Electrically conductive and fluorescent poly[1,4-bis(3-alkyl-2- thienyl)phenylenes]: syntheses and preliminary characterization aspects

doi:10.1016/S0379-6779(98)80019-2

Synthetic Metals

Volume 92, Issue 1, 15 January 1998, Pages 33-37

https://doi.org/10.1016/S0379-6779(98)80019-2 Get rights and content

Abstract

A series of polymers containing alternating phenylene and symmetrically substituted bithiophene repeat units have been synthesized and characterized using UV-Vis absorption spectroscopy, fluorescence emission spectroscopy, conductivity measurement and thermal analyses. The results reveal that the polymers have a bandgap energy of 2.5 eV and a fluorescence quantum yield of up to 26% with respect to quinine sulfate. The polymers show a maximum conductivity of 0.2 S cm⁻¹ upon doping with I₂ and display good thermal stability in both neutral and doped states. The influence of alkyl chain size on conductivity, spectral behavior and thermal stability is discussed.

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Quartz glass substrates (Herasil® 102, Heraeus Quarzglas) were cleaned with Neodisher® detergent (Miele) and sonication, then rinsed with water, isopropyl alcohol, and, finally, chloroform. Compounds (A)–(C) were synthesized according to the standard procedure previously reported in Ref. [25,26]. For the synthesis of the tetra-fluorinated “in” alkylated compound (D), magnesium and a catalytic amount of iodine were stirred with anhydrous THF at reflux.
Despite the general rule of strong acceptor substituents having a tendency to quench fluorescence due to molecular stacking, it is shown how tetra-fluorination of the central phenylene unit of para-bis(2-thienyl)phenylene can augment the quantum yields of solid state fluorescent dyes. Another significant part of the present research was the study of the influence of the position of the solubilization alkyl chains position on the fluorescent properties of the abovementioned non- and tetra-fluorinated materials. Tenfold augmentation of quantum yields, depending on the position of the alkyl chains is reported.
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Placing phenyl between two thiophenes may allow the fine tuning of the optical band gap and retain the easy connectivity and good optics of thiophenes [17]. Most of researches about these polymers are focused on their conducting, electroluminescent and photoluminescent properties and their potential application in electronic and electro-optic devices [18,19]. Recently, the electrochromic properties of this kind of polymers have been investigated.
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By changing the steric effect of substituents, the polymer emission was tuned from greenish-yellow to pure green. In solution, all the polymers depict the same absorption maxima at 398 nm in the UV/Vis spectra and the same fluorescence emission maxima at about 494 nm despite the thiophene moieties being substituted by alkyl groups of different chain lengths (98SM(92)33). However, film samples show a bathochromic shift (i.e., increasing Stokes shift) in the emission maxima on going from 563 to 565 with the increasing alkyl chain length, an effect tentatively attributed to increasing vibrational disorder in the latter polymer with consequently accentuated nonradiative loss.
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ArticleElectrically conductive and fluorescent poly[1,4-bis(3-alkyl-2- thienyl)phenylenes]: syntheses and preliminary characterization aspects

Abstract

Synth. Met.

Polymer

Synth. Met.

Tetrahedron Lett.

Synth. Met.

Synth. Met.

Chem. Phys. Lett.

Synth. Met.

Synth. Met.

Synth. Met.

Synth. Met.

Synth. Met.

Makromol. Chem.

Article
Electrically conductive and fluorescent poly[1,4-bis(3-alkyl-2- thienyl)phenylenes]: syntheses and preliminary characterization aspects