2ndc =

β

β

β β

α

α

α

α

α

14



1 CH2Cl2 3 days

2 50 ordmC vacuum

1 day



Channels 9x11 Aring

Monoclinic Cc

15


00 25 50 75 100 125 150

00

01

02

03

04

05

06

07

(d

Vd

D)

Диаметр нм

S (BET) = 820 m2 g-109 nm

15 nm

36 nm

77 K 092 Н2




16


C2H

2 adsorption

C2H

2 desorption

CO2 adsorption

CO2 desorption

CO adsorption

CO desorption

0 20 40 60 80 100

0

10

20

30

40

50

60

V m

lg

pp0

0 20 40 60 80 100

0

5

10

15

20

25

30

35

V m

lg

C2H

2 adsorption

C2H

2 desorption

CO2 adsorption

CO2 desorption

CO adsorption

CO desorption

pp0

273 K

298 K

C2H2

CO2

CO

C2H2

CO2

CO


17

DFT calculations





density

18







β

β

β β

α

α

α

α

α


[Zn2(ur)2(ndc)4] S(BET) = 1113 m2 g-1



00 02 04 06 08 1050

100

150

200

250

300

[Zn4(dmf)(ur)

2(ndc)

4]

[Zn4(ur)

2(ndc)

4]

V млг

pp0



21



SHOOC COOH

N

N

H2tdc dabco




ACIE 2004 43 5033)



framework dynamics

vacuum

solvent

Fully reversible

V = -3



23

0

50

100

150

200

250

300

350

400

450

500

0 01 02 03 04 05 06 07 08 09 1

Am

ount adsorb

ed m

Lg


Adsorption

Desorption



Porous properties


Langmuir = 2000 m2g




0

20

40

60

80

100

120

140

160

180

0 01 02 03 04 05 06 07 08 09 1

Am

ou

nt

ad

so

rbe

d

mL

g


Adsorption

Desorption




-- At 1 bar (273 K) = 162 mlg = 32

mass







2012 112 724






fragment (c)






28




K+ 1 + Cs+K+ +

2 3

Cs+

Cations exchange






Rb Cs) in NMP




adduct of 1 (red)




metal cations


Chiral MOFs for


0 10 20 30 40

R

S

32

Metal or cluster

cation


ligand (spacer)

Chiral porous MOF

Cl

Cl

N

N

OH

OH

O

O

O

OO

O

N

N

O O

O O

HO NH

N

O

O

P

P

O

O

OH

OH

OH

OH



Катион

металла

Хиральный

лиганд




МОКП

Жесткий

мостик










Zn(NO3)2

(+)-camphoric acid

+


DMF + Py



Zn(II) Camphorates


N

N

N

N

N

Ndabcobipy

bpe

Chiral

layers

Homochiral

porous



36


Vfree = 31

channel

3 35 Aring

Sarea = 520 m2g

Vfree = 51

channel

5 7 Aring

Sarea = 1040 m2g

Vfree = 56

channel

5 10 Aring



38


Zn(NO3)2

(S)-H2lac

OH

HO

O

O

H2bdc

DMF


Chiral chain

OO

OO

Linear

spacer


COOH

HO H

CH3

Chiral chain


Zn(NO3)2 +H

COOH

OH

CH3

H

COOH

OH

+

H2lac

H2man

H2ndc

H2bpdc

HO

O

OH

O

HO

O OH

O

DMF

Chiral porous MOFs

39


channel 4 x 5 Aring

window 5 x 5 Aring

channel 5 x 9 Aring

window 4 x 5 Aring


window 6 x 7 Aring


40


(R + S)

Racemic

mixture


CH3

O

HO 20 (S)

Sulforaphane

Zn(NO3)2 + +CH3

H

COOH

OH

OH

HO

O

O

[Zn2(S-lac)(bdc)]

SCH3

O

S

O

CH3

OH

HO


ee= ([R]-[S])([R]+[S])

Substrate ee()

60 (S)

55 (S)

21 (S)

25 (+)

no sorptionS

CH3

OChiral sorbent

[Zn2(S-lac)(bdc)]


41

Racemic

mixture

Separated

optical

isomers

Chiral

stationary

phase

[Zn2(bdc)(lac)]

0 10 20 30 40

R

S

Con

c (

ru

)

0 20 40 60 80

SR

Con

c (

ru

)

SCH3

O

S

O











conductivity




MIL-101


45

FOH

H2O H2O


zeolytic topology


2040










MIL-101 acidMIL-101






acid in acidMIL-101



(3 - 4 M)



2) Filtration



H2SO4

H3PO4









conductivity


80 degC and RH 10








drugs

Selective sorption

gas molecules

enantioseparation


Chiral catalysis







51

52



Acknowledgments


Prof OA Kholdeeva

Prof V Ponomareva

Prof K Kim

Prof M Schoumlder














Building units

Linear

Triangular

Tetrahedral

Square

Octahedral


М2(СОО)3

М2(СОО)4


O

O

O

O

O

O

COO

OOC

COO

COO

N

N

N

N

NN

coo

coo

coo

ooc

O

O O

O

O

OO

O

N NOH

HO

O

O

8


[Zn4O(OOC-R)6]

ВСБ

O

O O

O

O

O

O

O

O

O O

O

O

O O

O


++


10



S(BET) = 6240 m2g S(Lang) = 10400 m2g


11


Framework

magnetic

electric

optical


Pores and channels

storage

separation

ion exchange


Surface

catalysis

adsorption



12


13

MOF







Zn

Zn

Zn Zn

N

N

N

N

HOOC

COOH

H2ndc =

β

β

β β

α

α

α

α

α

14



1 CH2Cl2 3 days

2 50 ordmC vacuum

1 day



Channels 9x11 Aring

Monoclinic Cc

15


00 25 50 75 100 125 150

00

01

02

03

04

05

06

07

(d

Vd

D)

Диаметр нм

S (BET) = 820 m2 g-109 nm

15 nm

36 nm

77 K 092 Н2




16


C2H

2 adsorption

C2H

2 desorption

CO2 adsorption

CO2 desorption

CO adsorption

CO desorption

0 20 40 60 80 100

0

10

20

30

40

50

60

V m

lg

pp0

0 20 40 60 80 100

0

5

10

15

20

25

30

35

V m

lg

C2H

2 adsorption

C2H

2 desorption

CO2 adsorption

CO2 desorption

CO adsorption

CO desorption

pp0

273 K

298 K

C2H2

CO2

CO

C2H2

CO2

CO


17

DFT calculations





density

18







β

β

β β

α

α

α

α

α


[Zn2(ur)2(ndc)4] S(BET) = 1113 m2 g-1



00 02 04 06 08 1050

100

150

200

250

300

[Zn4(dmf)(ur)

2(ndc)

4]

[Zn4(ur)

2(ndc)

4]

V млг

pp0



21



SHOOC COOH

N

N

H2tdc dabco




ACIE 2004 43 5033)



framework dynamics

vacuum

solvent

Fully reversible

V = -3



23

0

50

100

150

200

250

300

350

400

450

500

0 01 02 03 04 05 06 07 08 09 1

Am

ount adsorb

ed m

Lg


Adsorption

Desorption



Porous properties


Langmuir = 2000 m2g




0

20

40

60

80

100

120

140

160

180

0 01 02 03 04 05 06 07 08 09 1

Am

ou

nt

ad

so

rbe

d

mL

g


Adsorption

Desorption




-- At 1 bar (273 K) = 162 mlg = 32

mass







2012 112 724






fragment (c)






28




K+ 1 + Cs+K+ +

2 3

Cs+

Cations exchange






Rb Cs) in NMP




adduct of 1 (red)




metal cations


Chiral MOFs for


0 10 20 30 40

R

S

32

Metal or cluster

cation


ligand (spacer)

Chiral porous MOF

Cl

Cl

N

N

OH

OH

O

O

O

OO

O

N

N

O O

O O

HO NH

N

O

O

P

P

O

O

OH

OH

OH

OH



Катион

металла

Хиральный

лиганд




МОКП

Жесткий

мостик










Zn(NO3)2

(+)-camphoric acid

+


DMF + Py



Zn(II) Camphorates


N

N

N

N

N

Ndabcobipy

bpe

Chiral

layers

Homochiral

porous



36


Vfree = 31

channel

3 35 Aring

Sarea = 520 m2g

Vfree = 51

channel

5 7 Aring

Sarea = 1040 m2g

Vfree = 56

channel

5 10 Aring



38


Zn(NO3)2

(S)-H2lac

OH

HO

O

O

H2bdc

DMF


Chiral chain

OO

OO

Linear

spacer


COOH

HO H

CH3

Chiral chain


Zn(NO3)2 +H

COOH

OH

CH3

H

COOH

OH

+

H2lac

H2man

H2ndc

H2bpdc

HO

O

OH

O

HO

O OH

O

DMF

Chiral porous MOFs

39


channel 4 x 5 Aring

window 5 x 5 Aring

channel 5 x 9 Aring

window 4 x 5 Aring


window 6 x 7 Aring


40


(R + S)

Racemic

mixture


CH3

O

HO 20 (S)

Sulforaphane

Zn(NO3)2 + +CH3

H

COOH

OH

OH

HO

O

O

[Zn2(S-lac)(bdc)]

SCH3

O

S

O

CH3

OH

HO


ee= ([R]-[S])([R]+[S])

Substrate ee()

60 (S)

55 (S)

21 (S)

25 (+)

no sorptionS

CH3

OChiral sorbent

[Zn2(S-lac)(bdc)]


41

Racemic

mixture

Separated

optical

isomers

Chiral

stationary

phase

[Zn2(bdc)(lac)]

0 10 20 30 40

R

S

Con

c (

ru

)

0 20 40 60 80

SR

Con

c (

ru

)

SCH3

O

S

O











conductivity




MIL-101


45

FOH

H2O H2O


zeolytic topology


2040










MIL-101 acidMIL-101






acid in acidMIL-101



(3 - 4 M)



2) Filtration



H2SO4

H3PO4









conductivity


80 degC and RH 10








drugs

Selective sorption

gas molecules

enantioseparation


Chiral catalysis







51

52



Acknowledgments


Prof OA Kholdeeva

Prof V Ponomareva

Prof K Kim

Prof M Schoumlder















[Zn4O(OOC-R)6]

ВСБ

O

O O

O

O

O

O

O

O

O O

O

O

O O

O


++


10



S(BET) = 6240 m2g S(Lang) = 10400 m2g


11


Framework

magnetic

electric

optical


Pores and channels

storage

separation

ion exchange


Surface

catalysis

adsorption



12


13

MOF







Zn

Zn

Zn Zn

N

N

N

N

HOOC

COOH

H2ndc =

β

β

β β

α

α

α

α

α

14



1 CH2Cl2 3 days

2 50 ordmC vacuum

1 day



Channels 9x11 Aring

Monoclinic Cc

15


00 25 50 75 100 125 150

00

01

02

03

04

05

06

07

(d

Vd

D)

Диаметр нм

S (BET) = 820 m2 g-109 nm

15 nm

36 nm

77 K 092 Н2




16


C2H

2 adsorption

C2H

2 desorption

CO2 adsorption

CO2 desorption

CO adsorption

CO desorption

0 20 40 60 80 100

0

10

20

30

40

50

60

V m

lg

pp0

0 20 40 60 80 100

0

5

10

15

20

25

30

35

V m

lg

C2H

2 adsorption

C2H

2 desorption

CO2 adsorption

CO2 desorption

CO adsorption

CO desorption

pp0

273 K

298 K

C2H2

CO2

CO

C2H2

CO2

CO


17

DFT calculations





density

18







β

β

β β

α

α

α

α

α


[Zn2(ur)2(ndc)4] S(BET) = 1113 m2 g-1



00 02 04 06 08 1050

100

150

200

250

300

[Zn4(dmf)(ur)

2(ndc)

4]

[Zn4(ur)

2(ndc)

4]

V млг

pp0



21



SHOOC COOH

N

N

H2tdc dabco




ACIE 2004 43 5033)



framework dynamics

vacuum

solvent

Fully reversible

V = -3



23

0

50

100

150

200

250

300

350

400

450

500

0 01 02 03 04 05 06 07 08 09 1

Am

ount adsorb

ed m

Lg


Adsorption

Desorption



Porous properties


Langmuir = 2000 m2g




0

20

40

60

80

100

120

140

160

180

0 01 02 03 04 05 06 07 08 09 1

Am

ou

nt

ad

so

rbe

d

mL

g


Adsorption

Desorption




-- At 1 bar (273 K) = 162 mlg = 32

mass







2012 112 724






fragment (c)






28




K+ 1 + Cs+K+ +

2 3

Cs+

Cations exchange






Rb Cs) in NMP




adduct of 1 (red)




metal cations


Chiral MOFs for


0 10 20 30 40

R

S

32

Metal or cluster

cation


ligand (spacer)

Chiral porous MOF

Cl

Cl

N

N

OH

OH

O

O

O

OO

O

N

N

O O

O O

HO NH

N

O

O

P

P

O

O

OH

OH

OH

OH



Катион

металла

Хиральный

лиганд




МОКП

Жесткий

мостик










Zn(NO3)2

(+)-camphoric acid

+


DMF + Py



Zn(II) Camphorates


N

N

N

N

N

Ndabcobipy

bpe

Chiral

layers

Homochiral

porous



36


Vfree = 31

channel

3 35 Aring

Sarea = 520 m2g

Vfree = 51

channel

5 7 Aring

Sarea = 1040 m2g

Vfree = 56

channel

5 10 Aring



38


Zn(NO3)2

(S)-H2lac

OH

HO

O

O

H2bdc

DMF


Chiral chain

OO

OO

Linear

spacer


COOH

HO H

CH3

Chiral chain


Zn(NO3)2 +H

COOH

OH

CH3

H

COOH

OH

+

H2lac

H2man

H2ndc

H2bpdc

HO

O

OH

O

HO

O OH

O

DMF

Chiral porous MOFs

39


channel 4 x 5 Aring

window 5 x 5 Aring

channel 5 x 9 Aring

window 4 x 5 Aring


window 6 x 7 Aring


40


(R + S)

Racemic

mixture


CH3

O

HO 20 (S)

Sulforaphane

Zn(NO3)2 + +CH3

H

COOH

OH

OH

HO

O

O

[Zn2(S-lac)(bdc)]

SCH3

O

S

O

CH3

OH

HO


ee= ([R]-[S])([R]+[S])

Substrate ee()

60 (S)

55 (S)

21 (S)

25 (+)

no sorptionS

CH3

OChiral sorbent

[Zn2(S-lac)(bdc)]


41

Racemic

mixture

Separated

optical

isomers

Chiral

stationary

phase

[Zn2(bdc)(lac)]

0 10 20 30 40

R

S

Con

c (

ru

)

0 20 40 60 80

SR

Con

c (

ru

)

SCH3

O

S

O











conductivity




MIL-101


45

FOH

H2O H2O


zeolytic topology


2040










MIL-101 acidMIL-101






acid in acidMIL-101



(3 - 4 M)



2) Filtration



H2SO4

H3PO4









conductivity


80 degC and RH 10








drugs

Selective sorption

gas molecules

enantioseparation


Chiral catalysis







51

52



Acknowledgments


Prof OA Kholdeeva

Prof V Ponomareva

Prof K Kim

Prof M Schoumlder














++


10



S(BET) = 6240 m2g S(Lang) = 10400 m2g


11


Framework

magnetic

electric

optical


Pores and channels

storage

separation

ion exchange


Surface

catalysis

adsorption



12


13

MOF







Zn

Zn

Zn Zn

N

N

N

N

HOOC

COOH

H2ndc =

β

β

β β

α

α

α

α

α

14



1 CH2Cl2 3 days

2 50 ordmC vacuum

1 day



Channels 9x11 Aring

Monoclinic Cc

15


00 25 50 75 100 125 150

00

01

02

03

04

05

06

07

(d

Vd

D)

Диаметр нм

S (BET) = 820 m2 g-109 nm

15 nm

36 nm

77 K 092 Н2




16


C2H

2 adsorption

C2H

2 desorption

CO2 adsorption

CO2 desorption

CO adsorption

CO desorption

0 20 40 60 80 100

0

10

20

30

40

50

60

V m

lg

pp0

0 20 40 60 80 100

0

5

10

15

20

25

30

35

V m

lg

C2H

2 adsorption

C2H

2 desorption

CO2 adsorption

CO2 desorption

CO adsorption

CO desorption

pp0

273 K

298 K

C2H2

CO2

CO

C2H2

CO2

CO


17

DFT calculations





density

18







β

β

β β

α

α

α

α

α


[Zn2(ur)2(ndc)4] S(BET) = 1113 m2 g-1



00 02 04 06 08 1050

100

150

200

250

300

[Zn4(dmf)(ur)

2(ndc)

4]

[Zn4(ur)

2(ndc)

4]

V млг

pp0



21



SHOOC COOH

N

N

H2tdc dabco




ACIE 2004 43 5033)



framework dynamics

vacuum

solvent

Fully reversible

V = -3



23

0

50

100

150

200

250

300

350

400

450

500

0 01 02 03 04 05 06 07 08 09 1

Am

ount adsorb

ed m

Lg


Adsorption

Desorption



Porous properties


Langmuir = 2000 m2g




0

20

40

60

80

100

120

140

160

180

0 01 02 03 04 05 06 07 08 09 1

Am

ou

nt

ad

so

rbe

d

mL

g


Adsorption

Desorption




-- At 1 bar (273 K) = 162 mlg = 32

mass







2012 112 724






fragment (c)






28




K+ 1 + Cs+K+ +

2 3

Cs+

Cations exchange






Rb Cs) in NMP




adduct of 1 (red)




metal cations


Chiral MOFs for


0 10 20 30 40

R

S

32

Metal or cluster

cation


ligand (spacer)

Chiral porous MOF

Cl

Cl

N

N

OH

OH

O

O

O

OO

O

N

N

O O

O O

HO NH

N

O

O

P

P

O

O

OH

OH

OH

OH



Катион

металла

Хиральный

лиганд




МОКП

Жесткий

мостик










Zn(NO3)2

(+)-camphoric acid

+


DMF + Py



Zn(II) Camphorates


N

N

N

N

N

Ndabcobipy

bpe

Chiral

layers

Homochiral

porous



36


Vfree = 31

channel

3 35 Aring

Sarea = 520 m2g

Vfree = 51

channel

5 7 Aring

Sarea = 1040 m2g

Vfree = 56

channel

5 10 Aring



38


Zn(NO3)2

(S)-H2lac

OH

HO

O

O

H2bdc

DMF


Chiral chain

OO

OO

Linear

spacer


COOH

HO H

CH3

Chiral chain


Zn(NO3)2 +H

COOH

OH

CH3

H

COOH

OH

+

H2lac

H2man

H2ndc

H2bpdc

HO

O

OH

O

HO

O OH

O

DMF

Chiral porous MOFs

39


channel 4 x 5 Aring

window 5 x 5 Aring

channel 5 x 9 Aring

window 4 x 5 Aring


window 6 x 7 Aring


40


(R + S)

Racemic

mixture


CH3

O

HO 20 (S)

Sulforaphane

Zn(NO3)2 + +CH3

H

COOH

OH

OH

HO

O

O

[Zn2(S-lac)(bdc)]

SCH3

O

S

O

CH3

OH

HO


ee= ([R]-[S])([R]+[S])

Substrate ee()

60 (S)

55 (S)

21 (S)

25 (+)

no sorptionS

CH3

OChiral sorbent

[Zn2(S-lac)(bdc)]


41

Racemic

mixture

Separated

optical

isomers

Chiral

stationary

phase

[Zn2(bdc)(lac)]

0 10 20 30 40

R

S

Con

c (

ru

)

0 20 40 60 80

SR

Con

c (

ru

)

SCH3

O

S

O











conductivity




MIL-101


45

FOH

H2O H2O


zeolytic topology


2040










MIL-101 acidMIL-101






acid in acidMIL-101



(3 - 4 M)



2) Filtration



H2SO4

H3PO4









conductivity


80 degC and RH 10








drugs

Selective sorption

gas molecules

enantioseparation


Chiral catalysis







51

52



Acknowledgments


Prof OA Kholdeeva

Prof V Ponomareva

Prof K Kim

Prof M Schoumlder
















S(BET) = 6240 m2g S(Lang) = 10400 m2g


11


Framework

magnetic

electric

optical


Pores and channels

storage

separation

ion exchange


Surface

catalysis

adsorption



12


13

MOF







Zn

Zn

Zn Zn

N

N

N

N

HOOC

COOH

H2ndc =

β

β

β β

α

α

α

α

α

14



1 CH2Cl2 3 days

2 50 ordmC vacuum

1 day



Channels 9x11 Aring

Monoclinic Cc

15


00 25 50 75 100 125 150

00

01

02

03

04

05

06

07

(d

Vd

D)

Диаметр нм

S (BET) = 820 m2 g-109 nm

15 nm

36 nm

77 K 092 Н2




16


C2H

2 adsorption

C2H

2 desorption

CO2 adsorption

CO2 desorption

CO adsorption

CO desorption

0 20 40 60 80 100

0

10

20

30

40

50

60

V m

lg

pp0

0 20 40 60 80 100

0

5

10

15

20

25

30

35

V m

lg

C2H

2 adsorption

C2H

2 desorption

CO2 adsorption

CO2 desorption

CO adsorption

CO desorption

pp0

273 K

298 K

C2H2

CO2

CO

C2H2

CO2

CO


17

DFT calculations





density

18







β

β

β β

α

α

α

α

α


[Zn2(ur)2(ndc)4] S(BET) = 1113 m2 g-1



00 02 04 06 08 1050

100

150

200

250

300

[Zn4(dmf)(ur)

2(ndc)

4]

[Zn4(ur)

2(ndc)

4]

V млг

pp0



21



SHOOC COOH

N

N

H2tdc dabco




ACIE 2004 43 5033)



framework dynamics

vacuum

solvent

Fully reversible

V = -3



23

0

50

100

150

200

250

300

350

400

450

500

0 01 02 03 04 05 06 07 08 09 1

Am

ount adsorb

ed m

Lg


Adsorption

Desorption



Porous properties


Langmuir = 2000 m2g




0

20

40

60

80

100

120

140

160

180

0 01 02 03 04 05 06 07 08 09 1

Am

ou

nt

ad

so

rbe

d

mL

g


Adsorption

Desorption




-- At 1 bar (273 K) = 162 mlg = 32

mass







2012 112 724






fragment (c)






28




K+ 1 + Cs+K+ +

2 3

Cs+

Cations exchange






Rb Cs) in NMP




adduct of 1 (red)




metal cations


Chiral MOFs for


0 10 20 30 40

R

S

32

Metal or cluster

cation


ligand (spacer)

Chiral porous MOF

Cl

Cl

N

N

OH

OH

O

O

O

OO

O

N

N

O O

O O

HO NH

N

O

O

P

P

O

O

OH

OH

OH

OH



Катион

металла

Хиральный

лиганд




МОКП

Жесткий

мостик










Zn(NO3)2

(+)-camphoric acid

+


DMF + Py



Zn(II) Camphorates


N

N

N

N

N

Ndabcobipy

bpe

Chiral

layers

Homochiral

porous



36


Vfree = 31

channel

3 35 Aring

Sarea = 520 m2g

Vfree = 51

channel

5 7 Aring

Sarea = 1040 m2g

Vfree = 56

channel

5 10 Aring



38


Zn(NO3)2

(S)-H2lac

OH

HO

O

O

H2bdc

DMF


Chiral chain

OO

OO

Linear

spacer


COOH

HO H

CH3

Chiral chain


Zn(NO3)2 +H

COOH

OH

CH3

H

COOH

OH

+

H2lac

H2man

H2ndc

H2bpdc

HO

O

OH

O

HO

O OH

O

DMF

Chiral porous MOFs

39


channel 4 x 5 Aring

window 5 x 5 Aring

channel 5 x 9 Aring

window 4 x 5 Aring


window 6 x 7 Aring


40


(R + S)

Racemic

mixture


CH3

O

HO 20 (S)

Sulforaphane

Zn(NO3)2 + +CH3

H

COOH

OH

OH

HO

O

O

[Zn2(S-lac)(bdc)]

SCH3

O

S

O

CH3

OH

HO


ee= ([R]-[S])([R]+[S])

Substrate ee()

60 (S)

55 (S)

21 (S)

25 (+)

no sorptionS

CH3

OChiral sorbent

[Zn2(S-lac)(bdc)]


41

Racemic

mixture

Separated

optical

isomers

Chiral

stationary

phase

[Zn2(bdc)(lac)]

0 10 20 30 40

R

S

Con

c (

ru

)

0 20 40 60 80

SR

Con

c (

ru

)

SCH3

O

S

O











conductivity




MIL-101


45

FOH

H2O H2O


zeolytic topology


2040










MIL-101 acidMIL-101






acid in acidMIL-101



(3 - 4 M)



2) Filtration



H2SO4

H3PO4









conductivity


80 degC and RH 10








drugs

Selective sorption

gas molecules

enantioseparation


Chiral catalysis







51

52



Acknowledgments


Prof OA Kholdeeva

Prof V Ponomareva

Prof K Kim

Prof M Schoumlder















Framework

magnetic

electric

optical


Pores and channels

storage

separation

ion exchange


Surface

catalysis

adsorption



12


13

MOF







Zn

Zn

Zn Zn

N

N

N

N

HOOC

COOH

H2ndc =

β

β

β β

α

α

α

α

α

14



1 CH2Cl2 3 days

2 50 ordmC vacuum

1 day



Channels 9x11 Aring

Monoclinic Cc

15


00 25 50 75 100 125 150

00

01

02

03

04

05

06

07

(d

Vd

D)

Диаметр нм

S (BET) = 820 m2 g-109 nm

15 nm

36 nm

77 K 092 Н2




16


C2H

2 adsorption

C2H

2 desorption

CO2 adsorption

CO2 desorption

CO adsorption

CO desorption

0 20 40 60 80 100

0

10

20

30

40

50

60

V m

lg

pp0

0 20 40 60 80 100

0

5

10

15

20

25

30

35

V m

lg

C2H

2 adsorption

C2H

2 desorption

CO2 adsorption

CO2 desorption

CO adsorption

CO desorption

pp0

273 K

298 K

C2H2

CO2

CO

C2H2

CO2

CO


17

DFT calculations





density

18







β

β

β β

α

α

α

α

α


[Zn2(ur)2(ndc)4] S(BET) = 1113 m2 g-1



00 02 04 06 08 1050

100

150

200

250

300

[Zn4(dmf)(ur)

2(ndc)

4]

[Zn4(ur)

2(ndc)

4]

V млг

pp0



21



SHOOC COOH

N

N

H2tdc dabco




ACIE 2004 43 5033)



framework dynamics

vacuum

solvent

Fully reversible

V = -3



23

0

50

100

150

200

250

300

350

400

450

500

0 01 02 03 04 05 06 07 08 09 1

Am

ount adsorb

ed m

Lg


Adsorption

Desorption



Porous properties


Langmuir = 2000 m2g




0

20

40

60

80

100

120

140

160

180

0 01 02 03 04 05 06 07 08 09 1

Am

ou

nt

ad

so

rbe

d

mL

g


Adsorption

Desorption




-- At 1 bar (273 K) = 162 mlg = 32

mass







2012 112 724






fragment (c)






28




K+ 1 + Cs+K+ +

2 3

Cs+

Cations exchange






Rb Cs) in NMP




adduct of 1 (red)




metal cations


Chiral MOFs for


0 10 20 30 40

R

S

32

Metal or cluster

cation


ligand (spacer)

Chiral porous MOF

Cl

Cl

N

N

OH

OH

O

O

O

OO

O

N

N

O O

O O

HO NH

N

O

O

P

P

O

O

OH

OH

OH

OH



Катион

металла

Хиральный

лиганд




МОКП

Жесткий

мостик










Zn(NO3)2

(+)-camphoric acid

+


DMF + Py



Zn(II) Camphorates


N

N

N

N

N

Ndabcobipy

bpe

Chiral

layers

Homochiral

porous



36


Vfree = 31

channel

3 35 Aring

Sarea = 520 m2g

Vfree = 51

channel

5 7 Aring

Sarea = 1040 m2g

Vfree = 56

channel

5 10 Aring



38


Zn(NO3)2

(S)-H2lac

OH

HO

O

O

H2bdc

DMF


Chiral chain

OO

OO

Linear

spacer


COOH

HO H

CH3

Chiral chain


Zn(NO3)2 +H

COOH

OH

CH3

H

COOH

OH

+

H2lac

H2man

H2ndc

H2bpdc

HO

O

OH

O

HO

O OH

O

DMF

Chiral porous MOFs

39


channel 4 x 5 Aring

window 5 x 5 Aring

channel 5 x 9 Aring

window 4 x 5 Aring


window 6 x 7 Aring


40


(R + S)

Racemic

mixture


CH3

O

HO 20 (S)

Sulforaphane

Zn(NO3)2 + +CH3

H

COOH

OH

OH

HO

O

O

[Zn2(S-lac)(bdc)]

SCH3

O

S

O

CH3

OH

HO


ee= ([R]-[S])([R]+[S])

Substrate ee()

60 (S)

55 (S)

21 (S)

25 (+)

no sorptionS

CH3

OChiral sorbent

[Zn2(S-lac)(bdc)]


41

Racemic

mixture

Separated

optical

isomers

Chiral

stationary

phase

[Zn2(bdc)(lac)]

0 10 20 30 40

R

S

Con

c (

ru

)

0 20 40 60 80

SR

Con

c (

ru

)

SCH3

O

S

O











conductivity




MIL-101


45

FOH

H2O H2O


zeolytic topology


2040










MIL-101 acidMIL-101






acid in acidMIL-101



(3 - 4 M)



2) Filtration



H2SO4

H3PO4









conductivity


80 degC and RH 10








drugs

Selective sorption

gas molecules

enantioseparation


Chiral catalysis







51

52



Acknowledgments


Prof OA Kholdeeva

Prof V Ponomareva

Prof K Kim

Prof M Schoumlder















13

MOF







Zn

Zn

Zn Zn

N

N

N

N

HOOC

COOH

H2ndc =

β

β

β β

α

α

α

α

α

14



1 CH2Cl2 3 days

2 50 ordmC vacuum

1 day



Channels 9x11 Aring

Monoclinic Cc

15


00 25 50 75 100 125 150

00

01

02

03

04

05

06

07

(d

Vd

D)

Диаметр нм

S (BET) = 820 m2 g-109 nm

15 nm

36 nm

77 K 092 Н2




16


C2H

2 adsorption

C2H

2 desorption

CO2 adsorption

CO2 desorption

CO adsorption

CO desorption

0 20 40 60 80 100

0

10

20

30

40

50

60

V m

lg

pp0

0 20 40 60 80 100

0

5

10

15

20

25

30

35

V m

lg

C2H

2 adsorption

C2H

2 desorption

CO2 adsorption

CO2 desorption

CO adsorption

CO desorption

pp0

273 K

298 K

C2H2

CO2

CO

C2H2

CO2

CO


17

DFT calculations





density

18







β

β

β β

α

α

α

α

α


[Zn2(ur)2(ndc)4] S(BET) = 1113 m2 g-1



00 02 04 06 08 1050

100

150

200

250

300

[Zn4(dmf)(ur)

2(ndc)

4]

[Zn4(ur)

2(ndc)

4]

V млг

pp0



21



SHOOC COOH

N

N

H2tdc dabco




ACIE 2004 43 5033)



framework dynamics

vacuum

solvent

Fully reversible

V = -3



23

0

50

100

150

200

250

300

350

400

450

500

0 01 02 03 04 05 06 07 08 09 1

Am

ount adsorb

ed m

Lg


Adsorption

Desorption



Porous properties


Langmuir = 2000 m2g




0

20

40

60

80

100

120

140

160

180

0 01 02 03 04 05 06 07 08 09 1

Am

ou

nt

ad

so

rbe

d

mL

g


Adsorption

Desorption




-- At 1 bar (273 K) = 162 mlg = 32

mass







2012 112 724






fragment (c)






28




K+ 1 + Cs+K+ +

2 3

Cs+

Cations exchange






Rb Cs) in NMP




adduct of 1 (red)




metal cations


Chiral MOFs for


0 10 20 30 40

R

S

32

Metal or cluster

cation


ligand (spacer)

Chiral porous MOF

Cl

Cl

N

N

OH

OH

O

O

O

OO

O

N

N

O O

O O

HO NH

N

O

O

P

P

O

O

OH

OH

OH

OH



Катион

металла

Хиральный

лиганд




МОКП

Жесткий

мостик










Zn(NO3)2

(+)-camphoric acid

+


DMF + Py



Zn(II) Camphorates


N

N

N

N

N

Ndabcobipy

bpe

Chiral

layers

Homochiral

porous



36


Vfree = 31

channel

3 35 Aring

Sarea = 520 m2g

Vfree = 51

channel

5 7 Aring

Sarea = 1040 m2g

Vfree = 56

channel

5 10 Aring



38


Zn(NO3)2

(S)-H2lac

OH

HO

O

O

H2bdc

DMF


Chiral chain

OO

OO

Linear

spacer


COOH

HO H

CH3

Chiral chain


Zn(NO3)2 +H

COOH

OH

CH3

H

COOH

OH

+

H2lac

H2man

H2ndc

H2bpdc

HO

O

OH

O

HO

O OH

O

DMF

Chiral porous MOFs

39


channel 4 x 5 Aring

window 5 x 5 Aring

channel 5 x 9 Aring

window 4 x 5 Aring


window 6 x 7 Aring


40


(R + S)

Racemic

mixture


CH3

O

HO 20 (S)

Sulforaphane

Zn(NO3)2 + +CH3

H

COOH

OH

OH

HO

O

O

[Zn2(S-lac)(bdc)]

SCH3

O

S

O

CH3

OH

HO


ee= ([R]-[S])([R]+[S])

Substrate ee()

60 (S)

55 (S)

21 (S)

25 (+)

no sorptionS

CH3

OChiral sorbent

[Zn2(S-lac)(bdc)]


41

Racemic

mixture

Separated

optical

isomers

Chiral

stationary

phase

[Zn2(bdc)(lac)]

0 10 20 30 40

R

S

Con

c (

ru

)

0 20 40 60 80

SR

Con

c (

ru

)

SCH3

O

S

O











conductivity




MIL-101


45

FOH

H2O H2O


zeolytic topology


2040










MIL-101 acidMIL-101






acid in acidMIL-101



(3 - 4 M)



2) Filtration



H2SO4

H3PO4









conductivity


80 degC and RH 10








drugs

Selective sorption

gas molecules

enantioseparation


Chiral catalysis







51

52



Acknowledgments


Prof OA Kholdeeva

Prof V Ponomareva

Prof K Kim

Prof M Schoumlder




















Zn

Zn

Zn Zn

N

N

N

N

HOOC

COOH

H2ndc =

β

β

β β

α

α

α

α

α

14



1 CH2Cl2 3 days

2 50 ordmC vacuum

1 day



Channels 9x11 Aring

Monoclinic Cc

15


00 25 50 75 100 125 150

00

01

02

03

04

05

06

07

(d

Vd

D)

Диаметр нм

S (BET) = 820 m2 g-109 nm

15 nm

36 nm

77 K 092 Н2




16


C2H

2 adsorption

C2H

2 desorption

CO2 adsorption

CO2 desorption

CO adsorption

CO desorption

0 20 40 60 80 100

0

10

20

30

40

50

60

V m

lg

pp0

0 20 40 60 80 100

0

5

10

15

20

25

30

35

V m

lg

C2H

2 adsorption

C2H

2 desorption

CO2 adsorption

CO2 desorption

CO adsorption

CO desorption

pp0

273 K

298 K

C2H2

CO2

CO

C2H2

CO2

CO


17

DFT calculations





density

18







β

β

β β

α

α

α

α

α


[Zn2(ur)2(ndc)4] S(BET) = 1113 m2 g-1



00 02 04 06 08 1050

100

150

200

250

300

[Zn4(dmf)(ur)

2(ndc)

4]

[Zn4(ur)

2(ndc)

4]

V млг

pp0



21



SHOOC COOH

N

N

H2tdc dabco




ACIE 2004 43 5033)



framework dynamics

vacuum

solvent

Fully reversible

V = -3



23

0

50

100

150

200

250

300

350

400

450

500

0 01 02 03 04 05 06 07 08 09 1

Am

ount adsorb

ed m

Lg


Adsorption

Desorption



Porous properties


Langmuir = 2000 m2g




0

20

40

60

80

100

120

140

160

180

0 01 02 03 04 05 06 07 08 09 1

Am

ou

nt

ad

so

rbe

d

mL

g


Adsorption

Desorption




-- At 1 bar (273 K) = 162 mlg = 32

mass







2012 112 724






fragment (c)






28




K+ 1 + Cs+K+ +

2 3

Cs+

Cations exchange






Rb Cs) in NMP




adduct of 1 (red)




metal cations


Chiral MOFs for


0 10 20 30 40

R

S

32

Metal or cluster

cation


ligand (spacer)

Chiral porous MOF

Cl

Cl

N

N

OH

OH

O

O

O

OO

O

N

N

O O

O O

HO NH

N

O

O

P

P

O

O

OH

OH

OH

OH



Катион

металла

Хиральный

лиганд




МОКП

Жесткий

мостик










Zn(NO3)2

(+)-camphoric acid

+


DMF + Py



Zn(II) Camphorates


N

N

N

N

N

Ndabcobipy

bpe

Chiral

layers

Homochiral

porous



36


Vfree = 31

channel

3 35 Aring

Sarea = 520 m2g

Vfree = 51

channel

5 7 Aring

Sarea = 1040 m2g

Vfree = 56

channel

5 10 Aring



38


Zn(NO3)2

(S)-H2lac

OH

HO

O

O

H2bdc

DMF


Chiral chain

OO

OO

Linear

spacer


COOH

HO H

CH3

Chiral chain


Zn(NO3)2 +H

COOH

OH

CH3

H

COOH

OH

+

H2lac

H2man

H2ndc

H2bpdc

HO

O

OH

O

HO

O OH

O

DMF

Chiral porous MOFs

39


channel 4 x 5 Aring

window 5 x 5 Aring

channel 5 x 9 Aring

window 4 x 5 Aring


window 6 x 7 Aring


40


(R + S)

Racemic

mixture


CH3

O

HO 20 (S)

Sulforaphane

Zn(NO3)2 + +CH3

H

COOH

OH

OH

HO

O

O

[Zn2(S-lac)(bdc)]

SCH3

O

S

O

CH3

OH

HO


ee= ([R]-[S])([R]+[S])

Substrate ee()

60 (S)

55 (S)

21 (S)

25 (+)

no sorptionS

CH3

OChiral sorbent

[Zn2(S-lac)(bdc)]


41

Racemic

mixture

Separated

optical

isomers

Chiral

stationary

phase

[Zn2(bdc)(lac)]

0 10 20 30 40

R

S

Con

c (

ru

)

0 20 40 60 80

SR

Con

c (

ru

)

SCH3

O

S

O











conductivity




MIL-101


45

FOH

H2O H2O


zeolytic topology


2040










MIL-101 acidMIL-101






acid in acidMIL-101



(3 - 4 M)



2) Filtration



H2SO4

H3PO4









conductivity


80 degC and RH 10








drugs

Selective sorption

gas molecules

enantioseparation


Chiral catalysis







51

52



Acknowledgments


Prof OA Kholdeeva

Prof V Ponomareva

Prof K Kim

Prof M Schoumlder
















1 CH2Cl2 3 days

2 50 ordmC vacuum

1 day



Channels 9x11 Aring

Monoclinic Cc

15


00 25 50 75 100 125 150

00

01

02

03

04

05

06

07

(d

Vd

D)

Диаметр нм

S (BET) = 820 m2 g-109 nm

15 nm

36 nm

77 K 092 Н2




16


C2H

2 adsorption

C2H

2 desorption

CO2 adsorption

CO2 desorption

CO adsorption

CO desorption

0 20 40 60 80 100

0

10

20

30

40

50

60

V m

lg

pp0

0 20 40 60 80 100

0

5

10

15

20

25

30

35

V m

lg

C2H

2 adsorption

C2H

2 desorption

CO2 adsorption

CO2 desorption

CO adsorption

CO desorption

pp0

273 K

298 K

C2H2

CO2

CO

C2H2

CO2

CO


17

DFT calculations





density

18







β

β

β β

α

α

α

α

α


[Zn2(ur)2(ndc)4] S(BET) = 1113 m2 g-1



00 02 04 06 08 1050

100

150

200

250

300

[Zn4(dmf)(ur)

2(ndc)

4]

[Zn4(ur)

2(ndc)

4]

V млг

pp0



21



SHOOC COOH

N

N

H2tdc dabco




ACIE 2004 43 5033)



framework dynamics

vacuum

solvent

Fully reversible

V = -3



23

0

50

100

150

200

250

300

350

400

450

500

0 01 02 03 04 05 06 07 08 09 1

Am

ount adsorb

ed m

Lg


Adsorption

Desorption



Porous properties


Langmuir = 2000 m2g




0

20

40

60

80

100

120

140

160

180

0 01 02 03 04 05 06 07 08 09 1

Am

ou

nt

ad

so

rbe

d

mL

g


Adsorption

Desorption




-- At 1 bar (273 K) = 162 mlg = 32

mass







2012 112 724






fragment (c)






28




K+ 1 + Cs+K+ +

2 3

Cs+

Cations exchange






Rb Cs) in NMP




adduct of 1 (red)




metal cations


Chiral MOFs for


0 10 20 30 40

R

S

32

Metal or cluster

cation


ligand (spacer)

Chiral porous MOF

Cl

Cl

N

N

OH

OH

O

O

O

OO

O

N

N

O O

O O

HO NH

N

O

O

P

P

O

O

OH

OH

OH

OH



Катион

металла

Хиральный

лиганд




МОКП

Жесткий

мостик










Zn(NO3)2

(+)-camphoric acid

+


DMF + Py



Zn(II) Camphorates


N

N

N

N

N

Ndabcobipy

bpe

Chiral

layers

Homochiral

porous



36


Vfree = 31

channel

3 35 Aring

Sarea = 520 m2g

Vfree = 51

channel

5 7 Aring

Sarea = 1040 m2g

Vfree = 56

channel

5 10 Aring



38


Zn(NO3)2

(S)-H2lac

OH

HO

O

O

H2bdc

DMF


Chiral chain

OO

OO

Linear

spacer


COOH

HO H

CH3

Chiral chain


Zn(NO3)2 +H

COOH

OH

CH3

H

COOH

OH

+

H2lac

H2man

H2ndc

H2bpdc

HO

O

OH

O

HO

O OH

O

DMF

Chiral porous MOFs

39


channel 4 x 5 Aring

window 5 x 5 Aring

channel 5 x 9 Aring

window 4 x 5 Aring


window 6 x 7 Aring


40


(R + S)

Racemic

mixture


CH3

O

HO 20 (S)

Sulforaphane

Zn(NO3)2 + +CH3

H

COOH

OH

OH

HO

O

O

[Zn2(S-lac)(bdc)]

SCH3

O

S

O

CH3

OH

HO


ee= ([R]-[S])([R]+[S])

Substrate ee()

60 (S)

55 (S)

21 (S)

25 (+)

no sorptionS

CH3

OChiral sorbent

[Zn2(S-lac)(bdc)]


41

Racemic

mixture

Separated

optical

isomers

Chiral

stationary

phase

[Zn2(bdc)(lac)]

0 10 20 30 40

R

S

Con

c (

ru

)

0 20 40 60 80

SR

Con

c (

ru

)

SCH3

O

S

O











conductivity




MIL-101


45

FOH

H2O H2O


zeolytic topology


2040










MIL-101 acidMIL-101






acid in acidMIL-101



(3 - 4 M)



2) Filtration



H2SO4

H3PO4









conductivity


80 degC and RH 10








drugs

Selective sorption

gas molecules

enantioseparation


Chiral catalysis







51

52



Acknowledgments


Prof OA Kholdeeva

Prof V Ponomareva

Prof K Kim

Prof M Schoumlder















00 25 50 75 100 125 150

00

01

02

03

04

05

06

07

(d

Vd

D)

Диаметр нм

S (BET) = 820 m2 g-109 nm

15 nm

36 nm

77 K 092 Н2




16


C2H

2 adsorption

C2H

2 desorption

CO2 adsorption

CO2 desorption

CO adsorption

CO desorption

0 20 40 60 80 100

0

10

20

30

40

50

60

V m

lg

pp0

0 20 40 60 80 100

0

5

10

15

20

25

30

35

V m

lg

C2H

2 adsorption

C2H

2 desorption

CO2 adsorption

CO2 desorption

CO adsorption

CO desorption

pp0

273 K

298 K

C2H2

CO2

CO

C2H2

CO2

CO


17

DFT calculations





density

18







β

β

β β

α

α

α

α

α


[Zn2(ur)2(ndc)4] S(BET) = 1113 m2 g-1



00 02 04 06 08 1050

100

150

200

250

300

[Zn4(dmf)(ur)

2(ndc)

4]

[Zn4(ur)

2(ndc)

4]

V млг

pp0



21



SHOOC COOH

N

N

H2tdc dabco




ACIE 2004 43 5033)



framework dynamics

vacuum

solvent

Fully reversible

V = -3



23

0

50

100

150

200

250

300

350

400

450

500

0 01 02 03 04 05 06 07 08 09 1

Am

ount adsorb

ed m

Lg


Adsorption

Desorption



Porous properties


Langmuir = 2000 m2g




0

20

40

60

80

100

120

140

160

180

0 01 02 03 04 05 06 07 08 09 1

Am

ou

nt

ad

so

rbe

d

mL

g


Adsorption

Desorption




-- At 1 bar (273 K) = 162 mlg = 32

mass







2012 112 724






fragment (c)






28




K+ 1 + Cs+K+ +

2 3

Cs+

Cations exchange






Rb Cs) in NMP




adduct of 1 (red)




metal cations


Chiral MOFs for


0 10 20 30 40

R

S

32

Metal or cluster

cation


ligand (spacer)

Chiral porous MOF

Cl

Cl

N

N

OH

OH

O

O

O

OO

O

N

N

O O

O O

HO NH

N

O

O

P

P

O

O

OH

OH

OH

OH



Катион

металла

Хиральный

лиганд




МОКП

Жесткий

мостик










Zn(NO3)2

(+)-camphoric acid

+


DMF + Py



Zn(II) Camphorates


N

N

N

N

N

Ndabcobipy

bpe

Chiral

layers

Homochiral

porous



36


Vfree = 31

channel

3 35 Aring

Sarea = 520 m2g

Vfree = 51

channel

5 7 Aring

Sarea = 1040 m2g

Vfree = 56

channel

5 10 Aring



38


Zn(NO3)2

(S)-H2lac

OH

HO

O

O

H2bdc

DMF


Chiral chain

OO

OO

Linear

spacer


COOH

HO H

CH3

Chiral chain


Zn(NO3)2 +H

COOH

OH

CH3

H

COOH

OH

+

H2lac

H2man

H2ndc

H2bpdc

HO

O

OH

O

HO

O OH

O

DMF

Chiral porous MOFs

39


channel 4 x 5 Aring

window 5 x 5 Aring

channel 5 x 9 Aring

window 4 x 5 Aring


window 6 x 7 Aring


40


(R + S)

Racemic

mixture


CH3

O

HO 20 (S)

Sulforaphane

Zn(NO3)2 + +CH3

H

COOH

OH

OH

HO

O

O

[Zn2(S-lac)(bdc)]

SCH3

O

S

O

CH3

OH

HO


ee= ([R]-[S])([R]+[S])

Substrate ee()

60 (S)

55 (S)

21 (S)

25 (+)

no sorptionS

CH3

OChiral sorbent

[Zn2(S-lac)(bdc)]


41

Racemic

mixture

Separated

optical

isomers

Chiral

stationary

phase

[Zn2(bdc)(lac)]

0 10 20 30 40

R

S

Con

c (

ru

)

0 20 40 60 80

SR

Con

c (

ru

)

SCH3

O

S

O











conductivity




MIL-101


45

FOH

H2O H2O


zeolytic topology


2040










MIL-101 acidMIL-101






acid in acidMIL-101



(3 - 4 M)



2) Filtration



H2SO4

H3PO4









conductivity


80 degC and RH 10








drugs

Selective sorption

gas molecules

enantioseparation


Chiral catalysis







51

52



Acknowledgments


Prof OA Kholdeeva

Prof V Ponomareva

Prof K Kim

Prof M Schoumlder















C2H

2 adsorption

C2H

2 desorption

CO2 adsorption

CO2 desorption

CO adsorption

CO desorption

0 20 40 60 80 100

0

10

20

30

40

50

60

V m

lg

pp0

0 20 40 60 80 100

0

5

10

15

20

25

30

35

V m

lg

C2H

2 adsorption

C2H

2 desorption

CO2 adsorption

CO2 desorption

CO adsorption

CO desorption

pp0

273 K

298 K

C2H2

CO2

CO

C2H2

CO2

CO


17

DFT calculations





density

18







β

β

β β

α

α

α

α

α


[Zn2(ur)2(ndc)4] S(BET) = 1113 m2 g-1



00 02 04 06 08 1050

100

150

200

250

300

[Zn4(dmf)(ur)

2(ndc)

4]

[Zn4(ur)

2(ndc)

4]

V млг

pp0



21



SHOOC COOH

N

N

H2tdc dabco




ACIE 2004 43 5033)



framework dynamics

vacuum

solvent

Fully reversible

V = -3



23

0

50

100

150

200

250

300

350

400

450

500

0 01 02 03 04 05 06 07 08 09 1

Am

ount adsorb

ed m

Lg


Adsorption

Desorption



Porous properties


Langmuir = 2000 m2g




0

20

40

60

80

100

120

140

160

180

0 01 02 03 04 05 06 07 08 09 1

Am

ou

nt

ad

so

rbe

d

mL

g


Adsorption

Desorption




-- At 1 bar (273 K) = 162 mlg = 32

mass







2012 112 724






fragment (c)






28




K+ 1 + Cs+K+ +

2 3

Cs+

Cations exchange






Rb Cs) in NMP




adduct of 1 (red)




metal cations


Chiral MOFs for


0 10 20 30 40

R

S

32

Metal or cluster

cation


ligand (spacer)

Chiral porous MOF

Cl

Cl

N

N

OH

OH

O

O

O

OO

O

N

N

O O

O O

HO NH

N

O

O

P

P

O

O

OH

OH

OH

OH



Катион

металла

Хиральный

лиганд




МОКП

Жесткий

мостик










Zn(NO3)2

(+)-camphoric acid

+


DMF + Py



Zn(II) Camphorates


N

N

N

N

N

Ndabcobipy

bpe

Chiral

layers

Homochiral

porous



36


Vfree = 31

channel

3 35 Aring

Sarea = 520 m2g

Vfree = 51

channel

5 7 Aring

Sarea = 1040 m2g

Vfree = 56

channel

5 10 Aring



38


Zn(NO3)2

(S)-H2lac

OH

HO

O

O

H2bdc

DMF


Chiral chain

OO

OO

Linear

spacer


COOH

HO H

CH3

Chiral chain


Zn(NO3)2 +H

COOH

OH

CH3

H

COOH

OH

+

H2lac

H2man

H2ndc

H2bpdc

HO

O

OH

O

HO

O OH

O

DMF

Chiral porous MOFs

39


channel 4 x 5 Aring

window 5 x 5 Aring

channel 5 x 9 Aring

window 4 x 5 Aring


window 6 x 7 Aring


40


(R + S)

Racemic

mixture


CH3

O

HO 20 (S)

Sulforaphane

Zn(NO3)2 + +CH3

H

COOH

OH

OH

HO

O

O

[Zn2(S-lac)(bdc)]

SCH3

O

S

O

CH3

OH

HO


ee= ([R]-[S])([R]+[S])

Substrate ee()

60 (S)

55 (S)

21 (S)

25 (+)

no sorptionS

CH3

OChiral sorbent

[Zn2(S-lac)(bdc)]


41

Racemic

mixture

Separated

optical

isomers

Chiral

stationary

phase

[Zn2(bdc)(lac)]

0 10 20 30 40

R

S

Con

c (

ru

)

0 20 40 60 80

SR

Con

c (

ru

)

SCH3

O

S

O











conductivity




MIL-101


45

FOH

H2O H2O


zeolytic topology


2040










MIL-101 acidMIL-101






acid in acidMIL-101



(3 - 4 M)



2) Filtration



H2SO4

H3PO4









conductivity


80 degC and RH 10








drugs

Selective sorption

gas molecules

enantioseparation


Chiral catalysis







51

52



Acknowledgments


Prof OA Kholdeeva

Prof V Ponomareva

Prof K Kim

Prof M Schoumlder














DFT calculations





density

18







β

β

β β

α

α

α

α

α


[Zn2(ur)2(ndc)4] S(BET) = 1113 m2 g-1



00 02 04 06 08 1050

100

150

200

250

300

[Zn4(dmf)(ur)

2(ndc)

4]

[Zn4(ur)

2(ndc)

4]

V млг

pp0



21



SHOOC COOH

N

N

H2tdc dabco




ACIE 2004 43 5033)



framework dynamics

vacuum

solvent

Fully reversible

V = -3



23

0

50

100

150

200

250

300

350

400

450

500

0 01 02 03 04 05 06 07 08 09 1

Am

ount adsorb

ed m

Lg


Adsorption

Desorption



Porous properties


Langmuir = 2000 m2g




0

20

40

60

80

100

120

140

160

180

0 01 02 03 04 05 06 07 08 09 1

Am

ou

nt

ad

so

rbe

d

mL

g


Adsorption

Desorption




-- At 1 bar (273 K) = 162 mlg = 32

mass







2012 112 724






fragment (c)






28




K+ 1 + Cs+K+ +

2 3

Cs+

Cations exchange






Rb Cs) in NMP




adduct of 1 (red)




metal cations


Chiral MOFs for


0 10 20 30 40

R

S

32

Metal or cluster

cation


ligand (spacer)

Chiral porous MOF

Cl

Cl

N

N

OH

OH

O

O

O

OO

O

N

N

O O

O O

HO NH

N

O

O

P

P

O

O

OH

OH

OH

OH



Катион

металла

Хиральный

лиганд




МОКП

Жесткий

мостик










Zn(NO3)2

(+)-camphoric acid

+


DMF + Py



Zn(II) Camphorates


N

N

N

N

N

Ndabcobipy

bpe

Chiral

layers

Homochiral

porous



36


Vfree = 31

channel

3 35 Aring

Sarea = 520 m2g

Vfree = 51

channel

5 7 Aring

Sarea = 1040 m2g

Vfree = 56

channel

5 10 Aring



38


Zn(NO3)2

(S)-H2lac

OH

HO

O

O

H2bdc

DMF


Chiral chain

OO

OO

Linear

spacer


COOH

HO H

CH3

Chiral chain


Zn(NO3)2 +H

COOH

OH

CH3

H

COOH

OH

+

H2lac

H2man

H2ndc

H2bpdc

HO

O

OH

O

HO

O OH

O

DMF

Chiral porous MOFs

39


channel 4 x 5 Aring

window 5 x 5 Aring

channel 5 x 9 Aring

window 4 x 5 Aring


window 6 x 7 Aring


40


(R + S)

Racemic

mixture


CH3

O

HO 20 (S)

Sulforaphane

Zn(NO3)2 + +CH3

H

COOH

OH

OH

HO

O

O

[Zn2(S-lac)(bdc)]

SCH3

O

S

O

CH3

OH

HO


ee= ([R]-[S])([R]+[S])

Substrate ee()

60 (S)

55 (S)

21 (S)

25 (+)

no sorptionS

CH3

OChiral sorbent

[Zn2(S-lac)(bdc)]


41

Racemic

mixture

Separated

optical

isomers

Chiral

stationary

phase

[Zn2(bdc)(lac)]

0 10 20 30 40

R

S

Con

c (

ru

)

0 20 40 60 80

SR

Con

c (

ru

)

SCH3

O

S

O











conductivity




MIL-101


45

FOH

H2O H2O


zeolytic topology


2040










MIL-101 acidMIL-101






acid in acidMIL-101



(3 - 4 M)



2) Filtration



H2SO4

H3PO4









conductivity


80 degC and RH 10








drugs

Selective sorption

gas molecules

enantioseparation


Chiral catalysis







51

52



Acknowledgments


Prof OA Kholdeeva

Prof V Ponomareva

Prof K Kim

Prof M Schoumlder




















β

β

β β

α

α

α

α

α


[Zn2(ur)2(ndc)4] S(BET) = 1113 m2 g-1



00 02 04 06 08 1050

100

150

200

250

300

[Zn4(dmf)(ur)

2(ndc)

4]

[Zn4(ur)

2(ndc)

4]

V млг

pp0



21



SHOOC COOH

N

N

H2tdc dabco




ACIE 2004 43 5033)



framework dynamics

vacuum

solvent

Fully reversible

V = -3



23

0

50

100

150

200

250

300

350

400

450

500

0 01 02 03 04 05 06 07 08 09 1

Am

ount adsorb

ed m

Lg


Adsorption

Desorption



Porous properties


Langmuir = 2000 m2g




0

20

40

60

80

100

120

140

160

180

0 01 02 03 04 05 06 07 08 09 1

Am

ou

nt

ad

so

rbe

d

mL

g


Adsorption

Desorption




-- At 1 bar (273 K) = 162 mlg = 32

mass







2012 112 724






fragment (c)






28




K+ 1 + Cs+K+ +

2 3

Cs+

Cations exchange






Rb Cs) in NMP




adduct of 1 (red)




metal cations


Chiral MOFs for


0 10 20 30 40

R

S

32

Metal or cluster

cation


ligand (spacer)

Chiral porous MOF

Cl

Cl

N

N

OH

OH

O

O

O

OO

O

N

N

O O

O O

HO NH

N

O

O

P

P

O

O

OH

OH

OH

OH



Катион

металла

Хиральный

лиганд




МОКП

Жесткий

мостик










Zn(NO3)2

(+)-camphoric acid

+


DMF + Py



Zn(II) Camphorates


N

N

N

N

N

Ndabcobipy

bpe

Chiral

layers

Homochiral

porous



36


Vfree = 31

channel

3 35 Aring

Sarea = 520 m2g

Vfree = 51

channel

5 7 Aring

Sarea = 1040 m2g

Vfree = 56

channel

5 10 Aring



38


Zn(NO3)2

(S)-H2lac

OH

HO

O

O

H2bdc

DMF


Chiral chain

OO

OO

Linear

spacer


COOH

HO H

CH3

Chiral chain


Zn(NO3)2 +H

COOH

OH

CH3

H

COOH

OH

+

H2lac

H2man

H2ndc

H2bpdc

HO

O

OH

O

HO

O OH

O

DMF

Chiral porous MOFs

39


channel 4 x 5 Aring

window 5 x 5 Aring

channel 5 x 9 Aring

window 4 x 5 Aring


window 6 x 7 Aring


40


(R + S)

Racemic

mixture


CH3

O

HO 20 (S)

Sulforaphane

Zn(NO3)2 + +CH3

H

COOH

OH

OH

HO

O

O

[Zn2(S-lac)(bdc)]

SCH3

O

S

O

CH3

OH

HO


ee= ([R]-[S])([R]+[S])

Substrate ee()

60 (S)

55 (S)

21 (S)

25 (+)

no sorptionS

CH3

OChiral sorbent

[Zn2(S-lac)(bdc)]


41

Racemic

mixture

Separated

optical

isomers

Chiral

stationary

phase

[Zn2(bdc)(lac)]

0 10 20 30 40

R

S

Con

c (

ru

)

0 20 40 60 80

SR

Con

c (

ru

)

SCH3

O

S

O











conductivity




MIL-101


45

FOH

H2O H2O


zeolytic topology


2040










MIL-101 acidMIL-101






acid in acidMIL-101



(3 - 4 M)



2) Filtration



H2SO4

H3PO4









conductivity


80 degC and RH 10








drugs

Selective sorption

gas molecules

enantioseparation


Chiral catalysis







51

52



Acknowledgments


Prof OA Kholdeeva

Prof V Ponomareva

Prof K Kim

Prof M Schoumlder















21



SHOOC COOH

N

N

H2tdc dabco




ACIE 2004 43 5033)



framework dynamics

vacuum

solvent

Fully reversible

V = -3



23

0

50

100

150

200

250

300

350

400

450

500

0 01 02 03 04 05 06 07 08 09 1

Am

ount adsorb

ed m

Lg


Adsorption

Desorption



Porous properties


Langmuir = 2000 m2g




0

20

40

60

80

100

120

140

160

180

0 01 02 03 04 05 06 07 08 09 1

Am

ou

nt

ad

so

rbe

d

mL

g


Adsorption

Desorption




-- At 1 bar (273 K) = 162 mlg = 32

mass







2012 112 724






fragment (c)






28




K+ 1 + Cs+K+ +

2 3

Cs+

Cations exchange






Rb Cs) in NMP




adduct of 1 (red)




metal cations


Chiral MOFs for


0 10 20 30 40

R

S

32

Metal or cluster

cation


ligand (spacer)

Chiral porous MOF

Cl

Cl

N

N

OH

OH

O

O

O

OO

O

N

N

O O

O O

HO NH

N

O

O

P

P

O

O

OH

OH

OH

OH



Катион

металла

Хиральный

лиганд




МОКП

Жесткий

мостик










Zn(NO3)2

(+)-camphoric acid

+


DMF + Py



Zn(II) Camphorates


N

N

N

N

N

Ndabcobipy

bpe

Chiral

layers

Homochiral

porous



36


Vfree = 31

channel

3 35 Aring

Sarea = 520 m2g

Vfree = 51

channel

5 7 Aring

Sarea = 1040 m2g

Vfree = 56

channel

5 10 Aring



38


Zn(NO3)2

(S)-H2lac

OH

HO

O

O

H2bdc

DMF


Chiral chain

OO

OO

Linear

spacer


COOH

HO H

CH3

Chiral chain


Zn(NO3)2 +H

COOH

OH

CH3

H

COOH

OH

+

H2lac

H2man

H2ndc

H2bpdc

HO

O

OH

O

HO

O OH

O

DMF

Chiral porous MOFs

39


channel 4 x 5 Aring

window 5 x 5 Aring

channel 5 x 9 Aring

window 4 x 5 Aring


window 6 x 7 Aring


40


(R + S)

Racemic

mixture


CH3

O

HO 20 (S)

Sulforaphane

Zn(NO3)2 + +CH3

H

COOH

OH

OH

HO

O

O

[Zn2(S-lac)(bdc)]

SCH3

O

S

O

CH3

OH

HO


ee= ([R]-[S])([R]+[S])

Substrate ee()

60 (S)

55 (S)

21 (S)

25 (+)

no sorptionS

CH3

OChiral sorbent

[Zn2(S-lac)(bdc)]


41

Racemic

mixture

Separated

optical

isomers

Chiral

stationary

phase

[Zn2(bdc)(lac)]

0 10 20 30 40

R

S

Con

c (

ru

)

0 20 40 60 80

SR

Con

c (

ru

)

SCH3

O

S

O











conductivity




MIL-101


45

FOH

H2O H2O


zeolytic topology


2040










MIL-101 acidMIL-101






acid in acidMIL-101



(3 - 4 M)



2) Filtration



H2SO4

H3PO4









conductivity


80 degC and RH 10








drugs

Selective sorption

gas molecules

enantioseparation


Chiral catalysis







51

52



Acknowledgments


Prof OA Kholdeeva

Prof V Ponomareva

Prof K Kim

Prof M Schoumlder















SHOOC COOH

N

N

H2tdc dabco




ACIE 2004 43 5033)



framework dynamics

vacuum

solvent

Fully reversible

V = -3



23

0

50

100

150

200

250

300

350

400

450

500

0 01 02 03 04 05 06 07 08 09 1

Am

ount adsorb

ed m

Lg


Adsorption

Desorption



Porous properties


Langmuir = 2000 m2g




0

20

40

60

80

100

120

140

160

180

0 01 02 03 04 05 06 07 08 09 1

Am

ou

nt

ad

so

rbe

d

mL

g


Adsorption

Desorption




-- At 1 bar (273 K) = 162 mlg = 32

mass







2012 112 724






fragment (c)






28




K+ 1 + Cs+K+ +

2 3

Cs+

Cations exchange






Rb Cs) in NMP




adduct of 1 (red)




metal cations


Chiral MOFs for


0 10 20 30 40

R

S

32

Metal or cluster

cation


ligand (spacer)

Chiral porous MOF

Cl

Cl

N

N

OH

OH

O

O

O

OO

O

N

N

O O

O O

HO NH

N

O

O

P

P

O

O

OH

OH

OH

OH



Катион

металла

Хиральный

лиганд




МОКП

Жесткий

мостик










Zn(NO3)2

(+)-camphoric acid

+


DMF + Py



Zn(II) Camphorates


N

N

N

N

N

Ndabcobipy

bpe

Chiral

layers

Homochiral

porous



36


Vfree = 31

channel

3 35 Aring

Sarea = 520 m2g

Vfree = 51

channel

5 7 Aring

Sarea = 1040 m2g

Vfree = 56

channel

5 10 Aring



38


Zn(NO3)2

(S)-H2lac

OH

HO

O

O

H2bdc

DMF


Chiral chain

OO

OO

Linear

spacer


COOH

HO H

CH3

Chiral chain


Zn(NO3)2 +H

COOH

OH

CH3

H

COOH

OH

+

H2lac

H2man

H2ndc

H2bpdc

HO

O

OH

O

HO

O OH

O

DMF

Chiral porous MOFs

39


channel 4 x 5 Aring

window 5 x 5 Aring

channel 5 x 9 Aring

window 4 x 5 Aring


window 6 x 7 Aring


40


(R + S)

Racemic

mixture


CH3

O

HO 20 (S)

Sulforaphane

Zn(NO3)2 + +CH3

H

COOH

OH

OH

HO

O

O

[Zn2(S-lac)(bdc)]

SCH3

O

S

O

CH3

OH

HO


ee= ([R]-[S])([R]+[S])

Substrate ee()

60 (S)

55 (S)

21 (S)

25 (+)

no sorptionS

CH3

OChiral sorbent

[Zn2(S-lac)(bdc)]


41

Racemic

mixture

Separated

optical

isomers

Chiral

stationary

phase

[Zn2(bdc)(lac)]

0 10 20 30 40

R

S

Con

c (

ru

)

0 20 40 60 80

SR

Con

c (

ru

)

SCH3

O

S

O











conductivity




MIL-101


45

FOH

H2O H2O


zeolytic topology


2040










MIL-101 acidMIL-101






acid in acidMIL-101



(3 - 4 M)



2) Filtration



H2SO4

H3PO4









conductivity


80 degC and RH 10








drugs

Selective sorption

gas molecules

enantioseparation


Chiral catalysis







51

52



Acknowledgments


Prof OA Kholdeeva

Prof V Ponomareva

Prof K Kim

Prof M Schoumlder















framework dynamics

vacuum

solvent

Fully reversible

V = -3



23

0

50

100

150

200

250

300

350

400

450

500

0 01 02 03 04 05 06 07 08 09 1

Am

ount adsorb

ed m

Lg


Adsorption

Desorption



Porous properties


Langmuir = 2000 m2g




0

20

40

60

80

100

120

140

160

180

0 01 02 03 04 05 06 07 08 09 1

Am

ou

nt

ad

so

rbe

d

mL

g


Adsorption

Desorption




-- At 1 bar (273 K) = 162 mlg = 32

mass







2012 112 724






fragment (c)






28




K+ 1 + Cs+K+ +

2 3

Cs+

Cations exchange






Rb Cs) in NMP




adduct of 1 (red)




metal cations


Chiral MOFs for


0 10 20 30 40

R

S

32

Metal or cluster

cation


ligand (spacer)

Chiral porous MOF

Cl

Cl

N

N

OH

OH

O

O

O

OO

O

N

N

O O

O O

HO NH

N

O

O

P

P

O

O

OH

OH

OH

OH



Катион

металла

Хиральный

лиганд




МОКП

Жесткий

мостик










Zn(NO3)2

(+)-camphoric acid

+


DMF + Py



Zn(II) Camphorates


N

N

N

N

N

Ndabcobipy

bpe

Chiral

layers

Homochiral

porous



36


Vfree = 31

channel

3 35 Aring

Sarea = 520 m2g

Vfree = 51

channel

5 7 Aring

Sarea = 1040 m2g

Vfree = 56

channel

5 10 Aring



38


Zn(NO3)2

(S)-H2lac

OH

HO

O

O

H2bdc

DMF


Chiral chain

OO

OO

Linear

spacer


COOH

HO H

CH3

Chiral chain


Zn(NO3)2 +H

COOH

OH

CH3

H

COOH

OH

+

H2lac

H2man

H2ndc

H2bpdc

HO

O

OH

O

HO

O OH

O

DMF

Chiral porous MOFs

39


channel 4 x 5 Aring

window 5 x 5 Aring

channel 5 x 9 Aring

window 4 x 5 Aring


window 6 x 7 Aring


40


(R + S)

Racemic

mixture


CH3

O

HO 20 (S)

Sulforaphane

Zn(NO3)2 + +CH3

H

COOH

OH

OH

HO

O

O

[Zn2(S-lac)(bdc)]

SCH3

O

S

O

CH3

OH

HO


ee= ([R]-[S])([R]+[S])

Substrate ee()

60 (S)

55 (S)

21 (S)

25 (+)

no sorptionS

CH3

OChiral sorbent

[Zn2(S-lac)(bdc)]


41

Racemic

mixture

Separated

optical

isomers

Chiral

stationary

phase

[Zn2(bdc)(lac)]

0 10 20 30 40

R

S

Con

c (

ru

)

0 20 40 60 80

SR

Con

c (

ru

)

SCH3

O

S

O











conductivity




MIL-101


45

FOH

H2O H2O


zeolytic topology


2040










MIL-101 acidMIL-101






acid in acidMIL-101



(3 - 4 M)



2) Filtration



H2SO4

H3PO4









conductivity


80 degC and RH 10








drugs

Selective sorption

gas molecules

enantioseparation


Chiral catalysis







51

52



Acknowledgments


Prof OA Kholdeeva

Prof V Ponomareva

Prof K Kim

Prof M Schoumlder














0

50

100

150

200

250

300

350

400

450

500

0 01 02 03 04 05 06 07 08 09 1

Am

ount adsorb

ed m

Lg


Adsorption

Desorption



Porous properties


Langmuir = 2000 m2g




0

20

40

60

80

100

120

140

160

180

0 01 02 03 04 05 06 07 08 09 1

Am

ou

nt

ad

so

rbe

d

mL

g


Adsorption

Desorption




-- At 1 bar (273 K) = 162 mlg = 32

mass







2012 112 724






fragment (c)






28




K+ 1 + Cs+K+ +

2 3

Cs+

Cations exchange






Rb Cs) in NMP




adduct of 1 (red)




metal cations


Chiral MOFs for


0 10 20 30 40

R

S

32

Metal or cluster

cation


ligand (spacer)

Chiral porous MOF

Cl

Cl

N

N

OH

OH

O

O

O

OO

O

N

N

O O

O O

HO NH

N

O

O

P

P

O

O

OH

OH

OH

OH



Катион

металла

Хиральный

лиганд




МОКП

Жесткий

мостик










Zn(NO3)2

(+)-camphoric acid

+


DMF + Py



Zn(II) Camphorates


N

N

N

N

N

Ndabcobipy

bpe

Chiral

layers

Homochiral

porous



36


Vfree = 31

channel

3 35 Aring

Sarea = 520 m2g

Vfree = 51

channel

5 7 Aring

Sarea = 1040 m2g

Vfree = 56

channel

5 10 Aring



38


Zn(NO3)2

(S)-H2lac

OH

HO

O

O

H2bdc

DMF


Chiral chain

OO

OO

Linear

spacer


COOH

HO H

CH3

Chiral chain


Zn(NO3)2 +H

COOH

OH

CH3

H

COOH

OH

+

H2lac

H2man

H2ndc

H2bpdc

HO

O

OH

O

HO

O OH

O

DMF

Chiral porous MOFs

39


channel 4 x 5 Aring

window 5 x 5 Aring

channel 5 x 9 Aring

window 4 x 5 Aring


window 6 x 7 Aring


40


(R + S)

Racemic

mixture


CH3

O

HO 20 (S)

Sulforaphane

Zn(NO3)2 + +CH3

H

COOH

OH

OH

HO

O

O

[Zn2(S-lac)(bdc)]

SCH3

O

S

O

CH3

OH

HO


ee= ([R]-[S])([R]+[S])

Substrate ee()

60 (S)

55 (S)

21 (S)

25 (+)

no sorptionS

CH3

OChiral sorbent

[Zn2(S-lac)(bdc)]


41

Racemic

mixture

Separated

optical

isomers

Chiral

stationary

phase

[Zn2(bdc)(lac)]

0 10 20 30 40

R

S

Con

c (

ru

)

0 20 40 60 80

SR

Con

c (

ru

)

SCH3

O

S

O











conductivity




MIL-101


45

FOH

H2O H2O


zeolytic topology


2040










MIL-101 acidMIL-101






acid in acidMIL-101



(3 - 4 M)



2) Filtration



H2SO4

H3PO4









conductivity


80 degC and RH 10








drugs

Selective sorption

gas molecules

enantioseparation


Chiral catalysis







51

52



Acknowledgments


Prof OA Kholdeeva

Prof V Ponomareva

Prof K Kim

Prof M Schoumlder














0

20

40

60

80

100

120

140

160

180

0 01 02 03 04 05 06 07 08 09 1

Am

ou

nt

ad

so

rbe

d

mL

g


Adsorption

Desorption




-- At 1 bar (273 K) = 162 mlg = 32

mass







2012 112 724






fragment (c)






28




K+ 1 + Cs+K+ +

2 3

Cs+

Cations exchange






Rb Cs) in NMP




adduct of 1 (red)




metal cations


Chiral MOFs for


0 10 20 30 40

R

S

32

Metal or cluster

cation


ligand (spacer)

Chiral porous MOF

Cl

Cl

N

N

OH

OH

O

O

O

OO

O

N

N

O O

O O

HO NH

N

O

O

P

P

O

O

OH

OH

OH

OH



Катион

металла

Хиральный

лиганд




МОКП

Жесткий

мостик










Zn(NO3)2

(+)-camphoric acid

+


DMF + Py



Zn(II) Camphorates


N

N

N

N

N

Ndabcobipy

bpe

Chiral

layers

Homochiral

porous



36


Vfree = 31

channel

3 35 Aring

Sarea = 520 m2g

Vfree = 51

channel

5 7 Aring

Sarea = 1040 m2g

Vfree = 56

channel

5 10 Aring



38


Zn(NO3)2

(S)-H2lac

OH

HO

O

O

H2bdc

DMF


Chiral chain

OO

OO

Linear

spacer


COOH

HO H

CH3

Chiral chain


Zn(NO3)2 +H

COOH

OH

CH3

H

COOH

OH

+

H2lac

H2man

H2ndc

H2bpdc

HO

O

OH

O

HO

O OH

O

DMF

Chiral porous MOFs

39


channel 4 x 5 Aring

window 5 x 5 Aring

channel 5 x 9 Aring

window 4 x 5 Aring


window 6 x 7 Aring


40


(R + S)

Racemic

mixture


CH3

O

HO 20 (S)

Sulforaphane

Zn(NO3)2 + +CH3

H

COOH

OH

OH

HO

O

O

[Zn2(S-lac)(bdc)]

SCH3

O

S

O

CH3

OH

HO


ee= ([R]-[S])([R]+[S])

Substrate ee()

60 (S)

55 (S)

21 (S)

25 (+)

no sorptionS

CH3

OChiral sorbent

[Zn2(S-lac)(bdc)]


41

Racemic

mixture

Separated

optical

isomers

Chiral

stationary

phase

[Zn2(bdc)(lac)]

0 10 20 30 40

R

S

Con

c (

ru

)

0 20 40 60 80

SR

Con

c (

ru

)

SCH3

O

S

O











conductivity




MIL-101


45

FOH

H2O H2O


zeolytic topology


2040










MIL-101 acidMIL-101






acid in acidMIL-101



(3 - 4 M)



2) Filtration



H2SO4

H3PO4









conductivity


80 degC and RH 10








drugs

Selective sorption

gas molecules

enantioseparation


Chiral catalysis







51

52



Acknowledgments


Prof OA Kholdeeva

Prof V Ponomareva

Prof K Kim

Prof M Schoumlder


















fragment (c)






28




K+ 1 + Cs+K+ +

2 3

Cs+

Cations exchange






Rb Cs) in NMP




adduct of 1 (red)




metal cations


Chiral MOFs for


0 10 20 30 40

R

S

32

Metal or cluster

cation


ligand (spacer)

Chiral porous MOF

Cl

Cl

N

N

OH

OH

O

O

O

OO

O

N

N

O O

O O

HO NH

N

O

O

P

P

O

O

OH

OH

OH

OH



Катион

металла

Хиральный

лиганд




МОКП

Жесткий

мостик










Zn(NO3)2

(+)-camphoric acid

+


DMF + Py



Zn(II) Camphorates


N

N

N

N

N

Ndabcobipy

bpe

Chiral

layers

Homochiral

porous



36


Vfree = 31

channel

3 35 Aring

Sarea = 520 m2g

Vfree = 51

channel

5 7 Aring

Sarea = 1040 m2g

Vfree = 56

channel

5 10 Aring



38


Zn(NO3)2

(S)-H2lac

OH

HO

O

O

H2bdc

DMF


Chiral chain

OO

OO

Linear

spacer


COOH

HO H

CH3

Chiral chain


Zn(NO3)2 +H

COOH

OH

CH3

H

COOH

OH

+

H2lac

H2man

H2ndc

H2bpdc

HO

O

OH

O

HO

O OH

O

DMF

Chiral porous MOFs

39


channel 4 x 5 Aring

window 5 x 5 Aring

channel 5 x 9 Aring

window 4 x 5 Aring


window 6 x 7 Aring


40


(R + S)

Racemic

mixture


CH3

O

HO 20 (S)

Sulforaphane

Zn(NO3)2 + +CH3

H

COOH

OH

OH

HO

O

O

[Zn2(S-lac)(bdc)]

SCH3

O

S

O

CH3

OH

HO


ee= ([R]-[S])([R]+[S])

Substrate ee()

60 (S)

55 (S)

21 (S)

25 (+)

no sorptionS

CH3

OChiral sorbent

[Zn2(S-lac)(bdc)]


41

Racemic

mixture

Separated

optical

isomers

Chiral

stationary

phase

[Zn2(bdc)(lac)]

0 10 20 30 40

R

S

Con

c (

ru

)

0 20 40 60 80

SR

Con

c (

ru

)

SCH3

O

S

O











conductivity




MIL-101


45

FOH

H2O H2O


zeolytic topology


2040










MIL-101 acidMIL-101






acid in acidMIL-101



(3 - 4 M)



2) Filtration



H2SO4

H3PO4









conductivity


80 degC and RH 10








drugs

Selective sorption

gas molecules

enantioseparation


Chiral catalysis







51

52



Acknowledgments


Prof OA Kholdeeva

Prof V Ponomareva

Prof K Kim

Prof M Schoumlder















28




K+ 1 + Cs+K+ +

2 3

Cs+

Cations exchange






Rb Cs) in NMP




adduct of 1 (red)




metal cations


Chiral MOFs for


0 10 20 30 40

R

S

32

Metal or cluster

cation


ligand (spacer)

Chiral porous MOF

Cl

Cl

N

N

OH

OH

O

O

O

OO

O

N

N

O O

O O

HO NH

N

O

O

P

P

O

O

OH

OH

OH

OH



Катион

металла

Хиральный

лиганд




МОКП

Жесткий

мостик










Zn(NO3)2

(+)-camphoric acid

+


DMF + Py



Zn(II) Camphorates


N

N

N

N

N

Ndabcobipy

bpe

Chiral

layers

Homochiral

porous



36


Vfree = 31

channel

3 35 Aring

Sarea = 520 m2g

Vfree = 51

channel

5 7 Aring

Sarea = 1040 m2g

Vfree = 56

channel

5 10 Aring



38


Zn(NO3)2

(S)-H2lac

OH

HO

O

O

H2bdc

DMF


Chiral chain

OO

OO

Linear

spacer


COOH

HO H

CH3

Chiral chain


Zn(NO3)2 +H

COOH

OH

CH3

H

COOH

OH

+

H2lac

H2man

H2ndc

H2bpdc

HO

O

OH

O

HO

O OH

O

DMF

Chiral porous MOFs

39


channel 4 x 5 Aring

window 5 x 5 Aring

channel 5 x 9 Aring

window 4 x 5 Aring


window 6 x 7 Aring


40


(R + S)

Racemic

mixture


CH3

O

HO 20 (S)

Sulforaphane

Zn(NO3)2 + +CH3

H

COOH

OH

OH

HO

O

O

[Zn2(S-lac)(bdc)]

SCH3

O

S

O

CH3

OH

HO


ee= ([R]-[S])([R]+[S])

Substrate ee()

60 (S)

55 (S)

21 (S)

25 (+)

no sorptionS

CH3

OChiral sorbent

[Zn2(S-lac)(bdc)]


41

Racemic

mixture

Separated

optical

isomers

Chiral

stationary

phase

[Zn2(bdc)(lac)]

0 10 20 30 40

R

S

Con

c (

ru

)

0 20 40 60 80

SR

Con

c (

ru

)

SCH3

O

S

O











conductivity




MIL-101


45

FOH

H2O H2O


zeolytic topology


2040










MIL-101 acidMIL-101






acid in acidMIL-101



(3 - 4 M)



2) Filtration



H2SO4

H3PO4









conductivity


80 degC and RH 10








drugs

Selective sorption

gas molecules

enantioseparation


Chiral catalysis







51

52



Acknowledgments


Prof OA Kholdeeva

Prof V Ponomareva

Prof K Kim

Prof M Schoumlder

















K+ 1 + Cs+K+ +

2 3

Cs+

Cations exchange






Rb Cs) in NMP




adduct of 1 (red)




metal cations


Chiral MOFs for


0 10 20 30 40

R

S

32

Metal or cluster

cation


ligand (spacer)

Chiral porous MOF

Cl

Cl

N

N

OH

OH

O

O

O

OO

O

N

N

O O

O O

HO NH

N

O

O

P

P

O

O

OH

OH

OH

OH



Катион

металла

Хиральный

лиганд




МОКП

Жесткий

мостик










Zn(NO3)2

(+)-camphoric acid

+


DMF + Py



Zn(II) Camphorates


N

N

N

N

N

Ndabcobipy

bpe

Chiral

layers

Homochiral

porous



36


Vfree = 31

channel

3 35 Aring

Sarea = 520 m2g

Vfree = 51

channel

5 7 Aring

Sarea = 1040 m2g

Vfree = 56

channel

5 10 Aring



38


Zn(NO3)2

(S)-H2lac

OH

HO

O

O

H2bdc

DMF


Chiral chain

OO

OO

Linear

spacer


COOH

HO H

CH3

Chiral chain


Zn(NO3)2 +H

COOH

OH

CH3

H

COOH

OH

+

H2lac

H2man

H2ndc

H2bpdc

HO

O

OH

O

HO

O OH

O

DMF

Chiral porous MOFs

39


channel 4 x 5 Aring

window 5 x 5 Aring

channel 5 x 9 Aring

window 4 x 5 Aring


window 6 x 7 Aring


40


(R + S)

Racemic

mixture


CH3

O

HO 20 (S)

Sulforaphane

Zn(NO3)2 + +CH3

H

COOH

OH

OH

HO

O

O

[Zn2(S-lac)(bdc)]

SCH3

O

S

O

CH3

OH

HO


ee= ([R]-[S])([R]+[S])

Substrate ee()

60 (S)

55 (S)

21 (S)

25 (+)

no sorptionS

CH3

OChiral sorbent

[Zn2(S-lac)(bdc)]


41

Racemic

mixture

Separated

optical

isomers

Chiral

stationary

phase

[Zn2(bdc)(lac)]

0 10 20 30 40

R

S

Con

c (

ru

)

0 20 40 60 80

SR

Con

c (

ru

)

SCH3

O

S

O











conductivity




MIL-101


45

FOH

H2O H2O


zeolytic topology


2040










MIL-101 acidMIL-101






acid in acidMIL-101



(3 - 4 M)



2) Filtration



H2SO4

H3PO4









conductivity


80 degC and RH 10








drugs

Selective sorption

gas molecules

enantioseparation


Chiral catalysis







51

52



Acknowledgments


Prof OA Kholdeeva

Prof V Ponomareva

Prof K Kim

Prof M Schoumlder

















Rb Cs) in NMP




adduct of 1 (red)




metal cations


Chiral MOFs for


0 10 20 30 40

R

S

32

Metal or cluster

cation


ligand (spacer)

Chiral porous MOF

Cl

Cl

N

N

OH

OH

O

O

O

OO

O

N

N

O O

O O

HO NH

N

O

O

P

P

O

O

OH

OH

OH

OH



Катион

металла

Хиральный

лиганд




МОКП

Жесткий

мостик










Zn(NO3)2

(+)-camphoric acid

+


DMF + Py



Zn(II) Camphorates


N

N

N

N

N

Ndabcobipy

bpe

Chiral

layers

Homochiral

porous



36


Vfree = 31

channel

3 35 Aring

Sarea = 520 m2g

Vfree = 51

channel

5 7 Aring

Sarea = 1040 m2g

Vfree = 56

channel

5 10 Aring



38


Zn(NO3)2

(S)-H2lac

OH

HO

O

O

H2bdc

DMF


Chiral chain

OO

OO

Linear

spacer


COOH

HO H

CH3

Chiral chain


Zn(NO3)2 +H

COOH

OH

CH3

H

COOH

OH

+

H2lac

H2man

H2ndc

H2bpdc

HO

O

OH

O

HO

O OH

O

DMF

Chiral porous MOFs

39


channel 4 x 5 Aring

window 5 x 5 Aring

channel 5 x 9 Aring

window 4 x 5 Aring


window 6 x 7 Aring


40


(R + S)

Racemic

mixture


CH3

O

HO 20 (S)

Sulforaphane

Zn(NO3)2 + +CH3

H

COOH

OH

OH

HO

O

O

[Zn2(S-lac)(bdc)]

SCH3

O

S

O

CH3

OH

HO


ee= ([R]-[S])([R]+[S])

Substrate ee()

60 (S)

55 (S)

21 (S)

25 (+)

no sorptionS

CH3

OChiral sorbent

[Zn2(S-lac)(bdc)]


41

Racemic

mixture

Separated

optical

isomers

Chiral

stationary

phase

[Zn2(bdc)(lac)]

0 10 20 30 40

R

S

Con

c (

ru

)

0 20 40 60 80

SR

Con

c (

ru

)

SCH3

O

S

O











conductivity




MIL-101


45

FOH

H2O H2O


zeolytic topology


2040










MIL-101 acidMIL-101






acid in acidMIL-101



(3 - 4 M)



2) Filtration



H2SO4

H3PO4









conductivity


80 degC and RH 10








drugs

Selective sorption

gas molecules

enantioseparation


Chiral catalysis







51

52



Acknowledgments


Prof OA Kholdeeva

Prof V Ponomareva

Prof K Kim

Prof M Schoumlder














Chiral MOFs for


0 10 20 30 40

R

S

32

Metal or cluster

cation


ligand (spacer)

Chiral porous MOF

Cl

Cl

N

N

OH

OH

O

O

O

OO

O

N

N

O O

O O

HO NH

N

O

O

P

P

O

O

OH

OH

OH

OH



Катион

металла

Хиральный

лиганд




МОКП

Жесткий

мостик










Zn(NO3)2

(+)-camphoric acid

+


DMF + Py



Zn(II) Camphorates


N

N

N

N

N

Ndabcobipy

bpe

Chiral

layers

Homochiral

porous



36


Vfree = 31

channel

3 35 Aring

Sarea = 520 m2g

Vfree = 51

channel

5 7 Aring

Sarea = 1040 m2g

Vfree = 56

channel

5 10 Aring



38


Zn(NO3)2

(S)-H2lac

OH

HO

O

O

H2bdc

DMF


Chiral chain

OO

OO

Linear

spacer


COOH

HO H

CH3

Chiral chain


Zn(NO3)2 +H

COOH

OH

CH3

H

COOH

OH

+

H2lac

H2man

H2ndc

H2bpdc

HO

O

OH

O

HO

O OH

O

DMF

Chiral porous MOFs

39


channel 4 x 5 Aring

window 5 x 5 Aring

channel 5 x 9 Aring

window 4 x 5 Aring


window 6 x 7 Aring


40


(R + S)

Racemic

mixture


CH3

O

HO 20 (S)

Sulforaphane

Zn(NO3)2 + +CH3

H

COOH

OH

OH

HO

O

O

[Zn2(S-lac)(bdc)]

SCH3

O

S

O

CH3

OH

HO


ee= ([R]-[S])([R]+[S])

Substrate ee()

60 (S)

55 (S)

21 (S)

25 (+)

no sorptionS

CH3

OChiral sorbent

[Zn2(S-lac)(bdc)]


41

Racemic

mixture

Separated

optical

isomers

Chiral

stationary

phase

[Zn2(bdc)(lac)]

0 10 20 30 40

R

S

Con

c (

ru

)

0 20 40 60 80

SR

Con

c (

ru

)

SCH3

O

S

O











conductivity




MIL-101


45

FOH

H2O H2O


zeolytic topology


2040










MIL-101 acidMIL-101






acid in acidMIL-101



(3 - 4 M)



2) Filtration



H2SO4

H3PO4









conductivity


80 degC and RH 10








drugs

Selective sorption

gas molecules

enantioseparation


Chiral catalysis







51

52



Acknowledgments


Prof OA Kholdeeva

Prof V Ponomareva

Prof K Kim

Prof M Schoumlder














Metal or cluster

cation


ligand (spacer)

Chiral porous MOF

Cl

Cl

N

N

OH

OH

O

O

O

OO

O

N

N

O O

O O

HO NH

N

O

O

P

P

O

O

OH

OH

OH

OH



Катион

металла

Хиральный

лиганд




МОКП

Жесткий

мостик










Zn(NO3)2

(+)-camphoric acid

+


DMF + Py



Zn(II) Camphorates


N

N

N

N

N

Ndabcobipy

bpe

Chiral

layers

Homochiral

porous



36


Vfree = 31

channel

3 35 Aring

Sarea = 520 m2g

Vfree = 51

channel

5 7 Aring

Sarea = 1040 m2g

Vfree = 56

channel

5 10 Aring



38


Zn(NO3)2

(S)-H2lac

OH

HO

O

O

H2bdc

DMF


Chiral chain

OO

OO

Linear

spacer


COOH

HO H

CH3

Chiral chain


Zn(NO3)2 +H

COOH

OH

CH3

H

COOH

OH

+

H2lac

H2man

H2ndc

H2bpdc

HO

O

OH

O

HO

O OH

O

DMF

Chiral porous MOFs

39


channel 4 x 5 Aring

window 5 x 5 Aring

channel 5 x 9 Aring

window 4 x 5 Aring


window 6 x 7 Aring


40


(R + S)

Racemic

mixture


CH3

O

HO 20 (S)

Sulforaphane

Zn(NO3)2 + +CH3

H

COOH

OH

OH

HO

O

O

[Zn2(S-lac)(bdc)]

SCH3

O

S

O

CH3

OH

HO


ee= ([R]-[S])([R]+[S])

Substrate ee()

60 (S)

55 (S)

21 (S)

25 (+)

no sorptionS

CH3

OChiral sorbent

[Zn2(S-lac)(bdc)]


41

Racemic

mixture

Separated

optical

isomers

Chiral

stationary

phase

[Zn2(bdc)(lac)]

0 10 20 30 40

R

S

Con

c (

ru

)

0 20 40 60 80

SR

Con

c (

ru

)

SCH3

O

S

O











conductivity




MIL-101


45

FOH

H2O H2O


zeolytic topology


2040










MIL-101 acidMIL-101






acid in acidMIL-101



(3 - 4 M)



2) Filtration



H2SO4

H3PO4









conductivity


80 degC and RH 10








drugs

Selective sorption

gas molecules

enantioseparation


Chiral catalysis







51

52



Acknowledgments


Prof OA Kholdeeva

Prof V Ponomareva

Prof K Kim

Prof M Schoumlder














Катион

металла

Хиральный

лиганд




МОКП

Жесткий

мостик










Zn(NO3)2

(+)-camphoric acid

+


DMF + Py



Zn(II) Camphorates


N

N

N

N

N

Ndabcobipy

bpe

Chiral

layers

Homochiral

porous



36


Vfree = 31

channel

3 35 Aring

Sarea = 520 m2g

Vfree = 51

channel

5 7 Aring

Sarea = 1040 m2g

Vfree = 56

channel

5 10 Aring



38


Zn(NO3)2

(S)-H2lac

OH

HO

O

O

H2bdc

DMF


Chiral chain

OO

OO

Linear

spacer


COOH

HO H

CH3

Chiral chain


Zn(NO3)2 +H

COOH

OH

CH3

H

COOH

OH

+

H2lac

H2man

H2ndc

H2bpdc

HO

O

OH

O

HO

O OH

O

DMF

Chiral porous MOFs

39


channel 4 x 5 Aring

window 5 x 5 Aring

channel 5 x 9 Aring

window 4 x 5 Aring


window 6 x 7 Aring


40


(R + S)

Racemic

mixture


CH3

O

HO 20 (S)

Sulforaphane

Zn(NO3)2 + +CH3

H

COOH

OH

OH

HO

O

O

[Zn2(S-lac)(bdc)]

SCH3

O

S

O

CH3

OH

HO


ee= ([R]-[S])([R]+[S])

Substrate ee()

60 (S)

55 (S)

21 (S)

25 (+)

no sorptionS

CH3

OChiral sorbent

[Zn2(S-lac)(bdc)]


41

Racemic

mixture

Separated

optical

isomers

Chiral

stationary

phase

[Zn2(bdc)(lac)]

0 10 20 30 40

R

S

Con

c (

ru

)

0 20 40 60 80

SR

Con

c (

ru

)

SCH3

O

S

O











conductivity




MIL-101


45

FOH

H2O H2O


zeolytic topology


2040










MIL-101 acidMIL-101






acid in acidMIL-101



(3 - 4 M)



2) Filtration



H2SO4

H3PO4









conductivity


80 degC and RH 10








drugs

Selective sorption

gas molecules

enantioseparation


Chiral catalysis







51

52



Acknowledgments


Prof OA Kholdeeva

Prof V Ponomareva

Prof K Kim

Prof M Schoumlder














Zn(NO3)2

(+)-camphoric acid

+


DMF + Py



Zn(II) Camphorates


N

N

N

N

N

Ndabcobipy

bpe

Chiral

layers

Homochiral

porous



36


Vfree = 31

channel

3 35 Aring

Sarea = 520 m2g

Vfree = 51

channel

5 7 Aring

Sarea = 1040 m2g

Vfree = 56

channel

5 10 Aring



38


Zn(NO3)2

(S)-H2lac

OH

HO

O

O

H2bdc

DMF


Chiral chain

OO

OO

Linear

spacer


COOH

HO H

CH3

Chiral chain


Zn(NO3)2 +H

COOH

OH

CH3

H

COOH

OH

+

H2lac

H2man

H2ndc

H2bpdc

HO

O

OH

O

HO

O OH

O

DMF

Chiral porous MOFs

39


channel 4 x 5 Aring

window 5 x 5 Aring

channel 5 x 9 Aring

window 4 x 5 Aring


window 6 x 7 Aring


40


(R + S)

Racemic

mixture


CH3

O

HO 20 (S)

Sulforaphane

Zn(NO3)2 + +CH3

H

COOH

OH

OH

HO

O

O

[Zn2(S-lac)(bdc)]

SCH3

O

S

O

CH3

OH

HO


ee= ([R]-[S])([R]+[S])

Substrate ee()

60 (S)

55 (S)

21 (S)

25 (+)

no sorptionS

CH3

OChiral sorbent

[Zn2(S-lac)(bdc)]


41

Racemic

mixture

Separated

optical

isomers

Chiral

stationary

phase

[Zn2(bdc)(lac)]

0 10 20 30 40

R

S

Con

c (

ru

)

0 20 40 60 80

SR

Con

c (

ru

)

SCH3

O

S

O











conductivity




MIL-101


45

FOH

H2O H2O


zeolytic topology


2040










MIL-101 acidMIL-101






acid in acidMIL-101



(3 - 4 M)



2) Filtration



H2SO4

H3PO4









conductivity


80 degC and RH 10








drugs

Selective sorption

gas molecules

enantioseparation


Chiral catalysis







51

52



Acknowledgments


Prof OA Kholdeeva

Prof V Ponomareva

Prof K Kim

Prof M Schoumlder














N

N

N

N

N

Ndabcobipy

bpe

Chiral

layers

Homochiral

porous



36


Vfree = 31

channel

3 35 Aring

Sarea = 520 m2g

Vfree = 51

channel

5 7 Aring

Sarea = 1040 m2g

Vfree = 56

channel

5 10 Aring



38


Zn(NO3)2

(S)-H2lac

OH

HO

O

O

H2bdc

DMF


Chiral chain

OO

OO

Linear

spacer


COOH

HO H

CH3

Chiral chain


Zn(NO3)2 +H

COOH

OH

CH3

H

COOH

OH

+

H2lac

H2man

H2ndc

H2bpdc

HO

O

OH

O

HO

O OH

O

DMF

Chiral porous MOFs

39


channel 4 x 5 Aring

window 5 x 5 Aring

channel 5 x 9 Aring

window 4 x 5 Aring


window 6 x 7 Aring


40


(R + S)

Racemic

mixture


CH3

O

HO 20 (S)

Sulforaphane

Zn(NO3)2 + +CH3

H

COOH

OH

OH

HO

O

O

[Zn2(S-lac)(bdc)]

SCH3

O

S

O

CH3

OH

HO


ee= ([R]-[S])([R]+[S])

Substrate ee()

60 (S)

55 (S)

21 (S)

25 (+)

no sorptionS

CH3

OChiral sorbent

[Zn2(S-lac)(bdc)]


41

Racemic

mixture

Separated

optical

isomers

Chiral

stationary

phase

[Zn2(bdc)(lac)]

0 10 20 30 40

R

S

Con

c (

ru

)

0 20 40 60 80

SR

Con

c (

ru

)

SCH3

O

S

O











conductivity




MIL-101


45

FOH

H2O H2O


zeolytic topology


2040










MIL-101 acidMIL-101






acid in acidMIL-101



(3 - 4 M)



2) Filtration



H2SO4

H3PO4









conductivity


80 degC and RH 10








drugs

Selective sorption

gas molecules

enantioseparation


Chiral catalysis







51

52



Acknowledgments


Prof OA Kholdeeva

Prof V Ponomareva

Prof K Kim

Prof M Schoumlder















Vfree = 31

channel

3 35 Aring

Sarea = 520 m2g

Vfree = 51

channel

5 7 Aring

Sarea = 1040 m2g

Vfree = 56

channel

5 10 Aring



38


Zn(NO3)2

(S)-H2lac

OH

HO

O

O

H2bdc

DMF


Chiral chain

OO

OO

Linear

spacer


COOH

HO H

CH3

Chiral chain


Zn(NO3)2 +H

COOH

OH

CH3

H

COOH

OH

+

H2lac

H2man

H2ndc

H2bpdc

HO

O

OH

O

HO

O OH

O

DMF

Chiral porous MOFs

39


channel 4 x 5 Aring

window 5 x 5 Aring

channel 5 x 9 Aring

window 4 x 5 Aring


window 6 x 7 Aring


40


(R + S)

Racemic

mixture


CH3

O

HO 20 (S)

Sulforaphane

Zn(NO3)2 + +CH3

H

COOH

OH

OH

HO

O

O

[Zn2(S-lac)(bdc)]

SCH3

O

S

O

CH3

OH

HO


ee= ([R]-[S])([R]+[S])

Substrate ee()

60 (S)

55 (S)

21 (S)

25 (+)

no sorptionS

CH3

OChiral sorbent

[Zn2(S-lac)(bdc)]


41

Racemic

mixture

Separated

optical

isomers

Chiral

stationary

phase

[Zn2(bdc)(lac)]

0 10 20 30 40

R

S

Con

c (

ru

)

0 20 40 60 80

SR

Con

c (

ru

)

SCH3

O

S

O











conductivity




MIL-101


45

FOH

H2O H2O


zeolytic topology


2040










MIL-101 acidMIL-101






acid in acidMIL-101



(3 - 4 M)



2) Filtration



H2SO4

H3PO4









conductivity


80 degC and RH 10








drugs

Selective sorption

gas molecules

enantioseparation


Chiral catalysis







51

52



Acknowledgments


Prof OA Kholdeeva

Prof V Ponomareva

Prof K Kim

Prof M Schoumlder














38


Zn(NO3)2

(S)-H2lac

OH

HO

O

O

H2bdc

DMF


Chiral chain

OO

OO

Linear

spacer


COOH

HO H

CH3

Chiral chain


Zn(NO3)2 +H

COOH

OH

CH3

H

COOH

OH

+

H2lac

H2man

H2ndc

H2bpdc

HO

O

OH

O

HO

O OH

O

DMF

Chiral porous MOFs

39


channel 4 x 5 Aring

window 5 x 5 Aring

channel 5 x 9 Aring

window 4 x 5 Aring


window 6 x 7 Aring


40


(R + S)

Racemic

mixture


CH3

O

HO 20 (S)

Sulforaphane

Zn(NO3)2 + +CH3

H

COOH

OH

OH

HO

O

O

[Zn2(S-lac)(bdc)]

SCH3

O

S

O

CH3

OH

HO


ee= ([R]-[S])([R]+[S])

Substrate ee()

60 (S)

55 (S)

21 (S)

25 (+)

no sorptionS

CH3

OChiral sorbent

[Zn2(S-lac)(bdc)]


41

Racemic

mixture

Separated

optical

isomers

Chiral

stationary

phase

[Zn2(bdc)(lac)]

0 10 20 30 40

R

S

Con

c (

ru

)

0 20 40 60 80

SR

Con

c (

ru

)

SCH3

O

S

O











conductivity




MIL-101


45

FOH

H2O H2O


zeolytic topology


2040










MIL-101 acidMIL-101






acid in acidMIL-101



(3 - 4 M)



2) Filtration



H2SO4

H3PO4









conductivity


80 degC and RH 10








drugs

Selective sorption

gas molecules

enantioseparation


Chiral catalysis







51

52



Acknowledgments


Prof OA Kholdeeva

Prof V Ponomareva

Prof K Kim

Prof M Schoumlder














Chiral chain


Zn(NO3)2 +H

COOH

OH

CH3

H

COOH

OH

+

H2lac

H2man

H2ndc

H2bpdc

HO

O

OH

O

HO

O OH

O

DMF

Chiral porous MOFs

39


channel 4 x 5 Aring

window 5 x 5 Aring

channel 5 x 9 Aring

window 4 x 5 Aring


window 6 x 7 Aring


40


(R + S)

Racemic

mixture


CH3

O

HO 20 (S)

Sulforaphane

Zn(NO3)2 + +CH3

H

COOH

OH

OH

HO

O

O

[Zn2(S-lac)(bdc)]

SCH3

O

S

O

CH3

OH

HO


ee= ([R]-[S])([R]+[S])

Substrate ee()

60 (S)

55 (S)

21 (S)

25 (+)

no sorptionS

CH3

OChiral sorbent

[Zn2(S-lac)(bdc)]


41

Racemic

mixture

Separated

optical

isomers

Chiral

stationary

phase

[Zn2(bdc)(lac)]

0 10 20 30 40

R

S

Con

c (

ru

)

0 20 40 60 80

SR

Con

c (

ru

)

SCH3

O

S

O











conductivity




MIL-101


45

FOH

H2O H2O


zeolytic topology


2040










MIL-101 acidMIL-101






acid in acidMIL-101



(3 - 4 M)



2) Filtration



H2SO4

H3PO4









conductivity


80 degC and RH 10








drugs

Selective sorption

gas molecules

enantioseparation


Chiral catalysis







51

52



Acknowledgments


Prof OA Kholdeeva

Prof V Ponomareva

Prof K Kim

Prof M Schoumlder















channel 4 x 5 Aring

window 5 x 5 Aring

channel 5 x 9 Aring

window 4 x 5 Aring


window 6 x 7 Aring


40


(R + S)

Racemic

mixture


CH3

O

HO 20 (S)

Sulforaphane

Zn(NO3)2 + +CH3

H

COOH

OH

OH

HO

O

O

[Zn2(S-lac)(bdc)]

SCH3

O

S

O

CH3

OH

HO


ee= ([R]-[S])([R]+[S])

Substrate ee()

60 (S)

55 (S)

21 (S)

25 (+)

no sorptionS

CH3

OChiral sorbent

[Zn2(S-lac)(bdc)]


41

Racemic

mixture

Separated

optical

isomers

Chiral

stationary

phase

[Zn2(bdc)(lac)]

0 10 20 30 40

R

S

Con

c (

ru

)

0 20 40 60 80

SR

Con

c (

ru

)

SCH3

O

S

O











conductivity




MIL-101


45

FOH

H2O H2O


zeolytic topology


2040










MIL-101 acidMIL-101






acid in acidMIL-101



(3 - 4 M)



2) Filtration



H2SO4

H3PO4









conductivity


80 degC and RH 10








drugs

Selective sorption

gas molecules

enantioseparation


Chiral catalysis







51

52



Acknowledgments


Prof OA Kholdeeva

Prof V Ponomareva

Prof K Kim

Prof M Schoumlder















(R + S)

Racemic

mixture


CH3

O

HO 20 (S)

Sulforaphane

Zn(NO3)2 + +CH3

H

COOH

OH

OH

HO

O

O

[Zn2(S-lac)(bdc)]

SCH3

O

S

O

CH3

OH

HO


ee= ([R]-[S])([R]+[S])

Substrate ee()

60 (S)

55 (S)

21 (S)

25 (+)

no sorptionS

CH3

OChiral sorbent

[Zn2(S-lac)(bdc)]


41

Racemic

mixture

Separated

optical

isomers

Chiral

stationary

phase

[Zn2(bdc)(lac)]

0 10 20 30 40

R

S

Con

c (

ru

)

0 20 40 60 80

SR

Con

c (

ru

)

SCH3

O

S

O











conductivity




MIL-101


45

FOH

H2O H2O


zeolytic topology


2040










MIL-101 acidMIL-101






acid in acidMIL-101



(3 - 4 M)



2) Filtration



H2SO4

H3PO4









conductivity


80 degC and RH 10








drugs

Selective sorption

gas molecules

enantioseparation


Chiral catalysis







51

52



Acknowledgments


Prof OA Kholdeeva

Prof V Ponomareva

Prof K Kim

Prof M Schoumlder














Racemic

mixture

Separated

optical

isomers

Chiral

stationary

phase

[Zn2(bdc)(lac)]

0 10 20 30 40

R

S

Con

c (

ru

)

0 20 40 60 80

SR

Con

c (

ru

)

SCH3

O

S

O











conductivity




MIL-101


45

FOH

H2O H2O


zeolytic topology


2040










MIL-101 acidMIL-101






acid in acidMIL-101



(3 - 4 M)



2) Filtration



H2SO4

H3PO4









conductivity


80 degC and RH 10








drugs

Selective sorption

gas molecules

enantioseparation


Chiral catalysis







51

52



Acknowledgments


Prof OA Kholdeeva

Prof V Ponomareva

Prof K Kim

Prof M Schoumlder






















conductivity




MIL-101


45

FOH

H2O H2O


zeolytic topology


2040










MIL-101 acidMIL-101






acid in acidMIL-101



(3 - 4 M)



2) Filtration



H2SO4

H3PO4









conductivity


80 degC and RH 10








drugs

Selective sorption

gas molecules

enantioseparation


Chiral catalysis







51

52



Acknowledgments


Prof OA Kholdeeva

Prof V Ponomareva

Prof K Kim

Prof M Schoumlder














MIL-101


45

FOH

H2O H2O


zeolytic topology


2040










MIL-101 acidMIL-101






acid in acidMIL-101



(3 - 4 M)



2) Filtration



H2SO4

H3PO4









conductivity


80 degC and RH 10








drugs

Selective sorption

gas molecules

enantioseparation


Chiral catalysis







51

52



Acknowledgments


Prof OA Kholdeeva

Prof V Ponomareva

Prof K Kim

Prof M Schoumlder























MIL-101 acidMIL-101






acid in acidMIL-101



(3 - 4 M)



2) Filtration



H2SO4

H3PO4









conductivity


80 degC and RH 10








drugs

Selective sorption

gas molecules

enantioseparation


Chiral catalysis







51

52



Acknowledgments


Prof OA Kholdeeva

Prof V Ponomareva

Prof K Kim

Prof M Schoumlder


















acid in acidMIL-101



(3 - 4 M)



2) Filtration



H2SO4

H3PO4









conductivity


80 degC and RH 10








drugs

Selective sorption

gas molecules

enantioseparation


Chiral catalysis







51

52



Acknowledgments


Prof OA Kholdeeva

Prof V Ponomareva

Prof K Kim

Prof M Schoumlder















H2SO4

H3PO4









conductivity


80 degC and RH 10








drugs

Selective sorption

gas molecules

enantioseparation


Chiral catalysis







51

52



Acknowledgments


Prof OA Kholdeeva

Prof V Ponomareva

Prof K Kim

Prof M Schoumlder



















conductivity


80 degC and RH 10








drugs

Selective sorption

gas molecules

enantioseparation


Chiral catalysis







51

52



Acknowledgments


Prof OA Kholdeeva

Prof V Ponomareva

Prof K Kim

Prof M Schoumlder
















drugs

Selective sorption

gas molecules

enantioseparation


Chiral catalysis







51

52



Acknowledgments


Prof OA Kholdeeva

Prof V Ponomareva

Prof K Kim

Prof M Schoumlder



















51

52



Acknowledgments


Prof OA Kholdeeva

Prof V Ponomareva

Prof K Kim

Prof M Schoumlder














52



Acknowledgments


Prof OA Kholdeeva

Prof V Ponomareva

Prof K Kim

Prof M Schoumlder














Acknowledgments


Prof OA Kholdeeva

Prof V Ponomareva

Prof K Kim

Prof M Schoumlder














В.П. Федин

Documents