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Title

A Pt(II) complex with both a phenanthroline and a tetrathiafulvalene-extended dithiolate ligand: Synthesis, crystal structure, electrochemical and spectroscopic properties

Authors
Jia, Chunyang
Liu, Shi-Xia
Neels, Antonia
Decurtins, Silvio
Published in Polyhedron. 2013, vol. 55, p. 87-91
Abstract The reaction of 4,5-bis(2'-cyano-ethylsulfanyl)-4',5'-dipropylthiotetrathiafulvalene with [Pt(phen)Cl2] (phen = 1,10-phenanthroline) with CsOH as base in CH3OH–THF affords the target complex 1 in 44% yield. This complex crystallizes in the monoclinic space group P21/c, M = 790.01, a = 12.1732(12), b = 15.851(2), c = 14.5371(16) Å, b = 107.693(12)˚, V = 2672.4(5) Å3 and Z = 4. It undergoes two reversible single-electron oxidation and two irreversible reduction processes. An intense electronic absorption band at 15200 cm-1 (658 nm) in CH2Cl2 is assigned to the intramolecular mixed metal/ligand-to-ligand charge transfer (LLCT) from a tetrathiafulvalene-extended dithiolate-based HOMO to a phenanthroline-based LUMO. This band shifts hypsochromically with increasing solvent polarity. Systematic changes in the optical spectra upon oxidation allow precise tuning of the oxidation states of 1 and reversible control over its optical properties. Irradiation of 1 at 15625 cm-1 (640 nm) in glassy solution below 150 K results in emission from the 3LLCT excited state.
Keywords TetrathiafulvaleneIntramolecular charge-transferSpectroelectrochemistry
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Research group Groupe Hauser
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JIA, Chunyang et al. A Pt(II) complex with both a phenanthroline and a tetrathiafulvalene-extended dithiolate ligand: Synthesis, crystal structure, electrochemical and spectroscopic properties. In: Polyhedron, 2013, vol. 55, p. 87-91. https://archive-ouverte.unige.ch/unige:32100

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Deposited on : 2013-12-13

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