Regensburg 2010 – scientific programme

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CPP: Fachverband Chemische Physik und Polymerphysik

CPP 12: Poster: Electronic and Optical Properties of Organic Systems

CPP 12.6: Poster

Monday, March 22, 2010, 16:30–18:00, Poster C

Spectroscopic and Theoretical Investigations on Pd(II) and Pt(II) Dithiocarbamates — •R. Wenisch¹, D. Forrer², S. Gross², M. Casarin², D. Montagner², A. Vittadini², M. Helm¹, E. Tondello², and S. Gemming¹ — ¹FZ Dresden-Rossendorf, Dresden, Germany — ²Dept. of Chemistry Univ. Padua, Padua, Italy

In coordination chemistry, the nature and strength of the metal-ligand interaction has attracted much interest. Metal-sulfur complexes, in particular in comparison with their oxygen-based analogues, are intriguing as the sulfur atoms are polarized more easily. The use of specifically tailored sulfur-based ligands allows for tuning the complex functional properties. Among them, electronic properties are very sensitive to changes in the sulfur coordination sphere, suggesting potential uses as molecular switches in optoelectronic devices. Metal dithiocarbamates [R₂NCS₂]_lM have been extensively studied by IR and UV-vis. spectroscopy, ESR and to a limited extent XPS and UPS. Here, we present experimental and theoretical studies investigating the electronic properties of a series of dithiocarbamates of Pd(II) and Pt(II): the pyrrolidine-based one and the 1-pyrrolidinecarbodithioate methyl ester (PyDTM). MX₂(PyDTM) (M=Pt/Pd; X=Cl/Br) were analyzed by XPS and by FT-IR spectroscopy. DFT calculations yielded details on the electronic structure and allowed for unambiguous assignment of the IR spectral features. Ionization energies were evaluated with the asymptotically correct LB94 potential and the two components ZORA.