self-assembly formation of mechanically interlocked [2 ... · pdf fileself-assembly formation...

Self-assembly formation of mechanically interlocked [2]- and [3]catenanes using lanthanide ion [Eu(III)] templation and ring closing metathesis reactions

Christophe Lincheneau, Bernard Jean-Denis and Thorfinnur Gunnlaugsson*

Electronic Supplementary Information

ESI.1: Molecular models of the complex L13.Eu and the catenane resulting from a triple RCM, obtained from calculation in the MM2 force field with Chem3D.

ESI.2: MM2 molecular models of the different isomers resulting from a triple RCM, depending on the number of inter- and intra-ligands RCM.

+3

Caténation par macrocyclisation intra-ligands

Caténation avec contributions inter-ligands

Démétallation Démétallation

- Ln - Ln

Isolé Non détecté Non détecté Non détecté

Non détecté Forme majoritaire

potentielle des adduits 15

3"inter(ligand"RCM"

+3




- Ln - Ln




2"inter(ligand"RCM"1"intra(ligand"RCM" 3"intra(ligand"RCM"

+3




- Ln - Ln




3"intra(ligand"RCM"

+

3

Caténation par

macrocyclisation intra-ligands

Caténation avec contributions

inter-ligands

Dém

étallation

Dém

étallation

- Ln

- Ln

Isolé N

on détecté N

on détecté

Non détecté

Non détecté

Forme m

ajoritaire

potentielle des adduits

15

Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is © The Royal Society of Chemistry 2014

ESI.3: Synthesis in 5 steps from the triethylenhglycol of the precursor 2 and synthesis protocols of compound 1-5, L1, L13.Eu and Cat• L23.Eu.

2,6-Pyridinedicarboxylic acid chloride (1):

2,6-Pyridinedicarboxylic acid (5 g, 29.9 mmol) was refluxed overnight in

thionylchloride (50 ml). The mixture was reduced to dryness under reduced

pressure, before compound 1 was obtained as a white powder in 99% yield (5.97

g). Calculated for C7H3NO2Cl2: [M+H]+ m/z = 202.9542; Found: 202.9563; δH (400 MHz, MeOD-

D4, 298.2 K) 8.39 (2H, d, J = 7.56 Hz, Ar-H4), 8.22 (1H, t, J = 7.56 Hz, Ar-H2); Selected IR bands

(cm-1): 1751s (υCO).

2-(2-(2-(allyloxy)ethoxy)ethoxy)ethanol (3):

To a solution of triethylene glycol (30g, 200 mmol) in toluene

(20 mL) at room temperature, allyl chloride (18.04 mL, 219.7

mmol) and NaOH (16 g, 400 mmol) were added. The resulting mixture was refluxed for 3 days.

Upon filtration of a white residue and evaporation of the solvent under reduced pressure, the brown

oil was dissolved in CH2Cl2 and washed with brine (50 mL) and distilled water (50 mL). The

resulting orange oil was further purified by silica column chromatography using hexane-EtOAc

from 7:3 to 1:1 gradient, yielding a colourless oil (10.38 g, 54.6 mmol, 27.3% yield) HRMS (m/z)

(ES+) Calculated for C9H19O4 [M+H+]+ m/z = 191.1286, Found 191.1286; δH (CDCl3; 400 MHz):

OHO

OHO

OHO

OO

OTsO

OO

N3

OO

ONH2

OO

O

3 4

5 2

NaOH, Toluene

Δ, 3 days

TsCl, pyridine

DCM, R.T. 48h

NaN3, CH3CN

Δ, 4 days

PPh3, THF

0°C→R.T., 4 days

NH2

OO

O

NCl

O

Cl

O 1

2

+

L1

i" ii"

L2

N O

HN

O

NH

O

O

O

O

22

N O

HN

O

NH

O

O

O

O

22


5.95 (m, 1H, CH=CH2), 5.28 (m, 2H, CH=CH2), 4.06 (m, 2H, CH2CH=CH2), 3.62 (m, 12H, CH2);

δc (CDCl3; 100 MHz): 134.6, 117.1, 72.5, 70.2-70.5, 61.6.; IR νmax (cm-1) = 3376, 2870, 1648, 1350,

1245, 1116, 1064, 934, 885.

2-(2-(2-(allyloxy)ethoxy)ethoxy)ethyl-4-methylbenzenesulfonate (4):

3 (500 mg, 2.6 mmol) and 5 equivalents of TsCl (2.5 g, 13 mmol)

were dissolved in dichloromethane (20 mL) before the resulting

mixture was stirred for 15 minutes. To that solution, pyridine (2.13 mL, 26 mmol) was added drop

wise before the resulting mixture was stirred at room temperature for 48h. The pyridine was

quenched with 1M HCl (1 mL) before the solvents were removed under reduced pressure. The

resulting mixture was extracted with CH3Cl (50 mL) before the organic layer was washed with H2O

(2×50 mL) and dried over MgSO4. Compound 4 was isolated as a yellow oil in 45% yield (404 mg,

1.17 mmol), after purification via silica column chromatography using CH2Cl2-CH3OH (9-1) as

eluent. HRMS (m/z) (ES+) Calculated for C16H24O6S [M+Na+]+ m/z = 367.1191, Found 367.1132;

δH (CDCl3; 400 MHz): 7.79 (d, 2H, 3J = 8.0 Hz, Ar-H), 7.33 (d, 2H, 3J = 8.0 Hz, Ar-H), 5.89 (m,

1H, CH=CH2), 5.28 (m, 1H, CH=CH2), 5.18 (m, 1H, CH=CH2), 4.16 (m, 2H, CH2-OTs), 4.01 (m,

2H, CH2CH=CH2), 3.68-3.59 (m, 12H, CH2), 2.44 (s, 3H, Ar-CH3); δc (CDCl3; 100 MHz): 144.3,

134.2, 132.5, 129.38, 127.5, 117.1, 71.8, 70.3, 70.2, 68.9, 68.8, 68.2, 21.2; IR νmax (cm-1) = 3389,

2876, 1598, 1452, 1351, 1211, 1188, 1120, 1095, 1033, 916, 816, 683, 662.

3-(2-(2-(2-azidoethoxy)ethoxy)ethoxy)propen-1-ene (5):

5 was synthesised by refluxing 4 (300 mg, 0.87 mmol), with NaN3

(680 mg, 10 mmol, 12 eq) in CH3CN for 4 days. The resulting white

suspension was isolated by filtration before the solvent was removed under reduced pressure. The

resulting yellow oil was dissolved in CH2Cl2 and washed twice with H2O (2 × 50 mL) to give 5 as a

yellow oil in 74% yield (140 mg, 0.64 mmol). δH (CDCl3; 400 MHz): 5.90 (m, 1H, CH=CH2), 5.28

(m, 1H, CH=CH2), 5.16 (m, 1H, CH=CH2), 4.02 (m, 2H, CH2CH=CH2), 3.68-3.59 (m, 12H, CH2),

3.38 (m, 2H, N3-CH2); δc (CDCl3; 100 MHz): 134.2, 116.7, 71.8, 70.3, 70.2, 69.5, 68.9, 50.2, 42.3;

IR νmax (cm-1) = 3422, 2866, 1452, 1348, 1287, 1248, 1094, 995, 927, 881, 838

3-(2-(2-(2-aminoethoxy)ethoxy)ethoxy)propen-1-ene (2):

To a solution of 5 (1.24 g, 5.5 mmol) in THF (50 mL) at 0ºC, PPh3

(1.66 g, 6.1 mmol) was added portionwise and the resulting mixture was


stirred at room temperature for 12h. The resulting oil was dissolved in H2O and washed with

toluene (2 × 20mL). 2 was obtained as a yellow oil after evaporation of the aqueous layer under

reduced pressure (759 mg, 4.0 mmol, 73%). δH (CDCl3; 400 MHz): 5.89 (m, 1H, CH=CH2), 5.28

(m, 1H, CH=CH2), 5.16 (m, 1H, CH=CH2), 4.01 (m, 2H, CH2CH=CH2), 3.65-3.49 (m, 12H, CH2),

2.85 (m, 2H, H2N-CH2); δc (CDCl3; 100 MHz): 134.3, 116.7, 114.8, 71.8, 70.3, 70.2, 69.6, 69.0,

50.2, 42.3; IR νmax (cm-1)= 3360, 2666, 1665, 1565, 1445, 1348, 1297, 1248, 1091, 995, 924, 881,

818.

N,N’-bis(2-(2-(2-(allyloxy)ethoxy)ethoxy)ethyl)pyridine-2,6-dicarboxamide (L1):

To a solution of 1 (300 mg, 1.5 mmol) and

triethylamine (270 mg, 6 mmol, 4 eq) at 0ºC in CH2Cl2

(50 mL) was added a solution of 2 (612 mg, 3.2 mmol, 2.2 eq) and triethylamine (148 mg, 1.6

mmol, 1.1 eq) in CH2Cl2 (20 mL) dropwise over a period of 15 min. The resulting mixture was

allowed to reach room temperature before being stirred for 48h. The solvent was removed under

reduced pressure before the resulting brown oil was re-dissolved in CH2Cl2 and washed with

distilled H2O (2 × 50 mL). The organic layer was dried over MgSO4 before the solvent was removed

and L1 was then obtained as an yellow oil in 48% yield (360 mg, 0.7 mmol). HRMS (m/z) (ES+)

Calculated for C25H39O8N3 [M+Na+]+ m/z = 532.2635, Found 532.2812; δH (CDCl3; 400 MHz):8.57

(s, 2H, NH), 8.35 (d, 3J = 7.6 Hz, 1H, Pyr-H), 8.03 (t, 3J = 8.2 Hz, 2H, Pyr-H), 5.88 (m, 2H,

CH=CH2), 5.26 (m, 2H, CH=CH2), 5.15 (m, 2H, CH=CH2), 3.98 (m, 2H, CH2CH=CH2), 3.72-3.66

(m, 20H, CH2), 3.59 (m, 2H, HN-CH2); δc (CDCl3; 100 MHz): 169.4, 151.3, 134.6, 126.5, 117.2,

72.0, 70.3, 70.2, 70.0, 69.2, 67.3, 45.4, 39.3; IR νmax (cm-1)= 3550, 3320, 2867, 1665, 1532, 1445,

1349, 1247, 1093, 998, 926, 846, 749, 679.

Complex, L13.Eu:

Ligand L1 (50 mg, 0.098 mmol) and Eu(CF3SO3)3 (19.6 mg; 0.032 mmol) were refluxed in CH3CN

(10 mL) for 12h. The solvent was removed under reduced pressure. The resulting concentrated

solution was poured over diethylether before complex L13.Eu was collected in 32% yield as pale

yellow oil (22.2 mg; 0.012 mmol). δH (CDCl3; 600 MHz): 8.53; 8.37; 8.05; 7.36; 5.88; 5.29; 4.04;

3.74-3.59; 3.52. IR νmax (cm-1): 3510, 3285; 1667; 1547; 1346; 1260; 1093; 1005; 980; 937; 752;

677.


Catenation of L13.Eu (Cat•L23.Eu):

Anhydrous complex L13.Eu (26 mg, 0.013 mmol) was dissolved in distilled CH2Cl2 (20 mL),

under an inert atmosphere. To this solution the 2nd generation Grubb’s catalyst (3.1 mg, 3.6 ×10-3

mmol, 0.3 eq) was added drop wise over a period of 5 minutes. The resulting mixture was stirred at

room temperature for 3 days under an inert atmosphere. The CH2Cl2 was removed under reduced

pressure and the resulting brown oil was dissolved in H2O. The aqueous layer was washed with

ethyl acetate (20 mL) before the H2O was removed under reduced pressure. The resulting orange oil

was triturated in CH2Cl2 and Cat•L23.Eu was obtained as a crude white solid (7 mg). The

dichloromethane was removed under reduced pressure and the compound Cat•L23 was obtained as

crude yellow oil (10 mg).

Cat•L23.Eu: HRMS: Calculated for C70H106N9F9O28SEu [M3+ + CF3SO3- + OH-]+ 1762.6044,

Found 1761.6688 δH (CDCl3; 600 MHz): 8.93; 8.34; 7.02; 7.36; 5.88; 5.29; 4.06; 3.73-3.69; 3.50.

IR νmax (cm-1): 3510, 3285; 1667; 1547; 1346; 1260; 1093; 1005; 980; 937; 752; 677.

Cat•L23: HRMS: Calculated for C69H105N9O24 [M + Na+]+ 1466.7170, Found 1466.7152 δH

(CDCl3; 600 MHz): 8.30; 8.15; 5.82; 4.00; 5.88; 5.29; 4.06; 3.73-3.71; 3.24. IR νmax (cm-1): 3552,

3314; 2865; 1665; 1532; 1445; 1345; 1310; 1245; 1099; 998; 852, 740.

Macrocyle L2:

Ligand L1 (50.8 mg, 0.1 mmol) was dissolved in freshly

distilled CH2Cl2 (100 mL), under inert atmosphere. To this

solution the 2nd generation Grubb’s catalyst (12.7 mg, 1.4

×10-3 mmol, 0.14 eq) was added drop wise over a period of

5 minutes. The CH2Cl2 is removed under reduced pressure

and the resulting mixture is washed with H2O (2×50 mL).

The organic layer was washed over MgSO4 and L2 was

obtained as brown oil (38.4 mg, 0.08 mmol, 80%). HRMS:

Calculated for C23H35N3O8 [M + Na+]+: 504.2322, Found 504.2316; δH (CDCl3; 400 MHz): 8.57 (s,

2H, NH), 8.34 (d, 3J = 7.7 Hz, 2H, Pyr-H), 8.02 (t, 3J = 7.8 Hz, 1H, Pyr-H), 5.89 (s, 2H, CH=CH),

4.07 (m, 4H, CH2CH=CH), 3.74-3.66 (m, 22H, CH2), 3.59 (m, 2H, HN-CH2); δc (CDCl3; 100 MHz):

163.6, 148.4, 138.2, 128.9, 124.2, 70.2, 70.1, 69.9, 69.7, 68.6, 39.0, 29.2; IR νmax (cm-1) = 3550,

3314, 2864, 1663, 1534, 1446, 1349, 1305, 1245, 1176, 1098, 999, 847, 749, 662.


ESI.4: Absorption, excitation (λem = 545 and 615 nm) and Emission (λex = 281 nm) spectra of L1 and the resulting Eu3+ and Tb3+ in acetonitrile at C = 2×10-5 M

ESI.5: Absorption, excitation (λem = 545 and 615 nm) and Emission (λex = 281 nm) spectra of L1 and the resulting Eu3+ and Tb3+ in acetonitrile at C = 2×10-5 M

0

0,1

0,2

0,3

0,4

200 250 300 350 400 0

20

40

60

80

100

120

300 400 500 600 700

Wavelength*(nm)*

Em

issi

on

Wavelength*(nm)*

Abs

orpt

ion

a.* b.*

400# 450# 500# 550# 600# 650# 700#0

50

100

150

200

250

300

350

0

0,05

0,1

0,15

0,2

0,25

0,3

0,35

0,4

0,45

0,5

200 300 400 500 600 700

Em

issi

on (a

.u.)

Abs

orba

nce

(a.u

.)

Wavelength (nm)

L1

L13.Ln (UV)

L13.Eu (Emission)

Excitation of L13.Ln

L13.Tb (Emission)


ESI.6: Evolution of the absorption and delayed emission spectra of a solution of L1 (2×10-5 M in acteonitrile) upon the addition of Eu(CF3SO3)3

ESI.6: Job’s plots experiments, performed by varying the molar fraction of Eu(CF3SO3)3 in solution (Ctot = 2×10-5 M in acetonitrile)


ESI.7: Evolution of the absorption and delayed emission spectra of a solution of L1 (2×10-5 M in acteonitrile) upon the addition of Tb(CF3SO3)3


ESI.8: Job’s plots experiments, performed by varying the molar fraction of Tb(CF3SO3)3 in solution (Ctot = 2×10-5 M in acetonitrile)

ESI.9: Speciation diagram and fit resulting from the data obtained from the UV-vis titration of L1 vs Eu(CF3SO3)3


ESI.10: Speciation diagram and fit resulting from the data obtained from the UV-vis titration of L1 vs Tb(CF3SO3)3

ESI.11: 1H-NMR (CDCl3, 400 MHz) of L1 and L2 and Mass-spectrum obtained in ESMS for L2

N

HN

O

HN

OOO

O O

O O

a

b

c

d

ef

g

a

b,c d

f

g e

N

HN

O

OO

OHN

OO

OO a

b

c

d

ef

gHcis

Htrans

e

f

g a

d b

c

H

(ppm)%

504.2316%

505.2350%

506.2350%

m/z%

3%4%5%6%7%8%9%

500% 505% 510%

100%

50%

0%

%%


ESI.12: 1H-NMR (MeOD-D4, 400 MHz) of Cat•L23

ESI.13: MALDI-ToF (DCTB matrix) Mass-Spectrum of the Cat•L23 compound resulting from an inter-ligand RCM (inset: calculated spectra for Cat•L23 + Na+ and Cat•L23 + K+)

(ppm) 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0 6.5 7.0 7.5 8.0 8.5

+Na+

+K+

0"

50"

100"

1466,717"

1467,7204"

1468,7237"

1469,7271"

1470,728"

%"

1466 1468 1470 m/z"

1466.7170"

1467.7204"

1468.7237"

1469.7246"0

50

100

1482.6910"

1483.6943"

1484.6977"

1485.7010"

1486.6958"1482 1484 1486

1482.6910"

1483.6943""

1484.6977""

1485.6924"

m/z"

%"

100"

50"

1466.7350"

1467.7489"

1482.7023"

1483.7076"

1484.7133"

1485.7191"

1632.6884"1633.6542"

1634.7094"

Matrix

1400" 1450" 1500" 1550" 1600" 1650" 1700" 1750"1350"0"

m/z"

%"


ESI.14: MALDI-ToF (DCTB matrix) Mass-Spectrum of the Cat•L23.Eu compound resulting from an intra-ligand RCM.

ESI.15: MS.MS spectra obtained for the fragment found at m/z = 1280.4 (Top) and 1761.6 (Bottom) for the [2]-Cat•L22.Eu and [3]-Cat•L23.Eu respectively during the MALDI.ToF analyses

+"CF3SO3("

+"OH("

="

+"CF3SO3("

+"OH("

="

DCTB"matrix"

0"

50"

100"

1760,6019"

1761,6052"

1762,6032"

1763,6066"

1764,6099"

1765,6133"1760" 1762" 1764" 1766"

1762.6044"

1763.6068"

1764.6085"

1760.6019"

0"

50"

100"

1" 2" 3" 4" 5" 6"1279" 1281" 1283" 1285"

"1281.3608"

"1282.3642"

1283.3675"

1279.3594""

1400" 1450" 1500" 1550" 1600" 1650" 1700" 1750"1350"1250" 1300"1200" 1800" 1850" 1900"

m/z"

100"

50"

0"

%"

1278.4253""

1280.4255""

1281.4308""

1570.6774""1571.6812""

1572.6879""1568.4463"" 1761.6686""

1759.6642"1763.6807"

+"2"CF3SO3("

+"H2O"

1910.5735""1430.3364"

+"2"CF3SO3("

+"H2O"

01-Jul-2009Christophe L (TG), CL54A02 in DCTB MSMS m/z 1280

m/z300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000 1050 1100 1150 1200 1250 1300 1350

%

0

100Q-TOF20090701JD017 153 (2.834) Cm (79:185) TOF MSMS 1280.00LD+

104332.2307

1280.5558

1278.5570

449.0727

403.0365

373.0469

474.0926607.1541

509.0796 604.27671236.5271824.2788710.2427632.2104

780.26661029.5519

982.4122884.3478

1281.5559

1284.7693

1289.8344

1291.9476

01-Jul-2009Christophe L (TG), CL54A02 in DCTB MSMS m/z 1 (triflate as ci)

m/z300 400 500 600 700 800 900 1000 1100 1200 1300 1400 1500 1600 1700 1800

%

0

100Q-TOF20090701JD016 171 (3.167) Cm (13:202) TOF MSMS 1762.00LD+

1181761.8353

1760.8015

332.2307

333.23651717.9016449.0572 631.2217

1762.8385

1762.9156

1763.8419

1763.9344

1771.0291

800# 1300#900# 1400#1000# 1200#1100#600# 700#500#400#300# 1500#

m/z#

1600# 1700# 1800#


ESI.16: Evolution of the absorption and emission spectra of L13.Eu and Cat•L23.Eu and L13.Eu upon the addition of DTPA (2×10-5 M in acetonitrile)


ESI.17: Mass-spectrum obtained after stirring a solution of L13.Eu with 1 equivalent of DTPA for 30 minutes

ESI.18: Mass-spectrum obtained after stirring a solution of Cat�L23.Eu with 1 equivalent of DTPA for 30 minutes

1280.5294)

1281.5295)

1380.4282)

1278.5175)

1570.8113)

1571.8022)

1572.8372)1566.5741)

1761.8043)

1762.8075)

1282.5686)

978.6592)

1077.5306)

1087.4609)

1105.5387)

100)

50)

0)

%)

1400) 1900)1500) 2000)1600) 1800)1700)1200) 1300)1100)1000)900) 2100)m/z)


ESI.19: Mass-spectrum (MALDI-ToF) obtained after stirring a solution of L2 with 0.3 equivalent of Eu(CF3SO3)3 for 30 minutes

ESI.20: Mass-spectrum (MALDI-ToF) obtained after stirring a solution of L2 + 0.3 Eu with 1 equivalent of DTPA for 30 minutes

L22.Eu&+&2&CF3SO3&

1411.3087(

1413.3104(

1414.3141(

1415.3130(

1416.3141(

L2.Eu&+&2&CF3SO3&

Matrix&

100(

50(

0(

%(

m/z(


self-assembly formation of mechanically interlocked [2 ... · pdf fileself-assembly formation...

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