Photochemistry of iodocuprate(I) complexes: formation and scavenging of hydrated electrons

✍ Scribed by Otto Horváth; Janos H. Fendler

• Book ID: 103994162
• Publisher: Elsevier Science
• Year: 1993
• Tongue: English
• Weight: 502 KB
• Volume: 71
• Category: Article
• ISSN: 1010-6030
• DOI: 10.1016/1010-6030(93)87005-8

✦ Synopsis

Irradiation

of iodocuprate(1) complexes at 308 nm results in the formation of hydrated electrons.

A quantum yield of 0.2350.015 is obtained for both CuI?and CIJI,~-at an ionic strength of 5 M. @= decreases with increasing ionic strength in the range 1-5 M. The hydrated electron formed in the primary photoreaction is efficiently scavenged by the ground state Cu(I) complexes; the rate constant of this reaction is (3.25 +0.25)x lo9 M-' s-l for CuI~'-; for CU.+-, due to the stronger electrostatic repulsion towards eaq-, k, is much smaller (7.5 x 10' M-' s-l). With increasing ionic strength, k, increases at low values of p (less than 1 M), in accordance with the Br@nsted-Bjerrum theory, but in the range 2-5 M it decreases due to the higher viscosity which hinders the diffusion of e,,-.