603113-19-5Relevant articles and documents
X-ray structures, photophysical characterization, and computational analysis of geometrically constrained copper(I) -Phenanthroline complexes
Cody, John,Dennisson, Jeanette,Gilmore, Joshua,VanDerveer, Donald G.,Henary, Maged M.,Gabrielli, Alan,Sherrill, C. David,Zhang, Yiyun,Pan, Chia-Pin,Burda, Clemens,Fahrni, Christoph J.
, p. 4918 - 4929 (2003)
A series of three geometrically constrained C2-symmetric Cu(I) mono-phenanthroline complexes were characterized by X-ray structural analysis, and their photophysical properties were investigated by absorption and emission spectroscopy. Visible light excitation yielded metal-to-ligand charge-transfer (MLCT) excited states with luminescence lifetimes up to 155 ns. Ultrafast ransient absorption spectroscopy provided further insights into the excited-state dynamics and suggests for all three complexes the formation of a phenanthroline radical anion. In agreement with electrochemical measurements, the data further indicate that coordinative rearrangements are involved in nonradiative deactivation of the excited states. According to time-dependent density functional theory calculations (B3LYP/6-31G**), the major MLCT transitions are polarized along the C2 axis of the complex and originate predominantly from the copper dxz orbital. The computational analysis identifies an excited-state manifold with a number of close-lying, potentially emissive triplet states and is in agreement with the multiexponential decay kinetics of the MLCT luminescence. The relationship between structural and photophysical data of the studied Cu(I) mono-phenanthroline complexes agrees well with current models describing the photophysics of the related Cu(I) bis-diimine complexes.
