Synthesis and electronic structure of dicyanofulvene-fused electron accepting molecule based on a 1,5-dihydro-s-indacene framework.

A novel dicyanofulvene dimer fused to a benzene ring (3a) has been synthesized as an electron-accepting molecule. The low-lying LUMO level was validated by measuring the ultraviolet photoelectron spectroscopy and electronic spectra. Cyclic voltammetry exhibited sequential reversible waves from 3a to 3a(4-) in a range of -0.30 to -2.14 V (vs Fc/Fc(+)). The electronic structure of 3a and its anionic species (3a(•-), 3a(2-), 3a(3•-), and 3a(4-)) were investigated by electronic spectra and X-ray crystallographic analyses.

Dimeric and trimeric tetrathiafulvalenes with strong intramolecular interactions in the oxidized states.

New dimeric and trimeric TTF derivatives with methylenedithio spacers (1a,b, 2a, and 2b) have been synthesized. X-ray structure analysis revealed that TTF units of the dimer 1b adopted distorted face-to-face overlapping arrangement both in intra- and intermolecular stacking. Cyclic voltammetric study indicated that trimeric 2a was in favor of taking di- and tetracationic states, while the dimeric 1a was in favor of taking a monocation. The absorption spectroscopic study suggested an existence of the strong face-to-face interaction particularly in di-, tri-, and tetracationic state of the trimeric TTF derivatives.

Unusual regioselective mercuration of metalloporphyrins and its potential applications.

The reaction of Hg(CF3CO2)2 with metalloporphyrins produces mercurated porphyrins regioselectively, the reaction, surprisingly occurring at the most hindered betaB-position; this behavior is in marked contrast to the usual electrophilic substitution reactions of porphyrins, whose reactions produce meso-substituted porphyrins; the obtained mercurated porphyrins are active to transition metal-catalyzed coupling reactions, such as the Mizoroki-Heck reaction.