Spectroscopic and photophysical studies of apparent cluster-to-organic-acceptor charge transfer in a molecular cadmium sulfide assembly

✍ Scribed by Dong I. Yoon; Donald C. Selmarten; Hong Lu; Hui-Jean Liu; Carolyn Mottley; Mark A. Ratner; Joseph T. Hupp

• Publisher: Elsevier Science
• Year: 1996
• Tongue: English
• Weight: 506 KB
• Volume: 251
• Category: Article
• ISSN: 0009-2614
• DOI: 10.1016/0009-2614(96)00046-2

✦ Synopsis

A nitrobenzene (NB) decorated cadmium sulfide cluster, [Cd,(S-NB),,][N(CH,),],, has been prepared and examined spectroscopically. The assembly exhibits an intense cluster-to-attached-acceptor charge-transfer band at 376 nm. Observation of back electron transfer (nitrobenzene to cluster) via time resolved luminescence yields a rate constant of 2 5 X lo9 SK'. Raman studies show that seven vibrational modes are coupled to the electron transfer reaction and that those exhibiting the greatest initial-state/final-state displacements are the Cd-S and N-O stretches. Despite the activity of Y~~_~, however, the electron donor is more appropriately characterized as an individual sulfur atom, rather than a delocalized assembly.