INOR 655 |
| The spectroscopic characteristics and reactivity of [Cu(dtp)2][B(C6F5)4] (1; dtp = 2,9-di-tert-butyl-1,10-phenanthroline) were investigated to assess the complex's potential as a dye for dye-sensitized solar cells and as a sensor. The steric burden imposed by four tert-butyl groups about Cu(I) produce outstanding luminescent properties and unique reactivity. Optical and fluorescence spectroscopies revealed the tert-butyl groups about Cu(I) prevent geometric reorganization of 1 upon excitation, reducing non-emissive relaxation. Maintaining the ground state geometry upon excitation results in a luminescence lifetime of 3 μs, greater than four times the highest value reported previously for phenanthroline-ligated Cu(I) complexes, and a quantum yield of 5% (in CH2Cl2), values comparable to those exhibited by Ru(bpy)32+. 1H NMR and vibrational studies reveal one dtp ligand is partially displaced to relieve steric crowding about the Cu(I) center in solution. This geometric reorganization facilitates total displacement of one dtp ligand from Cu(I) by common donor ligands such as CO, CH3CN and CH3NC in the ground state; previously ligand displacement reactions had only been reported for excited phenanthroline-ligated Cu(I) complexes. |
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Coordination Chemistry: Characterization and Applications
7:00 PM-10:00 PM, Tuesday, 12 September 2006 Moscone Center -- Hall D, Poster
Sci-Mix
Division of Inorganic Chemistry |