A Single- and Double-Flash Flash Photolysis Study of the Sequential Biphotonic Photoprocesses of Cu(I) Phenanthrolines. Comparison of the Helicate Complex, [Cu2(1,3-Bis(9-Methyl-1,10-Phenanthrolin-2-Yl)Propane) 2]2+, and [Cu(2,9-Dimethyl-1,10-Phenanthroline) 2]+ Photoprocesses

Photochemical processes induced when two photons are sequentially absorbed by the helicate complex [Cu2(mphenpr)2]2+, where mphenpr = 1,3-bis(9-methyl-1,10-phenanthrolin-2-yl)propane, and [Cu(dmp)2]+ were investigated in CH2Cl 2 containing solvents. A strong resemblance was observed between the fs-ns photophysics of [Cu2(mphenpr)2]2+ and Cu(i) phenanthroline complexes having a large steric hindrance. In the biphotonic regime, single-flash flash-photolyzed solutions were used for the determination of the product concentrations and quantum yields. The concentration of Cl- produced by the photoinduced decomposition of CH2Cl2 increases linearly with flash intensity as expected for a monophotonic process. In contrast, the concentration of a decomposed Cu(i) complex exhibits the quadratic dependence on flash intensity of a biphotonic process. Results of a sequential double-flash flash photolysis experiment are consistent with the decomposition of CH2Cl2 ahead of the flattened excited state formation and with the absorption of the second photon by the flattened MLCT excited state. © 2013 The Royal Society of Chemistry.