Synthesis and Computational and Experimental Investigations of a para-Nicotinic Acid-Bridged Dirhenium(I) Dimer Complex

[Image: see text] The Re(I) dimer complex, [fac(CO)(3)(phen)Re1-N(py)COORe2(phen)fac(CO)(3)](+) (py = pyridine; phen = 1,10-phenanthroline), contains two different Re(I) centers 9.3 Å apart, one with a nitrogen donor and the other with an acetate donor from the bridging isonicotinate ligand. The complexes were characterized by (1)H NMR, UV–vis, fluorescence, and IR spectroscopy, elemental analysis, and single-crystal X-ray diffraction. The absorption and emission properties of the dimer dominated by charge transfer transitions are analyzed with respect to those of the monomers, [fac(CO)(3)(phen)Re-N(pyCOOCH(3))](+) and [fac(CO)(3)(phen)ReOOCCH(3)]. Spectral comparison of these three complexes results in the unexpected finding that the dimer emission (575 nm) occurs near that of the nicotinate-containing monomer (580 nm) rather than near the lower energy-emitting state (650 nm) of the acetate-containing monomer. Density functional theory (DFT) calculations elucidate this unusual emission behavior. The geometries of the dimer and two monomers are optimized in the singlet ground and lowest-energy triplet excited states (LLTS’s) to interpret absorption and emission behaviors, respectively. The singlet excited states calculated using time-dependent DFT correlate well with the absorption spectra in the lowest-energy and other major electronic transitions. The energy gaps and low-lying singlet excited states of the dimer are close to those of the acetate-containing monomer. The lowest-energy Franck–Condon triplet excited state of the dimer arising from electronic transitions localized on the acetate moiety is unstable. The next higher Franck–Condon triplet excited state arises from long-range charge transfer transition, and its energy is close to that of the nicotinate-containing monomer. Optimization of the dimer LLTS yields a stable state based on a long-range charge transfer transition involving occupied orbitals partially localized on the bridging nicotinate moiety. The LLTS energies of the dimer and nicotinate-containing monomer are in very good agreement as are the emission energies of these complexes. The correlated spectroscopic and computational results corroborate to the understanding of charge transfer states and transitions toward the development of photosensitive compounds for photoelectrochemical solar energy conversion cells.