Are excimers formed along with hydrated electrons in the UV excitation of cyanocuprate(I) ions in aqueous solution?

Add time:08/10/2019    Source:sciencedirect.com

The three cyanocuprate(I) complexes, Cu(CN)2−, Cu(CN)32−, and Cu(CN)43−, photoeject electrons with high efficiency when excited in aqueous solution by 266 nm laser pulses of 7 ns duration with quantum yields of 0.37±0.06, 0.224±0.021, and 0.240±0.005, for Cu(CN)2− (at 2 M ionic strength), Cu(CN)32−, and Cu(CN)43− (both measured at 1 M ionic strength). Along with hydrated electrons, two transient intermediates, absorbing at 460 and 340 nm, respectively, form consecutively after excitation through bimolecular reactions with ground-state Cu(I) in solutions of Cu(CN)2−, and Cu(CN)32−, but not in Cu(CN)43−. All photoprocesses are essentially monophotonic. A mechanism is proposed that suggests the formation of a dinuclear excited-state complex such as an excimer.

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