Polythiophene 3-alkyl

Polythiophenes with substituents other than alkyl groups at the 3 position have been prepared by the polymerization of substituted monomers. Many of these polymers have been substituted alkylthiophenes (8) where example side chains are (R =) —(86—89), —OCH (68), —NHC(0) (CH2) qCH (6 )) —0502(0112)30112 (90). Ohiral side chains have also been employed (91,92). Poly(3-alkoxythiophenes) (9) (93—95) and... 

Polythiophene [78] is a promising material for certain future electronic applications, due to its relatively high stability and processability in the substituted form [79-81]. Upon substitution, with e.g. alkyl side-chains [79, 80], polythiophene exhibit properties such as solvalochromism [82] and thermochromism [83]. Presently, a large variety of substituted polythiophenes with various band gaps exists (for example see Ref. [81 ]). 

M. Pomerantz, H. Yang, and Y. Cheng, Poly(alkyl thiophene-3-carboxylates). Synthesis and characterization of polythiophenes with a carbonyl group directly attached to the ring, Macromolecules, 28 5706-5708, 1995. 

R.E. Gill, G.G. Malliaras, J. Wildeman, and G. Hadziioannou, Tuning of photo- and electroluminescence in alkylated polythiophenes with well-defined regioregularity, Adv. Mater., 6 132-135, 1994. 

M. Berggren, G. Gustaffson, O. Inganas, M.R. Andersson, O. Wennerstrom, and T. Hjertberg, Thermal control of near-infrared and visible electroluminescence in alkyl-phenyl substituted polythiophenes, Appl. Phys. Lett., 65 1489-1491, 1994. 

Whereas in solution the photoluminescence efficiency (Of) of poly(3-alkylthiophenes) (PATs) is 3(Mf)%, it drastically drops to 1-4% and lower in the solid state due to the increased contribution of nonradiative decay via interchain interactions and ISC caused by the heavy-atom effect of sulfur (97MM4608). Optoelectronic devices of this type of compounds have been studied (98SCI(280)1741 06SM(156)1241). Fibers of poly(3-hex-ylthiophene) for photovoltaic applications have been described (07MI1377). Poly(3-octylthiophene) showed a TTA band at 800 nm (96JPC15309). The photophysical properties of some alkyl and aryl polythiophenes have been studied (03JCP(118)1550). The absorption maximum of poly(3-octylthiophene) is at 438 nm, while the fluorescence was... 

Thiophene polymers, in particular, alkyl-substituted polythiophenes (PTH), are some of the conducting polymers being most actively investigated at present. This fact is attributable to their high degree of processability, environmental stability [49, 50] and, in some cases, ability to exhibit reversible electrochrom-ism [51] and thermochromism [52]. Another important family of sulfur-... 

Polythiophene (PT) is attractive in that it is stable in air, and when some of the hydrogens are substituted by alkyl or phenyl groups, it is soluble in most organic solvents <1986SM(15)169>. 

The reversible thermochromic effect observed here and in the solid state is associated with enhanced order of the alkyl side chains with decreasing temperature, facilitating coplanar conformers in the polythiophene backbones, with the attendant enhancement in the 7t-7t -transition of the thiophene ring electronic absorption spectra and improvement in electronic conduction of the doped film. 

Order-disorder, or rod-to-coil , transitions in dilute solution have been reported for polydiacetylenes (2, 5-11), polysilylenes (12-15), and alkyl-substituted polythiophenes (16). The interpretation of the experimental observations has been the subject of considerable controversy with respect to whether the observations represent a single-polymer-molecule phenomenon or a many-chain aggregation or precipitation process (3-16). Our own experimental evidence (12, 13) and that of others (5-8, 10, 16) weigh heavily in favor of the single-chain interpretation. In our theoretical interpretation, we will assume that the order-disorder transitions observed in dilute pol-ysilylene solutions represent equilibrium, single-chain phenomena. 

Polythiophene randomly grafted with alkyl and aniline tetramer groups (157) was synthesized. The tetramer was chosen because it is the minimum oligomer size that mimics the electrochemical behavior of polyaniline, which shows semiconduction and conduction behavior depending on its state of oxidation and the pH. Transition from one structure to the other is illustrated in equation 23, where the electron mobility of quinonoid states (158) rearranging to isolated free radicals (159) is precluded after reduction to 160. A correlation was found between the electrochemical behavior and the UVV-NIR spectra of the 157 polymers255. 

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