thermodynamics of molecular recognition and design of supramolecular architectures on the basis of...

THERMODYNAMICS OF MOLECULAR RECOGNITION AND DESIGN OF

SUPRAMOLECULAR ARCHITECTURES ON THE BASIS OF CALIXARENES

A.I.Konovalov, V.V.Gorbatchuk, I.S.Antipin

A.E.Arbuzov Institute of Organic and Physical Chemistry, Kazan Kazan State University

Chemistrymolecular supramolecular

Covalent interactions:

intramolecular binding

Covalent interactions:

intramolecular binding

Specific and nonspecific interactions:

intermolecular binding

Specific and nonspecific interactions:

intermolecular binding

atoms →molecules molecules →supermolecules

Supramolecular assemblies

Radicals

Ions

Ion-radicals

A + B → A―B AB + CD →A―B

C―D

Supermolecules

substrate receptor

guest host

OOO O

H H H H

SSS S

OOO O

H H H H

HOOH HO

OH

OHHOOH

HO

R RR

R

CALIX[4]ARENES

OH

OH

t-Bu

S

4

1872 – A.BayerOH

+ H-CHO polymer productsH+

OH

OH

HC

HO

R

OH4

+ R-CHOH+

OH OH

CH2

n

+ H-CHO OH-

n=4-8

+ S8

NaOH

1944 – A.Zinke, E.Zigler

1978 – C.D.Gutsche

1997 – H.Kumagai et al

R

R R

R

OH

OH

HO

HO

R

R R

R

OH

OH

HO

HO

Brouwer, E. B. et al . Phys. Chem. Chem. Phys. 1999, 1, 4043

Brouwer, E. B.; Enright, G. D.; Ratcliffe, C. I.; Facey, G. A.; Ripmeester, J. A. J. Phys. Chem. 1999, 103, 10604

Calixarenes in Action (Eds. L. Mandolini, R. Ungaro), Imperial College Press. – 2000. -250 p.

Problem: ‘Structure – thermodynamic property’ relationship for inclusion of volatile organic compounds by solid hosts

Experimental methodStatic method of GC headspace

analysis

Experimental methodStatic method of GC headspace

analysis

Solid phase

HOST

GUEST

Vapor phase

Experimental data vapor sorption isotherms

Experimental data vapor sorption isotherms

ResultsInclusion stoichiometry, free energy,

cooperativity

ResultsInclusion stoichiometry, free energy,

cooperativityVariation of host and guest molecular structure

Variation of host and guest molecular structure

Electropneumatic dosingB. Kolb, P. Pospisil, T. Borath and M. Auer, J. High Res. Chromatogr. & Chromatogr. Commun., 1979, 2, 283. Activity determinationA. Hussam and P. W. Carr, Anal. Chem., 1985, 57, 793.

Data examplesJ. H. Park, A. Hussam, P. Couasnon, D. Fritz and P. W. Carr, Anal. Chem., 1987, 59, 1970.

Electropneumatic dosingB. Kolb, P. Pospisil, T. Borath and M. Auer, J. High Res. Chromatogr. & Chromatogr. Commun., 1979, 2, 283. Activity determinationA. Hussam and P. W. Carr, Anal. Chem., 1985, 57, 793.

Data examplesJ. H. Park, A. Hussam, P. Couasnon, D. Fritz and P. W. Carr, Anal. Chem., 1987, 59, 1970.

ELECTROPNEUMATIC VALVE

SPLITTER

FUSED SILICA COLUMN

VIAL WITH SAMPLE

THERMOSTATE

DEVICE OF STATIC HEADSPACE GAS CHROMATOGRAPHIC ANALYSIS

solid phase binding of vapors in comparable conditions

0.00

0.50

1.00

1.50

2.00

0.00 0.50 1.00

Guest activity, P/P0

YS

, mo

l gue

st /

mo

l ho

st MeOHn-PrOHEtCN

0.0

0.4

0.8

1.2

1.6

0.0 0.5 1.0

P/P0

YS; m

ol g

uest

/mol

hos

t CCl4CHCl3CH3NO2

0.0

0.2

0.4

0.6

0.8

1.0

1.2

1.4

0.0 0.2 0.4 0.6 0.8 1.0

P/P0

YS; m

ol g

uest

/mol

hos

t С6Н6CHCl3Dioxane

0.0

1.0

2.0

3.0

4.0

5.0

6.0

0.0 0.5 1.0

P/P0

YS

; m

ol g

uest/m

ol h

ost TolueneBenzeneCHCl3CCl4

Isotherms

T=298 K

OOO OH H HH

HO

OH

OOO OH

HHH S – inclusion stoichiometry

N – cooperativity constant

))С(P/P/(1)SC(P/PYS N0

N0 ))С(P/P/(1)SC(P/PYS N

0N

0 Hill equation

inclusion threshold:50.0

1

0

ln)/ln( aRTdYPPRTG OC = RT(lnC)/N

- inclusion free energy

p-tert-Butylcalix[4]arene

1:1 host-guest complex of p-tert-butylcalix[4]arene with fluorobenzene

Brouwer, E. B.; Udachin, K. A.; Enright, G. D.; Ripmeester J. A. et al Chem. Commun. 2001, 565

Brouwer, E. B et al Phys. Chem. Chem. Phys. 1999, 1, 4043

-10

-5

0

5

10

15

20

0 10 20 30 40 50

MRD, cm3/mol

G

solv, k

J/m

ol

5

41

32

25

1718

43

20

2419

21

26

4427

28

29

30

3133,34

3645

3738

4039

46

1613,14

12,15

11

10

9

42 8

76

4

3

22

1

Solvents: alkanes and cycloalkanes

c-C8H1646

c-C7H1445

c-C6H1244

c-C5H1043

c-C4H842

1,2,4-C6H3Cl341

AmCOOMe40

2-Heptanone39

C6H5Br38

c-C6H11Cl37

c-C6H11NH236

BuCOOMe35

MeCOOBu34

C6H5Cl33

C6H5CH332

n-BuCOMe31

c-C6H11OH30

1-BuBr29

n-BuCOMe28

C6H5OH27

MeCOOPr26

CCl425

C6H624

1-BuCl23

Cl2C=CHCl22

Furfural21

PrCOMe20

C5H5N19

EtI18

1-PrSH17

(MeCO)2O16

Et2O15

MeCOOEt14

EtCOOMe13

1-BuOH12

CS211

EtCOMe10

CHCl39

THF8

MeI7

EtBr6

1-PrOH5

MeCOOMe4

Me2CO3

EtOH2

MeOH1

Gsolv, kJ/mol = -0.702 MRD + 14.0

R=0.9910, n=46, =1.1

B.N.Solomonov, V.V.Gorbatchuk,A.I. Konovalov. Zh. Obsch. Khim. 1981, Vol. 51, P.2688-2693.

-Hsolv / kJ/mol = 5.09 + 1.03 MRD

n=102, r=0.994, =1.56

0.00

0.20

0.40

0.60

0.80

1.00

1.20

1.40

0.0 10.0 20.0 30.0

MR D , cm3/mol

S, m

ol g

ue

st/

mo

l ho

st

1:1

1

8

76

5

4

32

1 CH3OH

14 c-Hexane 20 C6H5OCH3

2 CH3CN

15 n-Hexane 21 n-Heptane

3 EtOH

16 Pinacolone 22 o-Xylene

5 EtCN

17 Toluene 23 C6H5Et

6 (CH3)2CO

18 t-BuOAc 24 n-Octane

7 n-PrOH

8 CHCl39 1,4-Dioxane

10 n-Pentane11 n-BuCl12 C6H6

13 CCl4

19 C6H5NO2 25 n-Nonane0,0

0,5

1,0

1,5

2,0

2,5

0 10 20 30 40 50

MRD, cm3/mol

ST

OIC

HIO

ME

TR

Y,

mo

l g

ue

st

/ m

ol h

ost

15

12

1811

10 1416

19

133 17

20

8

76

5

2

1

21

22

23

24 25

14

2 : 1 guest / host

1 : 1

1 : 2

S~1~ const

V. V. Gorbatchuk, A. G. Tsifarkin, I. S. Antipin, B. N. Solomonov and A.

I. Konovalov, Mendeleev Commun., 1999, 11

Stoichiometry - guest size

1 MeOH 5 Me2CO2 MeCN 6 CH2Cl23 MeNO2 7 CHCl34 EtCN 8 CCl4

Lit.data (X-ray)

V. V. Gorbatchuk, A. G. Tsifarkin, I. S. Antipin, B. N. Solomonov, A. I. Konovalov, P.Lhotak, I.Stibor J. Phys. Chem.B. , 2002, 106(23); 5845-5851

p-tert-Butylcalix[4]arene

1:1 host-guest complex of p-tert-butylcalix[4]arene with fluorobenzene

Brouwer, E. B.; Udachin, K. A.; Enright, G. D.; Ripmeester J. A.; Ooms, K. J.; Halchuk P. A. Chem. Commun. 2001, 565

Brouwer, E. B.; Gougeon, R. D. M.; Hirschinger, J.; Udachin, K. A.; Harris, R. K.;Enright, G. D.; Ripmeester, J. A. Phys. Chem. Chem. Phys. 1999, 1, 4043

All-trans n-hexane, 1-chlorobutane, 1,4-dichlorobutane and 1,4 dichlorobenzene

All-trans n-hexane, 1-heptanol, 1-octanol and dodecane

K. A. Udachin et al. /J. Supramol. Chem. 1 (2001) 97–100

0.00

0.20

0.40

0.60

0.80

1.00

1.20

1.40

0.0 10.0 20.0 30.0

MR D , cm3/mol

S, m

ol g

ue

st/

mo

l ho

st

1:1

1

8

76

5

4

32

1 CH3OH

14 c-Hexane 20 C6H5OCH3

2 CH3CN

15 n-Hexane 21 n-Heptane

3 EtOH

16 Pinacolone 22 o-Xylene

5 EtCN

17 Toluene 23 C6H5Et

6 (CH3)2CO

18 t-BuOAc 24 n-Octane

7 n-PrOH

8 CHCl39 1,4-Dioxane

10 n-Pentane11 n-BuCl12 C6H6

13 CCl4

19 C6H5NO2 25 n-Nonane0,0

0,5

1,0

1,5

2,0

2,5

0 10 20 30 40 50

MRD, cm3/mol

ST

OIC

HIO

ME

TR

Y,

mo

l g

ue

st

/ m

ol h

ost

15

12

1811

10 1416

19

133 17

20

8

76

5

2

1

21

22

23

24 25

14

2 : 1 guest / host

1 : 1

1 : 2

S~1~ const

V. V. Gorbatchuk, A. G. Tsifarkin, I. S. Antipin, B. N. Solomonov and A.

I. Konovalov, Mendeleev Commun., 1999, 11


1 MeOH 5 Me2CO2 MeCN 6 CH2Cl23 MeNO2 7 CHCl34 EtCN 8 CCl4

Lit.data (X-ray)

V. V. Gorbatchuk, A. G. Tsifarkin, I. S. Antipin, B. N. Solomonov, A. I. Konovalov, P.Lhotak, I.Stibor J. Phys. Chem.B. , 2002, 106(23); 5845-5851

Akdas, H.; Bringel, L.; Graf, E.; Hosseini, M. W.; Mislin, G.; Pansanel, J.; de Cian, A.; Fischer, J. Tetrahedron Lett. 1998, 39, 2311

0.00

0.50

1.00

1.50

2.00

2.50

3.00

0 10 20 30 40

MR D , cm3/mol

S, m

ol g

uest

/ mo

l ho

st

2:1

1:1

112

11

1098

7

6

5

4

3

2

1 MeOH 7 CHCl32 MeCN 8 1,4-

Dioxane

3 EtCN 9 Pyridine

4 Me2CO 10 C6H6

5 1-PrOH 11 CCl46 1-PrCN 12 Et3N

HO

OH


V. V. Gorbatchuk, A. G. Tsifarkin, I. S. Antipin, B. N. Solomonov, A. I. Konovalov, J. Seidel, F. Baitalov, J. Chem.Soc. Perkin Trans. 2, 2000, N11, P.2287-2294

L. J. Barbour, S. A. Bourne, M. R. Caira, L. R. Nassimbeni, E. Weber, K. Skobridis and A. Wierig, Supramol. Chem., 1993, 1, 331

0.00

0.50

1.00

1.50

2.00

0.00 0.50 1.00

Guest activity, P/P0

YS

, mo

l gue

st /

mo

l ho

st MeOHn-PrOHEtCN

0.0

0.4

0.8

1.2

1.6

0.0 0.5 1.0

P/P0

YS; m

ol g

uest

/mol

hos

t CCl4CHCl3CH3NO2

0.0

0.2

0.4

0.6

0.8

1.0

1.2

1.4

0.0 0.2 0.4 0.6 0.8 1.0

P/P0

YS; m

ol g

uest

/mol

hos

t С6Н6CHCl3Dioxane

0.0

1.0

2.0

3.0

4.0

5.0

6.0

0.0 0.5 1.0

P/P0

YS

; m

ol g

uest/m

ol h

ost TolueneBenzeneCHCl3CCl4

Isotherms

T=298 K

OOO OH H HH

HO

OH

OOO OH

HHH S – inclusion stoichiometry

N – cooperativity constant

))С(P/P/(1)SC(P/PYS N0

N0 ))С(P/P/(1)SC(P/PYS N

0N

0 Hill equation

inclusion threshold:50.0

1

0

ln)/ln( aRTdYPPRTG OC = RT(lnC)/N

- inclusion free energy

N Guest MRD Gc(vap) Gc(vap) Gc(vap)

1 MeOH 8.3 -5.7 -4.8 -6.5

2 CH3CN 11.1 -9.3 -7.3 -7.93 EtOH 12.9 -8.6 * -6.94 EtCN 16 -12.1 -8.1 -9.5

5 Me2CO 16.1 -4.8 -4.2 -4.9

6 CH2Cl2 16.3 -10.3 -3.5 -7 1-PrOH 17.5 -11.4 * -9.78 n-PrCN 20.4 -11.9 * -11.1

9 CHCl3 21.3 -5.6 -4.5 -5.1

10 C5H5N 24.1 -17.0 * -13.3

11 C6H6 26.2 -12.4 * -6.5

12 CCl4 26.4 -8.6 -5.1 -5.8

13 c-C6H12 27.7 -10.5 * *14 n-C6H14 29.9 -8.7 * *15 Pinacolone 30 -9.9 * *

16 PhCH3 31.1 -13.7 * *17 t-BuOAc 31.7 -10.6 * *

18 PhOCH3 32.9 -19.8 * *

19 Et3N 33.8 -12.4 * -8.5

20 n-C7H16 34.5 -11.8 * *

21 o-C6H4Me2 35.9 -14.5 * *

22 n-C8H18 39.2 -14.2 * *

23 n-C9H20 43.8 -15.3 * *

24 MeNO2 12.9 * -9.3 -25 Dioxane 21.7 - * -10.0

HO

OH

* no binding

- not determined

0.0

5.0

10.0

15.0

20.0

25.0

0 10 20 30 40 50

MR D, cm3/mol

G

c(va

p),

kJ/m

ol

1

22

21

20

19

18

17

16

14

13

12

11

10

9

87

23

5

4

3

2

156

Guest vapor

solid host-guest compound

Gc(

vap)

OOO OH H HH

Benzene, toluene, o-xyleneAlcohols, ketones, esters, anisoleNitriles, pyridine, triethylamine

polychloromethanes

n-alcanes, cyclohexane

0.0

5.0

10.0

15.0

20.0

25.0

0 10 20 30 40 50

MR D, cm3/mol

G

c (va

p),

kJ/

mo

l

1

22

21

2019

18

17

16

14

13

12

11

10

9

87

23

5

4

3

2

156

Guest vapor


Gc(

vap)

OOO OH H HH

Guest vapor

toluene solution

Gso

lv

Alcohols, ketones, esters, anisoleNitriles, pyridine, triethylamine

polychloromethanes

Benzene, toluene, o-xylene


-6

-4

-2

0

2

4

6

8

10

12

14

0 10 20 30 40 50

MR D , cm3/mol

G

solv

, kJ/

mol

1

22

21

20

19

18

17

16

14

1312

11

10

9

8

76

5

3

2

154

23


polychloromethanes



0.0

5.0

10.0

15.0

20.0

25.0

-5.0 0.0 5.0 10.0 15.0

G solv , kJ/mol

G

c (va

p), k

J/m

ol

1

19

23

22

21

20

18

16

15

14

13

12

9

87

6

5

4

32

17

G c (vap) = G solv

6

10

11

Guest vapor

solution

Gso

lv

=+G cav

G int

Solvation process

cavity formation interaction

Gtr

ans

toluene solution



polychloromethanes



-12

-10

-8

-6

-4

-2

0

0 10 20 30 40 50

MR D , см3/моль

Gtr

ans, к

Дж

/мо

ль

1

22

21

20

1918

17

1614

13

12

11

10

9

8

7

6

5

4

3

2

15

23

OOO OH H HH

0.0

2.0

4.0

6.0

8.0

10.0

0 5 10 15 20 25 30

MR D, cm3/mol

G

c (va

p), k

J/m

ol

1

12

96

5

24

2

4

MeOH, acetone

MeCN, EtCN

polychloromethanes

nitromethane

Guest vapor

Gc(

vap)


-9.0

-8.0

-7.0

-6.0

-5.0

-4.0

-3.0

-2.0

-1.0

0.0

0 5 10 15 20 25 30

MR D , cm3/mol

Gtr

ans, k

J/m

ol

1

129

6

5

24

2

4

Gtr

ans

toluene solution


MeOH, acetone

MeCN, EtCN

polychloromethanes

nitromethane

Gtrans /kJ mol-1 = -12.24 + 0.568MRD

(n = 7, r = 0.972, RSD = 0.6)V. V. Gorbatchuk, A. G. Tsifarkin, I. S. Antipin, B. N. Solomonov, A. I. Konovalov, P.Lhotak, I.Stibor J. Phys. Chem.B. , 2002, 106(23); 5845-5851

-6

-5

-4

-3

-2

-1

0

1

2

0 10 20 30 40

MR D , cm3/mol

Gtr

ans -0

.236

G

HP

hOH

, kJ/

mol

1

7

58

12

1911

1043

2

9

25

Alcohols, acetone, dioxane

MeCN, EtCN, PrCN, pyridine, Et3N

CHCl3, CCl4benzene

Gtrans /kJ mol-1 = -5.58 + 0.200MRD + 0.391GHMeOH (n = 13, r = 0.955, RSD = 0.8)

Gtrans /kJ mol-1 = -5.76 + 0.204MRD + 0.236GHPhOH (n = 13, r = 0.954, RSD = 0.8)

HO

OH

V. V. Gorbatchuk, A. G. Tsifarkin, I. S. Antipin, B. N. Solomonov, A. I. Konovalov, J. Seidel, F. Baitalov, J. Chem.Soc. Perkin Trans. 2, 2000, N11, P.2287-2294

Dr.Gorbatchuk V.V.Prof.Antipin I.S. Dr.Tsifarkin A.G.Dr.Ziganshin M.A.Prof.Solomonov B.N.

Group cooperates withW.Habicher TU Dresden, GermanyJ.Seidel TU BA Freiberg, GermanyI.Stibor, P. Lhotak VSHT Prague, Czech Rep.

Support from RFBR (grants № 00-15-97411, 01-03-32079)

thermodynamics of molecular recognition and design of supramolecular architectures on the basis of...

Documents

gutsche1997 h

nonspecific interactions

data examplesj

basis of calixarenes

arbuzov institute of

solid phase binding

intramolecular bindingspecific

physical chemistry