Properties of Pt(II) complexes containing both a pyridyl N–N chelate ligand having a long alkyl chain and a sulfur-rich dithiolate ligand and their molecular interactions in the solid state
摘要:
Reactions of PtCl2(N-alkyl-pyridine-2-carbaldimine) [alkyl = C10H21 and C16H33; C-10-PYa and C-16-pya] with Na2C3S5 [C3S52- = 4,5-disulfanyl-1,3-dithiole-2-thionate(2-)] or Na2C8H4S8 [C8H4S82- = 2-{(4,5-ethylenedithio)-1,3-dithiole-2-ylidene}-1,3-dithiole-4,5-dithiolate(2-)] in methanol or ethanol afforded Pt(C3S5)(C-10-pya), Pt(C3S5)(C-16-pya) and Pt(C8H4S8)(C-10-pya). Their electronic absorption spectra exhibited mixed metal/ligand-to-ligand charge transfer bands in the region of 570-780 nm in solution which are sensitive to a solvent. The C3S5 complexes show almost reversible redox waves around +0.62 V (versus SCE) and the C8H4S8 complex at +0.17 and +0.51 V (versus SCE). They were reacted with excess amounts of iodine to afford [Pt(C3S5)(C-10-pya and C-16-pya)] (I-3)(0.7), [Pt(C3S5)(C-10-pya)] (I-3)(1.1) and [Pt(C8H4S8)(C-10-pya)] (I-3)(1.5), which exhibited electrical conductivities of 1 x (10(-7) - 10(-3)) S cm(-1) measured for compacted pellets at room temperature. Molecular interactions of the complexes and their oxidized species in the solid state are discussed. (C) 1999 Elsevier Science S.A. All rights reserved.