The synthesis of dicyanooligothiophenes NC(C4H2S)nCN (n = 3−6) is reported. For n 3, 4, and 5 the dinitriles are generated by treatment corresponding dibromo compounds with copper(I) cyanide in quinoline. 6 preparation involves Ni-catalyzed coupling 5-bromo-2,2':5',2''-terthiophene-5''-carbonitrile. structures all four dicyano derivatives have been determined X-ray crystallography. space group monoclinic C2/c, a 18.363(7), b 11.8356(9), c 30.666(4) Å, β 102.15(2)°, V 6515(3) Å3, Z 20. 4...

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTMolecular conductors from neutral-radical charge-transfer salts: preparation and characterization of an I doped hexagonal phase 1,2,3,5-dithiadiazolyl ([HCN2S2].bul.)C. D. Bryan, A. W. Cordes, R. C. Haddon, G. Hicks, K. Kennepohl, MacKinnon, T. Oakley, M. Palstra, S. Perel, et al..Cite this: J. Am. Chem. Soc. 1994, 116, 4, 1205–1210Publication Date (Print):February 1, 1994Publication History Published online1 May 2002Published inissue 1 February...

Condensation of oxamidrazone with sulfur dichloride in acetonitrile affords 4,4'-bis(1,2,3,5-dithiadiazolium) moderate yield. Reduction this salt triphenylantimony yields the diradical 4,4'-bis(1,2,3,5-dithiadiazolyl) [S2N2C−CN2S2], which has been isolated and characterized solid state as its dimer [S2N2C−CN2S2]2. The is disjoint, ab initio molecular orbital methods confirm a very small energy gap (<0.5 kcal/mol) between triplet singlet states, regardless torsion angle about central C−C...

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTCharge Transfer Salts of Benzene-Bridged 1,2,3,5-Dithiadiazolyl Diradicals. Preparation, Structures, and Transport Properties 1,3- 1,4-[(S2N2C)C6H4(CN2S2)][X] (X = I, Br)C. D. Bryan, A. W. Cordes, R. M. Fleming, N. George, S. H. Glarum, C. Haddon, MacKinnon, T. Oakley, Palstra, PerelCite this: J. Am. Chem. Soc. 1995, 117, 26, 6880–6888Publication Date (Print):July 1, 1995Publication History Published online1 May 2002Published inissue 1 July...

The green generation of X + (X = Br, I) using hydrogen peroxide in aqueous acetic acid allows access to aromatic heterocyclic halides yields and purities comparable syntheses employing N-bromosuccinimide. In activated unsubstituted thiophene rings, regioselectivity is quantitative for positions α the sulfur; pyrroles also give reactions, at least initially. Deactivated including furans thiazoles, as well thiophenes with strongly electron-withdrawing groups showed little no reactivity under...

The preparation of the bis(1,2,3,5-dithiadiazolyl) radicals [S2N2C]−X−[CN2S2], where X is a heterocyclic bridging group (X = piperazine, thiophene, bithiophene) described. Crystal structures piperazine- and bithiophene-bridged diradicals have been determined by single-crystal X-ray diffraction. two compounds are isostructural, belonging to monoclinic space P21/n; for piperazine derivative 5.9913(6) Å, b 19.1958(16) c 9.1244(6) β 100.314(7)°, Z 4. For bithiophene 5.9907(17) 24.272(3)...

A new method of brominating aromatic and heteroaromatic ring systems is investigated. The combination hydrobromic acid as the halogen source, hydrogen peroxide oxidant, ethanol, water, or no solvent are evaluated greener conditions than those that have been previously published. give high yields good regioselectivity for a variety substrates when activated by electron-donating groups heteroatoms. Phenols, anisole, thiophenes, pyrrole comparable superior results compared to traditional...

A new synthetic route to mononitrated oligothiophenes is described, as well the preparation of halogenated derivatives (Br, I) thereof. An unusual deep red colour observed and explained, with aid DFT calculations, arising from a significant quinoidal contribution molecular structure. The crystal structures two compounds, H(C 4 H 2 S) 3 NO Br(C , are presented. Both compounds have planar sheets held together by intermolecular short contacts (hydrogen bonds and, for latter, ···Br...

Thiol mimics are molecules that less chemically reactive than thiols but also attach to a metal surface through metal–thiolate bond; thus, they give an alternative method of attaching organic semiconductors surface. The synthesis and molecular characterization substituted bithiophenes terthiophenes containing at least one thionitrile substituent (a "protected thiol") presented. Photoluminescence spectroscopy shows the nitrile groups not in conjugation with oligothiophene core. Single-crystal...

The two ligands 3,3′-dicyanobiphenyl (3) and 5,5′-dicyano-2,2′-bithiophene (4) are geometrically similar but give rise to different coordination compounds when reacted with silver(I) salts. crystal structures of 3·AgClO4 3·AgBF4 have 1 : ligand cation ratios, while 42·ClO4 42·BF4 2 ratios. These ratios for the solid-state materials were constant, even stoichiometric used in reaction vessels. these four presented reasons difference environments discussed reference IR spectroscopic DFT...

Reactions of the ligand 5,5′-dicyano-2,2′-bithiophene (T2CN2) with a variety silver(I) salts are presented. In most cases, precipitates by itself without incorporating metal. However, when counterion is triflate, in benzene or THF, coordination compound formed. The crystal structure species grown from benzene, double-stranded one-dimensional polymer, reported. this structure, bithiophene twisted into uncommon syn orientation. reasons for lack reactivity discussed comparing relative strengths...

Electroreduction of 1,3- and 1,4-benzene-bridged bis(diselenadiazolium) salts [1,4-Se][SbF6]2 in acetonitrile, at a Pt wire the presence iodine affords 1:1 charge-transfer [1,4-Se][I] [1,3-Se][I]. Crystals belong to monoclinic space group C2/m, with FW = 598.9, 10.586(2), b 16.713(2), c 3.5006(14) Å, β 104.26(2)°, V 600.2(3) Å3, Z 2. [1,3-Se][I] orthorhombic Ima2, 28.489(7), 3.543(2), 12.283(2) 1239.8(8) 4. In an excess iodine, electrocrystallization [1,4-Se]2+ mixed iodide/triiodide salt...

A series of oligothiophene dinitriles, containing one, two, or three rings between nitrile donors NC-(C4H2S)n-CN are reacted with silver(I) salts to form coordination compounds. In most cases, the resulting metal–organic frameworks one-dimensional polymers roughly linear divalent Ag(I) centers. However, in case bithiophene (n = 2) and terthiophene 3) bridges, a three-dimensional structure is also possible if counterion just right size fit into diamondoid pores that four-coordinate...

Two new palladium(II) catalysts, each containing a phenylthiazole ligand (2-methyl- (1a) and 2-amino-4-phenyl-1,3-thiazole (1b)), are prepared characterized. The crystal structure of one, 2-methyl-4-phenyl)palladium(II) acetate (3a), is presented; it crystallizes as dimer, with the attached through nitrogen on thiazole ortho-carbon phenyl ring. organometallic compounds can be used catalysts in Suzuki–Miyaura aryl cross-coupling reactions. They compatible wide range functional groups,...