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Protonation of pyridyl-substituted TTF derivatives: substituent effects in solution and in the proton-electron correlated charge-transfer complexes.

Protonated pyridyl-substituted tetrathiafulvalene electron-donor molecules (PyH(+)-TTF) showed significant changes in the electron-donating ability and HOMO-LUMO energy gap compared to the neutral analogues and gave a unique N(+)-H⋅⋅⋅N hydrogen-bonded (H-bonded) dimer unit in the proton-electron correlated charge-transfer (CT) complex crystals. We have evaluated these features from the viewpoint of the molecular structure of the PyH(+)-TTF derivatives, that is, the substitution position of the Py group and/or the presence or absence of the ethylenedithio (EDT) group. Among 2-PyH(+)-TTF (1 oH(+)), 3-PyH(+)-TTF (1 mH(+)), 4-PyH(+)-TTF (1 pH(+)), and 4-PyH(+)-EDT-TTF (2 pH(+)) systems, the para-pyridyl-substituted donors 1 pH(+) and 2 pH(+) exhibit more marked changes upon protonation in solution; a larger redshift in the intramolecular CT absorption band and a larger decrease in the electron-donating ability. Furthermore, the EDT system 2 pH(+) has the smallest intramolecular Coulombic repulsion energy. These differences are reasonably interpreted by considering the energy levels and distributions of the HOMO and LUMO obtained by quantum chemical calculations. Such substituent effects related to protonation were also examined by comparing the structure and properties of a new H-bonded CT complex crystal based on 2 pH(+) with those of its 1 pH(+) analogue recently prepared by us: Both of them form a similar type of H-bonded dimer unit, however, its charge distribution as well as the overall molecular arrangement, electronic structure, and conductivity were significantly modulated by the introduction of the EDT group. These results provide a new insight into the structural and electronic features of the PyH(+)-TTF-based proton-electron correlated molecular conductors.