| Density Functional Theory (DFT) calculated HOMO-LUMO energy gaps and HOMO and LUMO energies linearly correlate (R2 = 0.99) with electrochemical DeltaE1/2, E1/2ox, and E 1/2red, respectively, [DeltaE1/2 = E1/2(ox) - E1/2(red)] for ten Ru(II) complexes containing bpy, bpm and bpz (bpy = 2,2'-bipyridine, bpm = 2,2'-bipyrimidine, bpz = 2,2'-bipyrazine). E1/2(red) is linearly dependent (R2 = 0.97) on the LUMO energies for [Re(CO) 3(CNx)L]+ with a slope of -0.81 (L = 1,10-phenanthroline (phen), 5-Cl-phen, 5-NO2-phen, 5-Me-phen, 5,6-Me2-phen and phenpyrrole; CNx = 2,6-dimethylphenyl-isocyanide).; Simulated spectral peaks based on the singlet excited states calculated using Time-Dependent (TD) DFT and Conductor-like Polarizable Continuum Model (CPCM) for [Ru(bpy)2(CNx)Cl]+ linearly correlate (slope = 2.65, intercept = -38100 cm-1 and R 2 = 0.99) with the lowest-energy absorption maxima in seven solvents of varied polarity. The major peaks of the simulated spectrum of [Ru(bpy) 2(CNx)(py)]2+ deviate by less than 500 cm-1 from the corresponding experimental peaks (py = pyridine). The emitting states of the Ru(II) and Re(I) complexes containing CNx ligand are 3MLLCT states.; The results of the singlet ground and lowest-lying triplet states geometry optimization of [Pt2(mu-P2O5H2) 4]4- and the dimer of [Pt(bph)(CO)2] yield Pt-Pt distances that are shorter in the triplet relative to ground state by 7% and 4% respectively. [Pt(bph)(CO)2] forms stable dimers, related to concentration-dependent emission. The TDDFT calculated singlet and triplet excited states of [Pt(bph)(CO)2] correlate with experimental UV-Vis and phosphorescence emission spectra. |
