Spectroelectrochemistry of Intrinsically Conducting Selenophene-3-Chlorothiophene Copolymers

Alakhras, Fadi

doi:10.5935/0103-5053.20150349

Fadi Alakhras ^**e-mail: falakhras@uod.edu.sa

Department of Chemistry, College of Science, University of Dammam, 31441 Dammam, Saudi Arabia

*e-mail: falakhras@uod.edu.sa

Figures (6)
Tables (3)

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Figure 1
(a) Anodic polarization curves of monomers and mixture; (b) CVs of homopolymers and copolymer; (c) CVs of copolymer at different scan rates and (d) dependence of redox currents on square root of scan rate. dE/dt = 100 mV s^-1.

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Figure 2
CVs of copolymer (100 cycles) deposited at E vs. SCE = 1.45 V in a BFEE + EE (2:1) with 10% of TFA (v/v) containing Se/ChrTh (mole ratio 1:1). dE/dt = 100 mV s^-1.

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Figure 3
Dependence of redox activity of polyselenophene, poly(3-chlorothiophene) and copolymer deposited at E vs. SCE = 1.45 V in a BFEE + EE (2:1) with 10% of TFA (v/v) containing Se/ChrTh (mole ratio 1:1) on cycle numbers.

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Figure 4
In situ UV-Vis spectra recorded at different applied potentials in a solution of acetonitrile + 0.1 mol L^-1 TBATFB of (a) PSe deposited at E vs. SCE = 1.30 V containing 0.1 mol L^-1 selenophene and (b) PChrTh deposited at E vs. SCE = 1.65 V containing 0.1 mol L^-1 3-chlorothiophene, both in BFEE + EE (2:1) with 10% of TFA (v/v).

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Figure 5
(a) Electrical conductivity of homopolymers (b) temperature dependence of electrical conductivity of as-prepared homopolymers (c) conductivity data of copolymers deposited at E vs. SCE = 1.45 and 1.60 V and (d) conductivity data of copolymers deposited at E vs. SCE = 1.45 V with different feed ratio.

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Figure 6
FTIR spectra of copolymer deposited at E vs. SCE = 1.45 V in a BFEE + EE (2:1) with 10% of TFA (v/v) containing Se/ChrTh (mole ratio 1:1) (a) as-prepared copolymer; (b) doped copolymer.

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Table 1
Peak potentials of copolymers prepared at E vs. SCE = 1.45 and 1.60 V from BFEE + EE (2:1) with 10% of TFA (v/v) solutions containing different monomer feed ratio

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Table 2
Absorption bands and band gaps of copolymers obtained from BFEE + EE (2:1, v/v) solution containing different monomer feed ratio at potentials E vs. SCE = 1.45 and 1.6 V

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Table 3
FTIR band assignments of PSe, PChrTh and a copolymer deposited at E vs. SCE = 1.45V, all figures in wavenumbers (cm^-1)

Se/ChrTh (mole ratio)	E_pol = 1.45 V		E_pol = 1.60 V
Se/ChrTh (mole ratio)	E_pa / V	E_pc / V	E_pa / V	E_pc / V
1:1	1.11	1.06	1.19	1.15
5:1	1.01	0.93	1.08	0.99
1:5	1.25	1.18	1.30	1.24

Se/ChrTh (mole ratio)	Polymerization potential	λ_{1 max}		λ_{2 max}		Band gap
Se/ChrTh (mole ratio)	Polymerization potential	nm	eV	nm	eV	nm	eV
1:1	1.45	488	2.54	800	1.55	617	2.01
1:1	1.6	472	2.63	782	1.59	598	2.07
5:1	1.45	505	2.45	807	1.54	636	1.95
5:1	1.6	493	2.51	790	1.57	614	2.02
1:5	1.45	470	2.64	795	1.56	605	2.05
1:5	1.6	452	2.74	772	1.61	588	2.11

Mode	PSe / cm^-1	PChrTh / cm^-1	As-prepared copolymer / cm^-1	Doped copolymer / cm^-1
ν^a a ν= stretching; (C=C)_ring	1400-1600	1450-1530	1430-1570	1390-1545
ν (C–C)_ring	1290	1350	1325	1290
δ^b b Δ = in-plane deformation; (C–H)	1020-1085	1070-1150	1082-1150	1060-1115
γ^c c γ = out-of-plane deformation. (C–H)	700-820	660-750	750-987	730-945
ν (C–Cl)	–	620	650	635
γ (Ring)	544	565	460-540	440-525

[1] *e-mail: falakhras@uod.edu.sa

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Spectroelectrochemistry of Intrinsically Conducting Selenophene-3-Chlorothiophene Copolymers