Synthesis, Characterization, and Properties of a Titanium(IV)-Tetrathiafulvalene-Based Complex
Résumé
To deeply investigate the interaction between a tetrathiafulvalene (TTF) unit and a Ti(IV) center, a monomeric heteroleptic octahedral Ti(IV) complex containing a diimine ligand composed of a 1,10-phenanthroline core fused with a TTF fragment (ligand 2a) was prepared. The stable complex formulated as Ti(1)$_2$(2a), where 1 is a 2,2′-biphenolato derivative, was efficiently synthesized by following a one-step approach. This complex and its model species [Ti(1)$_2$(2b)] were fully characterized in solution, and their solid-state structures were established by single-crystal X-ray diffraction analysis. Density functional theory calculations allowed the assignment of the frontier orbitals involved in the electronic transitions characterized by ultraviolet–visible absorption spectroscopy. Electrochemical and spectroelectrochemical studies revealed that the TTF unit within Ti(1)$_2$(2a) can undergo two reversible one-electron oxidation processes; a reversible one-electron reduction of the Ti(IV) atom was highlighted. The photophysical measurements performed for this donor–acceptor molecular system indicated that an electron transfer process upon light excitation occurred within Ti(1)$_2$(2a).
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