Dithienothiophene derivatives

The a,a-disubstituted bis(dithienothiophene)derivatives 116 (Table 2) have been deposited as active layers in organic thin-film transistors <1999SM(102)987>. 

Perylene bisimide-dithienothiophene derivatives have been prepared (09JPC(A)5039). A femtosecond transient absorption study showed the presence of two positive bands at 490 nm (perylene cation radical) and at 730 nm (perylene anion radical). 

The white emitting dithienothiophene derivative displayed good film forming properties and could be used as active material in light emitting diodes. The emissive layer was spin-coated between ITO/PEDOT PSS and LiF/Al, used as anode and cathode, respectively. The... 

Fig. 10 Dithienothiophene derivatives DTT1-DTT4 2,2-TetracMoro-ethane at 810 nm is expressed in GM... 

G. Sotgiu and G. BarbareUa, Synthesis of photostable amine-reactive fluorescent dyes by postsynthetic conversion of bromide dithienothiophene derivatives, J. Org. Chem., 72, 4925-4931 (2007). 

AYD 08] Aydogan B., Gundogan A.S., Ozturk T. et al, A dithienothiophene derivative as a long-wavelength photosensitizer for onium salt photoinitiated cationic polymerization , Macromolecules, vol. 41, no. 10, pp. 3468-3471, 2008. 

The synthesis of two a,a -disubstituted bis(dithienothiophene) (BDT) derivatives 163 and 166 for organic thin film transistors (TFT) has been performed. Substitution of dithienodithiophene 15 and subsequent oxidation with -BuLi and Fc(acac) gave the two derivatives (Scheme 18) <1999SM(102)987>. 

A 94% yield of 3,4 -dibromo-2,3 -dithienyl sulfide (184) was similarly achieved from 3-bromo-2-thienyllithium (180) and disulfide 182. Oxidative ring closure of the dilithium derivative of 184 gave dithienothiophene 8 in 29% yield [Eq. (53)]. 

There are no experimental data on the reactivity of thieno[3,4-cl-thiophene (4) except some indications of the ease of addition reactions of its alkyl- and phenyl-substituted derivatives. There are no reports of the reactions of the isomeric selenophenoselenophenes, selenopheno-thiophenes, and dithienothiophenes, except on the oxidation of the last. ... 

Intramolecular Pd-catalyzed cross-coupling of bromothiophene derivatives 423 and 425 gives dithienothiophenes 424 and 426, respectively (Equation 14) <1997TL4581>. Synthesis of benzonaphthothiophene-6,ll-diones 428 by Pd(OAc)2-mediated cyclization of 427 has been reported <2005H(65)1205>. 

The electrosynthesis of polythiophene (PT) from thiophene must be performed under extremely anhydrous conditions, quite in contrast to polypyrrole [334]. Polymerization of 3-methylthiophene and bithiophene is much less sensitive to water. The advantage of PT is a higher theoretical capacity and a very positive potential (cf. Table 7). It is for these reasons that its application as a positive electrode in rechargeable lithium batteries [335-338] and in a metal-free PPy/PT cell [339] has been considered. Derivatives such as dithienothiophene [340] or rra/is-l,2-di(2-thienyl)ethylene [341] have also been polymerized, but the polymer materials suffer from low theoretical capacities [337]. 

Amongst the derivatives of thiophene, the chemistry of thiophenium salts and S,C- and S,N-thiophenium ylids has also been reviewed <89AHC(45)151> as has the chemistry of the thiophene 1-oxides, 1,1-dioxides, and sesquioxides <85HC(44/l)572>. The chemistry of benzo[Z>]thiophenes has been reviewed by Scrowston <8iAHC(29)l7l> and there is a study by Gronowitz on the isomeric dithienothiophenes <94JHC64l>. 

The geometries, electronic structures and electronic spectra of stilbene derivatives and chromophores based on dithienothiophenes are systematically studied by AMI and INDO/CI method. On the basis of correct UV-Vis spectra, the position and strength of the two-photon absorption can be predicted (2001MI1). 

In addition to the various dithienothiophene polymers, the related thieno[3,4-h] thiophene (1) and its derivatives have received considerable attention. The first reported example was the alkyl-functionalized derivative, poly(2-decylthieno[3,4-h]thiophene) (73) reported by Pomerantz and Gu [109]. Polymer 73 was prepared by the FeCls oxidation of 2-decylthieno[3,4-l jthiophene, which was synthesized from 2-thiophenecarboxylic acid as illustrated in Scheme 12.16 [109,110]. Such methods produced a fairly high LLk material LLk = 90,000, M = 52,000, PDI =1.7) that was blue-green in color and soluble in a variety of organic solvents (CHCI3, THF, and chlorobenzene). Solvent cast films exhibited a transition at 925 nm with an onset at 1350 nm (F of 0.92 eV). FeCls-doped films gave a conductivity of 3.1 X 10 . Films doped with either I2 or NOBF4 gave lower conductivities (1.0—4.2 x 10 ). 

The coupling of thienyl-lithium derivatives with cupric chloride to yield symmetrically substituted bithienyls has during recent years been extensively used in connection with work on optically active bithienyl derivatives and in connection with the synthesis of thiophen analogues of fluorene, " and dithienothiophens. " Thus 3,3 -bithienyl and 4,4 -dibromo-3,3 -bithienyl prepared in this way were brominated to form hexabromo-3,3 -bithienyl. Halogen-metal exchange occurred selectively in the 5,5 -positions, yielding the acid (93) upon carbonation. (93) was resolved into... 

Stille coupling has been used by Li et al to synthesize the donor-acceptor co-polymer P23 consisting of dithienyl-DPP and fused thienothiophene (TT) units. OFET devices fabricated from this polymer showed a high hole mobility of 0.94 cm V s due to significant intermolecular %-% donor-acceptor interactions between TT and DPP fused heterocyclic units.Additionally, a stannyl derivative of dithienothiophene has been recently co-polymerized by Shahid et al. with bis(5-bromo-2-thiophenyl)- and bis(5-bromo-2-selenophe-nyl)-DPP comonomers. Both polymers exhibited ambipolar characteristics in OFET devices. The thiophene-based co-polymer analog showed a higher... 

A wide assortment of additional electron-transfer PSs for diaryliodonium salts have been described in the journal and patent literature. These include ketocoumarins [FOU 88], 9,10-phenanthraquinone [BAU 86], Mannich bases [DE 88b], 1,3-indanediones [TEH 13], benzoquinonylsulfanyl derivatives [SUG 03], acridinediones [SEE 01] and dimethylaminobenzylidine derivatives [ICH 87], In addition, the use of dyes such as eosine and Rhodamine [DE 88a, DE 89] have been employed to provide photosensitization in the visible region of the spectrum. A particularly interesting system devised by Yagci et al. [AYD 08] is the dithienothiophene, 48, used with diphenyliodonium hexaflurophosphate to carry out the cationic photopolymerizations of cyclohexene oxide, 3,4-epoxycyclohexylmethyl 3, 4 -epoxycyclohexane carboxylate, N-vinyl carbazole, n-butyl vinyl ether and styrene. These investigators have further applied this system to the preparation of metallic silver-filled epoxy nanocomposites [YAG 11]. 

Porphyrin derivatives reveal good photochemical and thermal stabilities due to their large 7 -conjugation systems which have been found suitable for organic photonic and electronic applications [145-147]. Porphyrin molecules have been well established to serve as potential photosensitizers in dye-sensitized solar cells. Soluble porphyrin-dithienothiophene copolymers have been synthesized using Sonogashira... 

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