(N-Methylthiocarbamoyl)tetrathiafulvalene derivatives and their radical cations: synthetic and X-ray structural studies

Lithiation of 4,5-bis(methylsulfanyl)-TTF 9, 4,5-(ethylenedisulfanyl)-TTF 10, 4,5-dimethyl-TTF 11 and 4,5,5'-trimethyl-TTF 12 (TTF = tetrathiafulvalene) followed by reaction with methyl isothiocyanate affords the corresponding (N-methylthio-carbamoyl)-TTF derivatives 14-17, respectively, in 54-70% yields. These new TTF derivatives display a broad intramolecular charge-transfer band in their UV-VIS spectra arising from conjugation between the donor TTF ring and the acceptor N-methylthiocarbamoyl moiety. Steric hindrance between the adjacent N-methylthiocarbamoyl and methyl substituents in 17 causes a marked hyposchromic shift in this band (lambda(max) 395 nm) compared to compounds 14-16 (lambda(max) 435-467 nm). Consistent with the electron-withdrawing properties of the N-methylthiocarbamoyl substituent, its attachment to the TTF ring raises slightly the oxidation potential of the system. Charge transfer complexes of these donors and (N-methylthiocarbamoyl)-TTF 2 with 7,7,8,8-tetracyano-p-quinodimethane (TCNQ) and salts with bromide anions are reported, some of which have high room temperature conductivity values. The X-ray crystal structures are presented for 16, 17 and the salts 2.Br, 14.TCNQ and (17)(2).20. The structure of 16 comprises orthogonal dimers (kappa packing) while in the structure of 17 individual molecules are orthogonal to each other. There is weak intermolecular hydrogen bonding in both 16 and 17. In the structure of 2.Br, the radical cations 2(+.) are almost planar and they form an infinite stair-like stack of dimers, with bromide anions situated between the stacks, and linked with the cation by a strong N-H ... Br bond. The structure of 14.TCNQ comprises mixed ...DDAADD... stacks; the N-methylthiocarbamoyl group engages in an interstack N-H ... N bond with a TCNQ anion. Analysis of the bond lengths in the structure suggests that there is partial charge transfer from 14 to TCNQ. In the structure of(17)(2).20 molecules form mixed ...DDADDA... stacks and analysis of bond lengths suggests that there is only a small degree of charge transfer from donor to acceptor. The geometries of compounds 2, 14, 16, 17 were optimised using the PM3 semi-empirical method and the results compare favourably with the X-ray structural data.