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Synthesis, Characterization, and Properties of a Titanium(IV)-Tetrathiafulvalene-Based Complex.

Jaison CasasStéphane A BaudronAntoine BonnefontAlain ChaumontJérôme ChauvinPierre MobianLaurent Ruhlmann
Published in: Inorganic chemistry (2024)
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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