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Synthesis, structures and properties of a new series of platinum-diimine-dithiolate complexes

Adams, Christopher J., Fey, Natalie, Parfitt, Matthew, Pope, Simon J. A. and Weinstein, Julia A. 2007. Synthesis, structures and properties of a new series of platinum-diimine-dithiolate complexes. Dalton Transactions 2007 (39) , pp. 4446-4456. 10.1039/b709252k

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The new square-planar platinum–diimine–dithiolate compounds [Pt(mesBIAN)SS] have been synthesised {mesBIAN = bis(mesityl)biazanaphthenequinone; SS = 1,2-dithiooxalate (dto) 1, maleonitriledithiolate (mnt) 2, 1,2-benzenedithiolate (bdt) 3, 3,4-toluenedithiolate (tdt) 4 and 1,3-dithia-2-thione-4,5-dithiolate (dmit) 5}, and the X-ray crystal structures of 3 and 5 determined. Cyclic voltammetry reveals that all the compounds form stable anions, and ESR spectroscopy of these anions shows that the SOMO is based upon the mesBIAN ligand; compounds 2–5 also show a reversible oxidation wave in their CV. Computational studies reveal that charge-transfer processes from orbitals that are combinations of metal and dithiolate ligand to a mesBIAN π*-based LUMO are responsible for the low energy absorptions seen in the UV/visible spectra of these compounds, and that the reverse process is responsible for the observed room-temperature solution luminescence of [Pt(mesBIAN)Cl2] and 1, 2 and 5. Compounds 3 and 4, containing aromatic thiolates, were not found to luminesce under the same conditions. Resonance Raman experiments have shown the origin of band-broadening of the lowest-energy absorption band in the absorption spectra of 2–5 to be due to vibronic structure within one electronic transition.

Item Type: Article
Date Type: Publication
Status: Published
Schools: Chemistry
Subjects: Q Science > QD Chemistry
Publisher: RSC
ISSN: 1477-9226
Last Modified: 04 Jun 2017 04:37

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