Thienyl polymer

H. Sarker, Y. Gofer, J. G. Killian, T. O. Poehler and P. C. Searson, Synthesis and characterization of a series of fluorine-substituted phenylene-thienyl polymers for battery applications, Synth. Met., 97, 1—6 (1998). 

As well as phenyl derivatives, other products have been prepared by hydrolysis of alkoxysilanes such as cyclohexenyl or naphthyl derivatives as well as heterocyclic compounds based on thienyl rings (Table 31, entries 28-33). Few practical applications have been reported for this type of compound, except for the styryl compound T81C6H4-A-CFI = CH2]s, and the fluorinated TslCeFsJs which have been used in polymer blending (Table 31, entries 13 and 28). ... 

The synthesis of luminescent organoboron quinolate polymers (21) (Fig. 15) via a three-step procedure starting from a silylated polystyrene has been communicated. The synthesis was initiated by the highly selective borylation of poly (4-trimethylsilylstyrene) (PS-Si), followed by the replacement of the bromine substituents in poly(4-dibromoborylstyrene) (PS-BBr) with substituted thienyl groups (R = H, 3-hexyl, 5-hexyl). In the final step, the 8-hydroxyquinolato moiety was introduced. The hexyl-substituted polymers efficiently emitted light at 513-514nm upon excitation at 395 nm.40... 

Zhang Y, Murphy CB, Jones WE Jr (2002) Poly[p-(phenyleneethynylene)-alt-(thienyle-neethynylene)] polymers with oligopyridine pendant groups highly sensitive chemosensors for transition metal ions. Macromolecules 35 630-636... 

Fig. 1 Building units of conducting polymers, (1) polyacetylene (PA) (2) polypyrrole (PPy), polythiophene (PTh), polyfurane (PFu) (3) polyphenylene (PP) (4) polyaniline (PANI) 5 polyindole (PIND) (6) polycarbazole (PCaz) (7) polyazulene (Paz) (8) polynaphthalene (PNa) (9) polyanthracene (PAnth) (10) polypyrene (PPyr) (11) polyfluorene (PFiu) (12) poly(isothionaphthalene) (PITN) (13) poly(dithienothiophene) (14) poly(thienopyrrole) (15) poly(dithienylbenzene) (1G) poly(3-alkylthiophene) (17) poly(phenylene vinylene) (18) poly(bipyrrole) (PBPy), poly(bithiophene) (PBT) (19) poly(phenylenesulfide) (20) 4-poly(thienothiophene) (21) poly(thienyl vinylene), poly(furane vinylene) (22) poly(ethylenedioxythiophene) (PEDOT).

The preparation of bis(thienyl)furans of type 33 and 34 has been descibed. These compounds have been proposed as suitable precursors for electroactive molecular species and conducting polymers <99JOC6418>. 

Hessen and co-workers discovered that the reaction of ethylene with [Cp 2La(C4H3S)]2 (prepared from [Cp 2LaH]2 and thiophene) in the presence of thiophene formed thienyl-capped PE, H(CH2CH2)42-C4H3S) (e.g., 80 °C, ethylene 7.5 atm, activity = 27 g-polymer mmol-La h , 4/ =1300, PDI = 1.4). They revealed that C-H activation of thiophene was the only chain-transfer mechanism that is in operation, and that all of the PE chains produced under the conditions they examined were capped on one side by a thienyl group. 

Several such polymers have shown electrochromic behavior, among them poly(n-vinylcarbazole) [73] which switches from colorless in the neutral state to green in the doped state (Scheme 10) and poly(Ar-phenyl-2-(2 -thienyl)-5-(5"-vinyl-2"-thienyl)pyrrole) [74], which changes from yellow to reddish brown upon oxidation (Scheme 11). A study of the electrochromic properties of blends consist-... 

Our group has recently become interested in these novel systems from an elec-trochromic and sensor standpoint. Our polymers are centered around bis(sali-cylidene)thienyl cores that can undergo site-directed electro-polymerization to... 

The vinyl functionality attached to the 3-position of the thienyl ring should be an excellent candidate for radical-induced cross-linking of these systems since poly thiophenes are relatively inert to free radicals (95MM4608). Two different synthetic routes were used to achieve the target polymers. One of the routes leads to polymers which adhere very strongly to polar substrates. The photoluminescence properties of some of these compounds have been studied (95SM(69)377). 

Exposure of the monomer MET to ambient lighting produced a gumlike polymer, poly[(3-thienyl)ethyl methacrylate] (Scheme 28). 

Some other 3-thienyl ether derivatives have been prepared. Poly[3-oligo(oxyethylene)-4-methyltiophene] showed an absorption peak at 550 nm (95JCS(CC)2293). On the other hand, poly[3-(N-succinimido(tetra-ethoxy)oxy)-4-methylthiophene] was prepared and it is able to react with amines to give the corresponding carbamate with a 15-crown-5 attached substructure. This polymer showed absorption at 429 nm and fluorescence at 543 nm (04T11169). 

Di(2-thienyl)thieno[3,4-c][l,2,5]thiadiazole (178) has been polymerized to give a narrow band gap heterocyclic polymer with interesting optical and electrochemical properties <93SM1251>. Stable dithiazolyl radicals, such as (18) and (19), are useful as inhibitors and stabilizers for radical reactions <82EGP156366>. 

Synthesis of 2-[5-(l//-pyrrol-2-yl)-2-thienyl]-l//-pyrrole 1355, monomer for polyconjugated polymers, is based on the reaction of l,4-di(l//-pyrrol-2-yl)-l,4-butanedione 1354 with Lawesson s reagent (Equation 292) <1997CM2876>. Compound 1356 was prepared by Triton B-catalyzed condensation of 17/-pyrrole-2-carbaldehyde and the appropriate nitrile derivative (Equation 293). 

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