Intramolecular metal...sulfur interactions of platinum(II) 1,4,7-trithiacyclononane complexes with bipyridyl ligands: the relationship between molecular and electronic structures

Five platinum(II) 1,4,7-trithiacyclononane (ttcn) complexes with bidentate-substituted 2,2'-bipyridine ligands have been prepared and structurally characterized: Pt(bpy)(ttcn)](PF6)2 (bpy = 2,2'-bipyridine), triclinic, P1, a = 10.2529(3) A, b = 10.7791(3) A, c = 10.7867(3) A, alpha = 83.886(1) degrees, beta = 87.565(1) degrees, gamma = 84.901(1), V = 1179.99(6) A3, Z = 2; Pt(4,4'-dmbpy)(ttcn)](PF6)2 x CH3CN x H2O (4,4'-dmbpy = 4,4'-dimethyl-2,2'-bipyridine), triclinic, P1, a = 10.1895(3) A, b = 11.8566(4) A, c = 13.1004(4) A, alpha = 77.345(1) degrees, beta = 79.967(1) degrees, gamma = 72.341(1) degrees, V = 1461.56(8) A3, Z = 2; Pt(5,5'-dmbpy)(ttcn)](PF6)2 (5,5'-dmbpy = 5,5'-dimethyl-2,2'-bipyridine), triclinic, P1, a = 10.6397(4) A, b = 10.8449(4) A, c = 11.2621(4) A, alpha = 90.035(1) degrees, beta = 98.061(1) degrees, gamma = 91.283(1) degrees, V = 1286.32(8) A3, Z = 2; Pt(dbbpy)(ttcn)](PF6)2 x CH3NO2 (dbbpy = 4,4'-di-tert-butyl-2,2'-bipyridine), triclinic, P1, a = 11.5422(7) A, b = 11.6100(7) A, c = 13.6052(9) A, alpha = 85.902(1) degrees, beta = 89.675(1) degrees, gamma = 74.942(1) degrees, V = 1755.90(19) A3, Z = 2; and Pt(dtfmbpy)(ttcn)](PF6)2 x CH3CN (dtfmbpy = 5,5'-di-trifluoromethyl-2,2'-bipyridine): monoclinic, P2(1)/c, a = 13.1187(9) A, b = 20.9031(15) A, c = 11.3815(8) A, beta = 105.789(2) degrees, V = 3003.3(4) A3, Z = 4. For each salt, the platinum(II) center of the cation is bonded to two nitrogen atoms of the chelating diimine and two sulfur atoms of the thioether macrocycle. The third sulfur atom of ttcn forms a long apical interaction with the metal center (2.84-2.97 A), resulting in a flattened square pyramid structure. An examination of these and 17 other structures of platinum(II) ttcn complexes reveals a correlation between the apical Pt...S distance and the donor properties of the ancillary ligands, suggesting a means for using variations in ligand electronic properties to tune molecular structure. The room-temperature absorption spectra in acetonitrile solution show a broad and comparatively low-energy MLCT band maximizing near approximately 390 nm for the bpy and dialkyl-substituted bipyridyl derivatives. The maximum is dramatically red-shifted to 460 nm in the spectrum of the dtfmbpy complex as a result of the electron-withdrawing properties of the -CF(3) groups. The 3:1 EtOH/MeOH 77 K glassy solution emission spectra exhibit low-energy emission bands (lambdamax, 570-645 nm), tentatively assigned as originating from a lowest, predominantly spin-forbidden MLCT excited state that is stabilized by apical Pt...S interactions.