title: Photophysical and ab Initio Studies of Mononuclear Copper(I) Complexes.
abstract: Described are the photophysical properties of the mononuclear copper(I) complexes CuL(4)(+) (L = pyridine (py), 4-methylpyridine, 4-phenylpyridine, or acetonitrile), Cu(lut)(3)(+) (lut = 2,6-lutidine), and Cu(lut)(2)(+). Each of these compounds as their solid PF(6)(-) salts display a relatively long-lived (>1 &mgr;s), visible range emission at both ambient temperature and at 77 K but not in fluid solutions. Also reported are the results for ab initio calculations at the restricted Hartree-Fock self-consistent field level to probe the natures of lower energy excited states of the hypothetical species CuL(n)()(+) (L = NH(3), CH(3)CN, or py; n = 1-4). These results point to an assignment of the lowest energy, luminactive excited states as being largely metal centered, d --> s in character for each of the above complexes with the possible exception of the CuL(4)(+) species where L is py or a substituted analogue. In the case of Cu(py)(4)(+) the ab initiocalculations indicate a metal-to-ligand charge transfer to be the lowest energy Franck-Condon state, although the similarities of emission band shapes, energies, and lifetimes among the various complexes suggest a common d --> s assignment.
authors.affiliation: Department of Chemistry, University of California, Santa Barbara, California 93106.
authors.forename: Jerald A.
authors.initials: JA
authors.lastname: Simon
authors.forename: William E.
authors.initials: WE
authors.lastname: Palke
authors.forename: Peter C.
authors.initials: PC
authors.lastname: Ford