CRYOSPECTROSCOPIC STUDIES OF COPPER(NN) (P)(2+) SYSTEMS: MULTIPLE LUMINESCENCE AND THE TUNING OF EXCITED STATES (MULTIPLE EMISSION, PHOTOPHYSICS)
Abstract
The absorption and luminescence spectra, relative quantum yields, and lifetimes of complexes of the type Cu(5-X-phen)(PPh(,3))(,2)BF(,4) (X = -H, -NH(,2), -CH(,3), -Cl, and -Ph; phen = 1,10-phenanthroline), Cu(X(,2)-phen)(PPh(,3))(,2)('+) (X = -CH(,3), -Cl, and -Ph), Cu(dmp) (P)(,2)BF(,4) (P = (P(p-tolyl)(,3), PPh(,3), and P(p-ClPh)(,3); dmp = 2,9-dimethyl-1,10-phenanthroline), and Cu(dmp) (P-P)BF(,4) (P-P = bis(1,2-diphosphino)ethane, bis(1,3-diphenylphosphino)propane, and bis(1,4-diphenylphosphino)butane) have been obtained at 77 K in a 4:1 ethanol/methanol glass. All of the compounds except those containing phosphine chelates exhibit multistate luminescence from ('3)d(pi)* (metal-to-ligand charge transfer) and ('3)(pi)(pi)* (intraligand from the coordinated phenanthroline) states. The compounds containing chelating phosphines show only ('3)d(pi)* luminescence. The results obtained are discussed in terms of variation of the triplet-triplet energy gap ((DELTA)) and possible electron transfer and state admixture (pseudo Jahn-Teller) effects. Correlation and assignment of the spectral properties of the uncoordinated ligands are also attempted, and the results are used to provide supporting evidence for the multiple emission observed. The effects of solvent variation and modification of intramolecular potentials due to matrix effects are discussed.
Degree
Ph.D.
Subject Area
Chemistry
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