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
2014
The mixed-ligand complexes [M(II)(Et2dazdt)(mnt)] (M = Ni, 1; Pd, 2; Pt, 3) [Et2dazdt = N,N′-diethyl-perhydrodiazepine-2,3-dithione; mnt = maleonitrile-2,3-dithiolate] have been prepared and fully characterized. X-ray diffractometric studies on 1–3 (the structure of 1 was already known) show that the crystals are isostructural (triclinic, P–1), 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–S bond distances involving the two ligands are similar, while the C–S bond distances in the C2S2 units exhibit a significant difference in Et2dazdt (dithione) and mnt (dithiolato) ligands. 1–3 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 neg...
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