Role of the Acceptor in Tuning the Properties of Metal [M(II) = Ni, Pd, Pt] Dithiolato/Dithione (Donor/Acceptor) Second-Order Nonlinear Chromophores: Combined Experimental and Theoretical Studies

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• 作者：Davide Espa ; Luca Pilia ; Christodoulos Makedonas ; Luciano Marchiò ; M. Laura Mercuri ; Angela Serpe ; Alberto Barsella ; Alain Fort ; Christiana A. Mitsopoulou ; Paola Deplano
• 刊名：Inorganic Chemistry
• 出版年：2014
• 出版时间：January 21, 2014
• 年：2014
• 卷：53
• 期：2
• 页码：1170-1183
• 全文大小：572K
• ISSN：1520-510X

文摘

The mixed-ligand complexes [M(II)(Et₂dazdt)(mnt)] (M = Ni, 1; Pd, 2; Pt, 3) [Et₂dazdt = N,N鈥?diethyl-perhydrodiazepine-2,3-dithione; mnt = maleonitrile-2,3-dithiolate] have been prepared and fully characterized. X-ray diffractometric studies on 1鈥?b>3 (the structure of 1 was already known) show that the crystals are isostructural (triclinic, P鈥?), and two independent molecular entities are present in the unit cell. These entities differ in the orientation of the ethyl substituents with respect to the epta-atomic ring. In the C₂S₂MS₂C₂ dithiolene core the four sulfur atoms define a square-planar coordination environment of the metal where the M鈥揝 bond distances involving the two ligands are similar, while the C鈥揝 bond distances in the C₂S₂ units exhibit a significant difference in Et₂dazdt (dithione) and mnt (dithiolato) ligands. 1鈥?b>3 show in the visible region one or two moderately strong absorption peaks, having ligand-to-ligand charge-transfer (CT) character with some contribution of the metal, and show negative solvatochromism and molecular quadratic optical nonlinearity, which was determined by the EFISH (electric-field-induced second-harmonic generation) technique. These complexes are redox active and show two reversible reduction waves and one irreversible oxidation wave. Theoretical calculations based on DFT and TD-DFT calculations on complexes 1鈥?b>3 as well as on [Pt(Bz₂pipdt)(mnt)] (4) and [Pt(Bz₂pipdt)(dmit)] (5) highlight the factors which affect the optical properties of these second-order redox-active NLO chromophores. Actually, the torsion angle of the dithione system (未₂) inversely correlates either with the oscillator strengths of the main transition of the complexes or with their beta values. The high beta value of 5 can be attributed both to its lowest torsion angles and to the extent of the 蟺 system of its dithiolate ligand, dmit.