Dithieno pyrroles

Poly(iV-substituted dithieno[3,2-3 2, 3 -rf pyrroles (PDTPs) 167a,b) <2005MM4545>, a class of soluble (chiral) conjugated polymers with a stable oxidized state, were prepared by an oxidative coupling by FeClj in chloroform under an argon atmosphere. The crude material was reduced with hydrazine to afford compound 167 (Scheme 19) <2005MM4545>. 

Af-Functionalized dithieno[3,Z-b Z, 3 - pyrrole (DTP) 23 analogues have been synthesized from 3-bromothiophene 298 <2003JOC2921>. 3-Bromothiophene 298 which reacts with amines in the presence of NaO Bu to give a mixture of alkyl... 

A new class of photochromic diarylethenes containing thieno[3,2-b] thiophenes, dithieno[3,2-b 2, 3 -d]thiophene (08CC5203), and dithieno [3,2-fc 2, 3 -d]pyrroles (09CEJ10005) with photoswitchable luminescence properties were synthesized by Suzuki cross-coupling reactions (Scheme 48). 

The synthesis, characterization, electrical conductivity, and field effect mobility of a series of novel soluble N-alkyl dithieno[3,2-b 2, 3 -d]pyrrole (DTP) and thiophene (TH)-based copolymers (DTP-co-THs) were reported (06MM1771 08JA13167). The incorporation of DTP units extends n conjugation, and the introduction of thiophene subunits imparts good solubility, high conductivity, and high charge carrier mobility. Therefore, the incorporation of DTP units and various substituted thiophenes into the polymer backbone affords the ability to enhance the solubility, lower the band gap, and achieve the enhanced electronic properties. 

Thermal decomposition of 3-azido-2,2 -bithienyl (284) and 3-azido-2,3 -bithienyl (285) gave 4H-dithieno[3,2-Z> 2, 3 -d]pyrrole (286) and 4//-dithieno[2,3-Z> 2, 3 -Other isomers gave polymers or intractable materials <83JCS(P1)2551>. 

Fig. 10.24 Structures of polymers absorbing beyond 600 nm (a) poly(dithieno(3,4-b 2, 3 -d)thiophene), (b) tbiophene/isothianaphthalene copolymers, and (c) a thienyl-pyrrole/benzothiazole copolymer.

Dithieno[3,2-6 2, 3 -(/]pyrrole-based materials Synthesis and appHcation to organic electronics 13PPS1773. 

K. Ogawa and S. C. Rasmussen, N-functionalized poly(dithieno[3,2-b 2, 3 - ]pyrrole)s highly fluorescent materials with reduced bandgaps. Macromolecules, 39, 1771-1778 (2006). 

Example 12 Stille Crosscoupling of Thieno 3,4 c)pyrrole-4,6-[Pg.430]

Bistrimethylstannyl-4,4 -bis-(2-ethylhexyl)-dithieno[3,2-b 2, 3 -d]germole 22 (0.881 mmol, 695mg), l,3-dibromo-5-octyl-4/f-thieno[3,4-c]pyrrole-... 

Horie and coworkers used phosphine-free conditions in NMP to couple 4,4-bis(2-alkyl)-4//-eyelopenta[2,l-ft 3,4-fc ]dithiophene (CPDT), A -(l-alkyl)dithieno[3,2-b 2, 3 -fi(]pyrrole and 4,4 -bis(2-alkyl)dithieno[3,2- ) 2, 3 -t/]-silole with dibrominated (hetero)arenes to give polymers 19-23 (Chart 19.5). Polymers with high molecular weights were only achieved for 19 (M = 72 kDa, PDI = 4.5) due to side reactions and insolubiUty of the other polymers. ... 

Chu TY, Lu J, Beaupre S, Zhang Y, Pouliot JR, Wakim S, Zhou J, Leclerc M, Li Z, Ding J, Tao Y (2011) Bulk heterojunction solar cells using thieno[3,4-c]pyrrole-4,6-dione and dithieno [3,2-b 2,3-d]silole copolymer with a power conversion efficiency of 7.3%. J Am Chem Soc 133 4250 253... 

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