Vincent M. Miskowski

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The electronic structure of the binuclear copper complex [Cu(2)(L)](3+) [L = N(CH(2)CH(2)N(H)CH(2)CH(2)N(H)CH(2)CH(2))(3)N] has been investigated by resonance Raman and electroabsorption spectroscopy. Crystallographic Cu(2) distances of 2.364(1) and 2.415(1) A determined for the nitrate and acetate salts, respectively, are consistent with a substantial(More)
Binuclear copper complexes have important functional roles in many metalloproteins,1 a noteworthy example being cytochrome c oxidase, whose resting state contains a mixed-valence Cu2 site,1,2 the CuA center. The importance of direct Cu-Cu bonding in this protein site remains unclear at this time. The work reported here demonstrates that the Cu-Cu bonding(More)
Tunable dye laser excitation in the intense similar to 600-nm absorption band of azurin, plastocyanin, and ceruloplasmin provides resonance enhanced Raman spectra. They consist of a complex set of bands, at least three or four in number, between 350 and 473 cm-1, which are assignable to Cu-N or Cu-O bond stretching, and a weak band near 270 cm-1, which(More)
Absorption and emission spectra of Pt(diimine)L2 complexes (diimine = 2,2'-bipyridine (bpy) or 4,4'-dimethyl-2,2'-bipyridine (dmbpy); L = pyrazolate (pz-), 3,5-dimethylpyrazolate (dmpz-), or 3,4,5-trimethylpyrazolate (tmpz-)) have been measured. Solvent-sensitive absorption bands (370-440 nm) are attributed to spin-allowed metal-to-ligand charge-transfer(More)
We present studies of the resonance Raman and electronic luminescence spectra of the [Au(2)(dmpm)(3)](ClO(4))(2) (dmpm = bis(dimethylphosphine)methane) complex, including excitation into an intense band at 256 nm and into a weaker absorption system centered about approximately 300 nm. The resonance Raman spectra confirm the assignment of the 256 nm(More)
Acknowledgment. This study was supported at the University of Virginia by P.H.S. Grant CA38544, awarded by the National Cancer Institute. much lower in the absence of O2 (Figure l ) , and 1802-labeling experiments confirmed that the oxygen atom in the formed C ~ H S C H O was derived predominantly (>60%) from o2 for three of the oxidants employed. Also(More)
The synthesis and X-ray structural and spectroscopic characterization for LAuC triple bond CAuL x 4CHCl(3) and LAuC triple bond C--C triple bond CAuL x 2CH(2)Cl(2) (1 x 4CHCl(3) and 2 x 2CH(2)Cl(2), respectively; L = PCy(3), tricyclohexylphosphine) are reported. The bridging C(n)(2-) units are structurally characterized as acetylene or diacetylene units,(More)
The anion [Au2(CS3)2]2- has an unusually short Au-Au distance (2.80 A) for a binuclear Au(I) complex. We report detailed Raman studies of the nBu4N+ salt of this complex, including FT-Raman of the solid and UV/vis resonance Raman of dimethyl sulfoxide solutions. All five totally symmetric vibrations of the anion have been located and assigned. A band at(More)
A previously reported program for the calculation of vibronically resolved electronic absorption and emission spectra has been substantially improved to allow for the inclusion of up to five linearly coupled vibronic modes, in addition to the original three quadratically coupled modes, and for energy-weighted line broadening. The simulation of vibrouic(More)
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