Photoinduced Electron Transfer Reactions of Highly Conjugated Thiophenes for Initiation of Cationic Polymerization and Conjugated Polymer Formation

Date

2012-10-09

Author

Aydogan, Binnur
Yağcı, Yusuf
Toppare, Levent Kamil
Jockusch, Steffen
Turro, Nicholas J.

Metadata

Show full item record

This work is licensed under a Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International License.

Item Usage Stats

128
views

0
downloads

Photoinduced electron transfer reactions of highly conjugated thiophene derivatives, 4,7-di(2,3-dihydrothieno[3,4-b] [1,4]dioxin-5-yl)benzo[1,2,5]thiadiazole (DTDT) and 5,8-bis(2,3-dihydrothieno[3,4-b][1,4]dioxin-5-yl)-2,3-di(thiophen-2-yl)quinoxaline (DTDQ), with diphenyl-iodonium hexafluorophosphate (Ph2I+PF6-) and triphenylsulfonium hexafluorophosphate (Ph3S+PF6-) were investigated by laser flash photolysis, fluorescence and phosphorescence spectroscopy, and polymerization studies. High fluorescence quantum yields, long fluorescence lifetimes (similar to 10 ns in aprotic solvents), and absence of detectable phosphorescence at 77 K for both compounds indicate inefficient intersystem crossing into the triplet state and dominant role of singlet excited state. Photolysis of DTDT or DTDQ in the presence of iodonium salt with visible light results in the formation of radical cations of DTDT and DTDQ as detected by laser flash photolysis. Sulfonium salts do not undergo such electron transfer reactions due to the unfavorable redox potentials. The importance of the described photoinduced electron transfer process with respect to the initiation of cationic polymerization and formation of conjugated polymers was demonstrated.

Subject Keywords

Photodissociation, Thiophenes, Salts, Fluorescence, Cationic polymerization

URI

https://hdl.handle.net/11511/47254

Journal

MACROMOLECULES

DOI

https://doi.org/10.1021/ma301546d

Collections

Department of Chemistry, Article

Suggestions

OpenMETU
Core

Electrochemical behaviour and electrochemical polymerization of fluoro-substituted anilines Cihaner, A; Önal, Ahmet Muhtar (2002-08-01) The electrochemical behaviour of three fluoro-substituted aniline monomers, 2-fluoroaniline (2FAN), 3-fluoroaniline (3FAN) and 4-fluoroaniline (4FAN), was investigated in aqueous acidic and organic media by means of cyclic voltammetry (CV) studies. Constant potential electrolysis (CPE) of the monomers in acetonitrile-water mixture (1: 1 by volume) using NaClO4 as supporting electrolyte yielded soluble polymers. The mechanism of electrochemical polymerization was investigated using in situ electron spin reso...
Photogalvanic effect in aqueous Methylene blue nickel mesh systems: Conversion of light into electricity Bayer, IS; Eroğlu, İnci; Turker, L (Wiley, 2001-03-10) The photogalvanic effect in electrochemical cells, employing aqueous Methylene blue and Fe(II)/Fe(III) couple electrolyte and nickel-mesh electrodes, were experimentally investigated. Five different standard H-cell configurations were set-up by modifying the electrolyte. Long-term open-circuit Voltage measurements were conducted in order to test the stability of the cells. Light on-off reproducibility experiments were also carried out during lengthy cell operations. By comparing experimental quantum yield w...
ELECTROCHEMICAL BEHAVIOR OF MOCLOBEMIDE AT MERCURY AND GLASSY CARBON ELECTRODES AND VOLTAMMETRIC METHODS FOR ITS DETERMINATION Altunöz Erdoğan, Deniz; Tasdemir, Ibrahim Hudai; Erk, Nevin; Kilic, Esma (2011-01-01) Electrochemical oxidation and reduction properties of Moclobemide (MCB) were investigated at glassy carbon electrode (GCE) and hanging mercury drop electrode (HMDE). Diffusion-adsorption behavior and some extra electrochemical parameters such as diffusion coefficient, number of transferred electrons and proton participated to its electrode mechanisms on both electrode and surface coverage coefficient were calculated from the results of cyclic voltammetry and square-wave voltammetry. Reversible catalytic hyd...
Benzyl functionalized benzotriazole containing conjugated polymers: effect of substituent position on electrochromic properties and synthesis of crown ether functionalized electrochromic polymers Yiğitsoy, Başak; Toppare, Levent Kamil; Department of Chemistry (2011) A new class of π-conjugated monomers was synthesized with combination of electron donating and electron-withdrawing heterocyclics to understand the effects of structural differences on electrochemical and optoelectronic properties of the resulting polymers. Electron deficient benzotriazole, substititued with benzyl from two available sites, coupled with stannylated electron donating groups, ethylenedioxythiophene (EDOT) and thiophene (Th), to yield four different monomers; 1-benzyl-4,7-di(thiophen-2-yl))-2H...
Immobilization of invertase in conducting copolymers of 3-methylthienyl methacrylate Çırpan, Ali; Toppare, Levent Kamil; Yagci, Y. (Elsevier BV, 2003-4) Immobilization of invertase in conducting copolymer matrices of 3-methylthienyl methacrylate with pyrrole and thiophene was achieved by constant potential electrolysis using sodium dodecyl sulfate (SDS) as the supporting electrolyte. Polythiophene (PTh) was also used in entrapment process for comparison. Kinetic parameters, Michaelis-Menten constant, Km, and the maximum reaction rate, Vmax, were investigated. Operational stability and temperature optimization of the enzyme electrodes were also examined.

Citation Formats

B. Aydogan, Y. Yağcı, L. K. Toppare, S. Jockusch, and N. J. Turro, “Photoinduced Electron Transfer Reactions of Highly Conjugated Thiophenes for Initiation of Cationic Polymerization and Conjugated Polymer Formation,” MACROMOLECULES, pp. 7829–7834, 2012, Accessed: 00, 2020. [Online]. Available: https://hdl.handle.net/11511/47254.