Cis and trans-bis(tetrathiafulvalene-acetylide) platinum(II) complexes: syntheses, crystal structures, and influence of the ancillary ligands on their electronic properties. - Université de Rennes Accéder directement au contenu
Article Dans Une Revue Dalton Transactions Année : 2013

Cis and trans-bis(tetrathiafulvalene-acetylide) platinum(II) complexes: syntheses, crystal structures, and influence of the ancillary ligands on their electronic properties.

Résumé

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)(C≡CMe(3)TTF)(2), cis-Pt(tBu(2)bipy)(C≡CMe(3)TTF)(2), cis-Pt(dppe)(C≡CMe(3)TTF)(2) and trans-Pt(PPh(3))(2)(C≡CMe(3)TTF)(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)(C≡CMe(3)TTF)(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)(C≡CMe(3)TTF)(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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Dates et versions

hal-00808976 , version 1 (15-07-2013)

Identifiants

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Antoine Vacher, Frédéric Barrière, Franck Camerel, Jean-François Bergamini, Thierry Roisnel, et al.. Cis and trans-bis(tetrathiafulvalene-acetylide) platinum(II) complexes: syntheses, crystal structures, and influence of the ancillary ligands on their electronic properties.. Dalton Transactions, 2013, 42 (2), pp.383-94. ⟨10.1039/c2dt31686b⟩. ⟨hal-00808976⟩
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