Phosphino-aminothiazoline platinum(II) and platinum(II)/gold(I) complexes: Structural, chemical and vapoluminescent properties

Phosphino-amino-thiazolines and -thiazoles can exist in solution in two tautomeric forms, in which the N-H proton involves the endo-cyclic or exo-cyclic nitrogen atom. The two tautomers show different reactivities toward alcoholysis; the imino form degrades more rapidly. Their bischelated platinum complexes were studied in the solid state by single crystal X-ray diffraction. Thus, the unique stereo electronic features of the [Pt(PNth)] (PNth = diphenylposphino-aminothiazoline) moiety were revealed. The complex cis-[Pt(PNth)2] reacts with gold(I) salts to yield dimetallic compounds, the molecular structures of which have been determined by X-ray diffraction. Solid cis-[Pt(PNth)2] shows vapoluminescent properties if exposed to alcohol vapors. A combined photophysical and crystallographic investigation has been carried out to clarify the unprecedented rigidochromic role of the alcohol in this phenomenon. © 2007 Wiley-VCH Verlag GmbH & Co, KGaA.