Hydrogen-Bonding-Assisted Self-Doping in Tetrathiafulvalene (TTF) Conductor

摘要: The synthesis, characterization, and carrier generation mechanism of self-doping in a tetrathiafulvalene (TTF) conductor, ammonium tetrathiafulvalene-2-carboxylate (TTFCOO−NH4+), are described together with molecular orbital characteristics. Insulating TTFCOOH changes into hole-doped conductor TTFCOO−NH4+ conductivity σ = 2.0 × 10−4 S/cm (300 K), upon salt formation NH3. A radical species, TTF•+COO−NH4+, is generated via protonation the TTF moiety as demonstrated by UV−vis, ESR, 1H NMR spectra. X-ray crystallographic structure reveals supramolecular arrays TTFCOO− moieties short S···S contact, assisted one-dimensional hydrogen-bonding network composed carboxylate ions. Molecular calculations cluster models show that singly occupied (SOMO) TTF•+COO−NH4+ array not at highest energy level, which characterized quasi-closed-shell state. ab initio periodic ca...