Influence of the Steric/Electronic Properties of -Aryl Substituents in Cycloplatinated Guanidinate(1-) Complexes on the Formation of Discrete Pt → Ag Complexes and One-Dimensional Coordination Polymer.

The reactions of cycloplatinated guanidinate(1-) complexes - with AgTFA (TFA = OC(O)CF) in 1:1 and 1:2 Pt/Ag molar ratios afforded complexes containing three types of PtAg skeletons (-, , and ), one 1D CP containing PtAg skeleton (), and a PtAg complex () in 91-95% (method 1), 73-82% (method 2) (-), and 54-79% (, , , and ) yields. The reactions of with 2,6-XylNC (2,6-Xyl = 2,6-MeCH) and 4-DMAP (4-dimethylaminopyridine) gave a neutral complex and an ionic complex , respectively. Molecular structures of 12 complexes were unambiguously determined by single-crystal X-ray diffraction. Ten complexes contain unprecedented PtAg skeletons and are shown to contain multiple number of dative Pt → Ag bonds supported by the TFA ligand, platinated carbon of the TAG ligand, or both these ligands in conjunction with the Ag-Ag contacts stabilized by argentophilic interaction. Further, the new complexes were characterized by analytical, IR, and multinuclear NMR (F, H, C{H}, and Pt) spectroscopies, powder X-ray diffraction, and TGA/DTA. In solution, and exist in more than one form as identified by multinuclear NMR, and this behavior is ascribed to the restricted (N)C-N(H)Ar single-bond rotation of the TAG ligand. The photophysical properties of and are reported.