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This study focuses on a series of PtII(L-L')(dppm)n+ complexes, where dppm is bis(diphenylphosphino)methane and L-L' are C-C' (n = 0), C-N (n = 1), and N-N' (n = 2) aromatic ligands. Structural characteristics are as follows: for [Pt(phen)(dppm)](PF6)2, a N-N' derivative, monoclinic, C2/c, a = 33.583(6) A, b = 11.399(2) A, c = 22.158(4) A, Z = 8; for [Pt(phq)(dppm)](PF6), a C-N derivative, triclinic, P1, a = 11.415(3) A, b = 13.450(3) A, c = 14.210(4) A, Z = 2; for [Pt(phpy)(dppm)](PF6), a C-N derivative, triclinic, P1, a = 10.030(3) A, b = 13.010(2) A, c = 15.066(4) A, Z = 2; and for [Pt(bph)(dppm)], a C-C' derivative, P2(1)/c, a = 17.116(7) A, b = 21.422(6) A, c = 26.528(6) A, Z = 12, where phen is 1,10-phenanthroline, phq is 2-phenylquinoline, phpy is 2-phenylpyridine, and bph is 2,2'-biphenyl. Structural features indicate that the Pt-C bond distance is shorter than the Pt-N bond distance in symmetrical complexes and that the Pt-P bond distance trans to N is shorter than the Pt-P bond trans to C. This is consistent with the 31P NMR spectra where the chemical shift of the P trans to C is approximately 10 ppm less than found for P trans to N. The energy maxima of the metal-to-ligand charge-transfer band for the complexes containing various L-L' ligands occur in the near-UV region of the spectrum and fall into the energy series bpy > bph > phen > 2-phpy > 2-ptpy > 2-phq > 7,8-bzq, where bpy is 2,2'-bipyridine, 2-phpy is 2-phenylpyridine, 2-ptpy is 2-p-tolylpyridine, and 7,8-bzq is 7,8-benzoquinoline. The emission energy maxima, ascribed to variance in metal-perturbed triplet ligand centered emission, commence near 500 nm and follow the series phen > bpy > 7,8-bzq > 2-phpy > 2-ptpy > bph > 2-phq. In general, emission is observed at 77 K and in solution at low temperatures, but the temperature dependence of the emission lifetimes indicates thermal activation to another state occurs with an energy of approximately 1800 cm-1 for the complexes, with the exception of [Pt(bph)(dppm)], which has an activation energy of approximately 2300 cm-1.

By a combination of Q-band pulsed ENDOR (electron nuclear double resonance) and X-band ESEEM (electron stimulated echo envelope modulation) techniques, we have determined the hyperfine tensors for ethylene (C1) and cyano (C2) carbons and N, of [Ni(mnt)(2)](-), along with the quadrupole tensor for nitrogen. These measurements give pi electron spin densities of rho(C1) approximately 0.03 in the C1 2p(z)() orbital, rho(C2) < 0.003, rho(N) approximately 0.01, such that in total, approximately 0.15 of the spin resides on the ligand atoms C and N, while the rest resides in the NiS(4) core, giving rho(NiS(4)(-)) = 0.85. These results are compared with extended Hückel and density functional (BLYP) MO calculations, as well as with Xalpha calculations reported earlier.