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A series of four platinum(II) complexes bearing two tetrathiafulvalene acetylide ligands coordinated either cis or trans to the metal center are reported: cis-Pt(bipy)(CCMe3TTF)2, cis-Pt(tBu2bipy)(CCMe3TTF)2, cis-Pt(dppe)(CCMe3TTF)2 and trans-Pt(PPh3)2(CCMe3TTF)2. The X-ray diffraction studies of the four complexes are reported and discussed. The electrochemical investigations carried out by cyclic voltammetry (CV) and differential pulse voltammetry (DPV) evidenced different redox behavior as a function of the ancillary ligand. Only for the cis-Pt(dppe)(CCMe3TTF)2 complex is the first oxidation wave resolved (ΔE = 70 mV) into two one-electron processes. Spectroelectrochemical investigations performed on the four complexes did not evidence any electronic interactions between the two organic electrophores. The splitting of the first oxidation wave observed in cis-Pt(dppe)(CCMe3TTF)2 is mainly explained by the non-equivalence of the two TTF moieties induced by the geometrical constraint imposed by the ancillary dppe ligand as found by density functional theory calculations.
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