Synthesis of ferrocenecarbonyl chloride - Springer …10.1007... · Web viewSynthesis of soluble ferrocene-based polythiophenes and their properties Contents Synthesis of ferrocenecarbonyl

Supporting Information

Synthesis of soluble ferrocene-based polythiophenes and their properties

ContentsSynthesis of ferrocenecarbonyl chloride.........................................................................S1

Synthesis of 2-(thiophen-3-yl) ethyl ferrocenoate (TEF)...............................................S3

Synthesis of 2-(thiophen-3-yl) methyl ferrocenoate (TMF)...........................................S3

Polymerization of 3-ethanolthiophene (3ET).................................................................S4

Polymerization of TEF....................................................................................................S6

Polymerization of TMF...................................................................................................S7

Polymerization of 3-hexylthiophene (3HT)....................................................................S8

Copolymerization of 3TE and 3HT................................................................................S9

Copolymerization of TEF and 3HT..............................................................................S10

Copolymerization of TMF and 3HT.............................................................................S11

Synthesis of ferrocenecarbonyl chloride

The ferrocenecarbonyl chloride was synthesized by using two different chlorinating agents

as shown in Scheme S1. The details are given as follow.

First method

In the first method oxylyl chloride was used as chlorinating agent [1]. In a typical

procedure vacuum dried 10 g (43.47 mmol) ferrocenecarboxylic acid, 150 ml freshly dried

dichloro methane (DCM), and 100 drops of pyridine (dried over molecular sieves) were

added to pre-baked three necked flask. Then 12.5 ml (143 mmol) oxylyl chloride was

added to the reaction mixture slowly. The reaction mixture was refluxed for 16 hours

under argon atmosphere and then extra oxylyl chloride and solvent were evaporated under

vacuum. Then petroleum ether (dried over A4 molecular sieves) was added to the crude

mixture and refluxed for half an hour. Petroleum ether with dissolved product was filtered

using cannula into another pre-weighed and pre-backed round bottom flask. Petroleum S1

ether was evaporated and product was weighed (55.5% yield) and kept under positive

pressure of dry argon until used for next reaction.

Scheme S1: Schematic illustration of synthesis of TEF and TMF.

Second method

The second method was executed using thionyl chloride as chlorinating agent, DCM as

solvent, and TEA as catalyst [2]. In the typical procedure a pre-baked three necked round

bottomed flask was filled with 6.90 g (30mmol) ferrocenecarboxylic acid, and 2.6 ml (35

mmol) thionyl chloride mixed with 18.5 ml freshly dried DCM under argon atmosphere.

Whole mixture was stirred for 10 minutes. In another round bottom flask, after purging

with nitrogen, 8.3 ml TEA and 10 ml DCM (freshly dried) were mixed. The mixture of

TEA and DCM was added to the previously prepared mixture in three necked flask very

slowly drop by drop with vigorous stirring. The whole reaction mixture was stirred at 0°C

for 2 hours and for half an hour at room temperature. Extra solvent and thionyl chloride

was evaporated under vacuum. Then diethyl ether was added to the crude mixture and

refluxed for half an hour. Diethyl ether with dissolved product was filtered using cannula

into a round bottom flask. Diethyl ether was evaporated leaving behind pure product. As

the product was highly reactive and sensitive to moisture, so it was used immediately for

next reaction or otherwise kept in argon atmosphere.

S2

Synthesis of 2-(thiophen-3-yl) ethyl ferrocenoate (TEF)

Ferrocene carbonyl chloride (4.528g, 18.22mmol) and 3-thiopheneethanol (3TE) (2.3454

g, 18.22mmol) were dissolved in freshly dried DCM (20 ml) under argon atmosphere in a

pre-baked round bottom flask. Then pyridine (1.62 ml, 20.12mmol) was added under

stirring. The whole system was refluxed for 30 hours at 40°C and then the reaction

mixture was quenched with deionized water (15 ml) followed by washing with 5% sod.

carbonate solution (30 ml x 2), and finally washed with water (20 ml x 2). The organic

layer was dried with MgSO4 (anhydrous) over night, filtered and solvent was evaporated.

The product was further dried in vacuum oven at 40°C [3].

Table S1: Details of the synthesis of TEF.Ferrocene carbonyl

chloride (A)3-thiopheneethanol

(B)Mol

e ratio

Time

Temperature

g mmol mol/L g mmol

mol/L

A:B hours

°C

4.528

18.22 1.08 2.3454

18.22

1.129 1:1 30 40

Synthesis of 2-(thiophen-3-yl) methyl ferrocenoate (TMF)

Ferrocene carbonyl chloride (5.8577g, 23.57 mmol) and 3-thiophene methanol (2.2970 g,

20.12mmol) were dissolved in freshly dried DCM (20 ml) under argon atmosphere. Then

pyridine (1.62 ml, 20.12mmol) was added during stirring. The whole system was refluxed

for 30 hours at 40°C and the resulting reaction mixture was quenched with deionized

water (15 ml) followed by washing with 5% sod. carbonate solution (30 ml x 2) and water

(20 ml x 2). The organic layer was dried with MgSO4 over night. Solvent was evaporated,

and the product was dried in vacuum oven at 40°C [3].

S3

Figure S1: 1H-NMR spectrum of TEF.

Table S 2: Details of the synthesis of TMF.Ferrocene carbonyl

chloride (A)3-Thiophenemethanol

(B)Mole ratio

Time

Temperature

g mmol mol/L g mmol

mol/L

A:B hours

°C

5.8577

23.57 1.17 2.297 20.12 1.129 1:1 30 40

Polymerization of 3-ethanolthiophene (3ET)

All the polymerization reactions were carried out at room temperature (25°C). 3ET was

polymerized according to the reported procedure [4, 5] with little modifications. In a

reaction flask, anhydrous FeCl3 (3.244 g, 20 mmol) was taken and dried under vacuum at

100 °C. After drying 150 ml of dried CHCl3 was added and the mixture was stirred for 10

minutes under argon atmosphere. Then a solution of 3ET (0.64095 g, 5 mmol) in 50 ml

CHCl3 was slowly added to the mixture of FeCl3 and CHCl3. The resulting whole mixture

was stirred for 8 hours, concentrated, precipitated in methanol, and filtered. The residues

were added to CHCl3 and refluxed with ammonia solution for one hour. The organic layer

was separated and washed with ammonia solution and 0.5 M EDTA solution. Finally the

S4

organic layer was washed with distilled water. The solvent was evaporated and product

was dried under vacuum.

Figure S2: 1H-NMR spectrum of TMF.

S5

Scheme S2: Polymerization of 3ET, TEF, TMF, and 3HT.

Polymerization of TEF

TEF was polymerized according to the reported procedure [4, 5] with little modifications.

FeCl3 (0.9504 g, 5.8 mmol) was taken in reaction flask and dried under vacuum at 100 °C.

After cooling down in argon atmosphere 60 ml of dried CHCl3 was added. The mixture

was stirred for 10 minutes and then TEF (1.000 g, 2.930 mmol) (dissolved in 30 ml of

dried CHCl3) was added slowly. The whole mixture was stirred for 8 hours, concentrated,

precipitated in methanol, and filtered. The residues were added to CHCl3 and resulting

mixture was refluxed with ammonia solution for one hour. The organic layer was

separated and washed with ammonia solution and 0.5 M EDTA solution. Finally the

organic layer was washed with distilled water. The solvent was evaporated and product

was dried under vacuum.

Table S3: Reaction conditions of polymerization of 3ET.3ET (A) FeCl3 Anhydrous (B) Mole

ratioTime Temperature

g mmol mol/L g mmol mol/L A:B hours °C0.6409 5 0.025 3.244 20 0.1 1:4 8 25

S6

Figure S3: 1H-NMR spectrum of P3ET.

Table S4: Reaction conditions of polymerization of TEF.TEF (A) FeCl3 Anhydrous (B) Mole

ratioTime Temperature

g mmol

mol/L g mmol mol/L A:B hours °C

1.0000 2.93 0.05 0.9504 5.8 0.2 1:4 8 25

S7

Figure S4: 1H-NMR spectrum of PTEF.

Table S5: Reaction conditions for polymerization of TMF.TMF (A) FeCl3 Anhydrous (B) Mole

ratioTime Temperature

g mmol

mol/L G mmol mol/L A:B hours °C

1.0000 3.06 0.05 0.9945 6.13 0.2 1:4 8 25

Polymerization of TMF

TMF was polymerized in the same way as TEF [4, 5]. FeCl3 (0.9945 g, 6.13 mmol) was

taken in reaction flask and dried under vacuum at 100 °C for 1 hour. After cooling down

in argon atmosphere 60 ml of dried CHCl3 was added. Then the TMF (1.000 g, 3.06

mmol) (dissolved in 30 ml of dried CHCl3) was added and the whole mixture was stirred

for 8 hours. The reaction mixture was concentrated, precipitated in methanol, and filtered.

The residues were added to CHCl3 and resultant mixture was refluxed with ammonia

solution for one hour. The organic layer was separated and washed with ammonia solution

and 0.5 M EDTA solution. Finally the organic layer was washed with distilled water. The

solvent was evaporated and product was dried under vacuum.

S8

Figure S5: 1H-NMR spectrum of PTMF.

Polymerization of 3-hexylthiophene (3HT)

3-Hexylthiophene (3HT) was polymerized by following the typical procedure [4, 5]. FeCl3

(6.4880G, 40 mmol) was taken in pre-baked reaction flask, purged with Ar gas and dried

under vacuum at 100°C with continuous stirring. Then 400 ml CHCl3 was added and

stirred for five minutes to make good suspension. Then 3HT (1.683 g, 10 mmol),

dissolved in 30 ml of dried CHCl3, was added and the whole mixture was stirred for 8

hours at room temperature. The mixture was concentrated and precipitated in methanol.

Precipitates were dissolved again in to the CHCl3 and resulting solution was refluxed with

ammonia solution for one hour. The organic layer was separated and washed with

ammonia solution and 0.5 M EDTA solution. Finally the organic layer was washed with

distilled water. The organic layer was filtered to remove the insoluble particles. The

solvent was evaporated and the product was dried in vacuum oven.

Table S6: Reaction conditions for polymerization of 3HT.3HT (A) FeCl3 Anhydrous (B) Mole ratio Time Temperature

g mmol mol/L g mmol mol/L A:B hours °C1.68

310 0.025 6.4880 40 0.1 1:4 8 25

S9

Figure S6: 1H-NMR spectrum of P3HT.

Copolymerization of 3TE and 3HT

3-Thiopheneethanol was copolymerized with the 3HT [4, 5]. In a typical procedure

anhydrous FeCl3 (6.4880 g, 40 mmol) was taken in pre-baked reaction flask and dried

under vacuum at 100 °C. After cooling down under argon atmosphere 300 ml of dried

CHCl3 was added. The mixture was stirred for 10 minutes. In another flask 3TE and 3HT

(10 mmol each) dissolved in CHCl3 (100 ml) and resulting solution was added slowly to

the FeCl3 and CHCl3 mixture. Then the resulting whole mixture was stirred for 8 hours.

The reaction mixture was concentrated, precipitated in methanol, and filtered. The

residues were added to CHCl3 and resulting mixture was refluxed with ammonia solution

for one hour. The organic layer was separated and washed with ammonia solution and 0.5

M EDTA solution. Finally the organic layer was washed with distilled water. The

dissolved product was filtered to remove the insoluble part. The solvent was evaporated to

concentrate the product and re-precipitated in methanol 2 times. The product was dried

under vacuum.

Table S7: Reaction condition for the copolymerization of 3TE with 3HT.

3TE (A) 3HT (B) FeCl3 Anhydrous (C) Mole ratio Time T

g mmol mol/L g mmol mol/L g mmol mol/L A:B:C hours °C

S10

1.2819 3.06 0.025 1.683 10 0.25 6.488 40 0.1 1:1:4 8 25

Figure S7: 1H-NMR spectrum of poly (3TE-co-3HT).Copolymerization of TEF and 3HT

TEF was also copolymerized with the 3HT [4]. In a typical procedure anhydrous FeCl3

(3.8084 g, 23.84 mmol) was taken in reaction flask and dried under vacuum at 100 °C

after cooling down in argon atmosphere 125 ml of dried CHCl3 was added. The mixture

was stirred for 10 minutes. In another flask TEF and 3HT (5.87 mmol each) were

dissolved in 125 ml of dried CHCl3 and resulting solution was slowly added to the FeCl3

and CHCl3 mixture. The whole mixture was stirred for 8 hours. The reaction mixture was

concentrated, precipitated in methanol, and filtered. The residues were added to CHCl3

and resulting mixture was refluxed with ammonia solution for one hour. The organic layer

was separated and washed again with ammonia solution and 0.5 M EDTA solution.

Finally the organic layer was washed with distilled water. The dissolved product was

filtered to remove the insoluble part. The solvent was evaporated to concentrate the

product and re-precipitated in methanol 2 times. The product was dried under vacuum.

Table S8: Reaction conditions for the copolymerization of TEF with 3HT.

TEF (A) 3HT (B) FeCl3 Anhydrous (C) Mole ratio Time T

g mmol mol/L g mmol mol/L g mmol mol/L A:B:C hours °C

2 5.87 0.025 0.9879 5.87 0.25 3.8084 23.84 0.1 1:1:4 8 25

S11

Copolymerization of TMF and 3HT

TMF was copolymerized with the 3HT in the same way as the TEF was [4]. In a typical

procedure anhydrous FeCl3 (1.9853 g, 12.24 mmol) was taken in reaction flask and dried

under vacuum at 100 °C. After cooling down in argon atmosphere 64 ml of dried CHCl3

was added. The mixture was stirred for 10 minutes. In another flask TMF and 3HT (3.06

mmol each) were dissolved in 60 ml of dried CHCl3 and the resulting solution was slowly

added to the FeCl3 and CHCl3 mixture. The whole mixture was stirred for 8 hours. The

reaction mixture was concentrated, precipitated in methanol, and filtered. The residues

were added to CHCl3 and resulting mixture was refluxed with ammonia solution for one

hour. The organic layer was separated and washed with ammonia solution and 0.5 M

EDTA solution. Finally the organic layer was washed with distilled water. Dissolved

product was filtered to remove the insoluble part. The solvent was evaporated to

concentrate the product and re-precipitated in methanol 2 times. The product was dried

under vacuum.

Table S9: Reaction conditions forcopolymerization of TMF with 3HT.

TMF (A) 3HT (B) FeCl3 Anhydrous (C) Mole ratio Time T

g mmol mol/L g mmol mol/L g mmol mol/L A:B:C hours °C

1 3.06 0.025 0.5149 3.06 0.025 1.9853 12.24 0.1 1:1:4 6 25

Figure S 8: 1H-NMR spectrum of poly (TMF-co-3HT).

S12

Figure S9: Possible ways of electron transfer between electrode and a) 3HT, b) TEF, and c) poly (TEF-co-3HT) respectively.

References:

[1] Q. Tan, L. Wang, L. Ma, H. Yu, J. Ding, Q. Liu, A. Xiao, G. Ren, J. Phys. Chem. B, 112 (2008) 11171-11176.[2] M.S. Khan, A. Nigar, M. Bashir, Z. Akhter, Synth. Commun., 37 (2007) 473-482.[3] C.L. Ferreira, C.B. Ewart, C.A. Barta, S. Little, V. Yardley, C. Martins, E. Polishchuk, P.J. Smith, J.R. Moss, M. Merkel, M.J. Adam, C. Orvig, Inorg. Chem., 45 (2006) 8414-8422.[4] Y. Zhu, Y. Dan, Sol. Energy Mater. Sol. Cells., 94 (2010) 1658-1664.[5] M.R. Andersson, D. Selse, M. Berggren, H. Jaervinen, T. Hjertberg, O. Inganaes, O. Wennerstroem, J.E. Oesterholm, Macromolecules, 27 (1994) 6503-6506.

S13