Photophysikalische und photochemische Eigenschaften von Metalldithiolenen

Die Bis(dithiolen)-Komplexe des Typs [ML2][NBu4]2 (1–6), M = Zn, Cd, Hg, L = cyclisches oder acyclisches 1,2-Ethylendithiolat, fluoreszieren und phosphoreszieren in Ethanol oder 2-Methyltetrahydrofuranglas bei 77 K. Eine Emission bei Raumtemperatur wird nur im Falle der Komplexe mit aromatischen Liganden (5, 6) erhalten. In den Komplexen 1–3 mit acyclischen Liganden stammt der uberwiegende Teil der Fluoreszenz von einem photochemisch gebildeten Monodithiolen-Komplex und entspricht dem Emissionsspektrum von [LZn(NH3)2]. Als photochemischer Primarschritt wird im Falle der acyclischen Liganden eine cis-trans-Isomerisierung des Liganden, im Falle der cyclischen Liganden eine reversible Offnung der M–S-Bindung angenommen. Emissions- und Zersetzungsquantenausbeuten liegen im Bereich von 0.01–0.08 und sind weder vom Losungsmittel noch von der Belichtungswellenlange abhangig. Den in Absorption und Emission beobachteten angeregten Zustanden wird ein uberwiegender Intraligandcharakter zugeordnet. Photophysical and Photochemical Properties of Metal Dithiolenes Bis(dithiolene) complexes of the type [ML2][NBu4] (1–6), M = Zn, Cd, Hg, L = cyclic or acyclic 1,2-ethylenedithiolate, fluoresce and phosphoresce in ethanol or 2-methyltetrahydrofuran glass at 77 K. Emission at room temperature is found only in the case of complexes with aromatic ligands (5, 6). In the case of compounds with acyclic ligands (1–3) the major part of the fluorescence originates from a photochemically produced monodithiolene complex and matches the emission spectrum of [LZn(NH3)2]. The primary photoprocess is assumed to be ligand cis-trans isomerisation in the case of acyclic ligands and reversible M–S cleavage in the case of cyclic ligands. Quantum yields for emission and decomposition are in the range of 0.01 to 0.08 and do not depend on solvent or irradiation wavelength. Predominant intraligand character is assigned to the excited states observed in absorption and emission.

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