Synthesis and characterization of a metal-to-polyoxometalate charge transfer molecular chromophore

Chongchao Zhao; Zhuangqun Huang; William Rodríguez-Córdoba; Choon Sung Kambara; Kevin P O'Halloran; Ken I Hardcastle; Djamaladdin G Musaev; Tianquan Lian; Craig L Hill

doi:10.1021/ja209360x

Synthesis and characterization of a metal-to-polyoxometalate charge transfer molecular chromophore

J Am Chem Soc. 2011 Dec 21;133(50):20134-7. doi: 10.1021/ja209360x. Epub 2011 Nov 23.

Authors

Chongchao Zhao¹, Zhuangqun Huang, William Rodríguez-Córdoba, Choon Sung Kambara, Kevin P O'Halloran, Ken I Hardcastle, Djamaladdin G Musaev, Tianquan Lian, Craig L Hill

Affiliation

¹ Department of Chemistry and Cherry L. Emerson Center for Scientific Computation, Emory University, Atlanta, Georgia 30322, USA.

PMID: 22092140
DOI: 10.1021/ja209360x

Abstract

[P(4)W(35)O(124){Re(CO)(3)}(2)](16-) (1), a Wells-Dawson [α(2)-P(2)W(17)O(61)](10-) polyoxometalate (POM)-supported [Re(CO)(3)](+) complex containing covalent W(VI)-O-Re(I) bonds has been synthesized and characterized by several methods, including X-ray crystallography. This complex shows a high visible absorptivity (ε(470 nm) = 4000 M(-1) cm(-1) in water) due to the formation of a Re(I)-to-POM charge transfer (MPCT) band. The complex was investigated by computational modeling and transient absorption measurements in the visible and mid-IR regions. Optical excitation of the MPCT transition results in instantaneous (<50 fs) electron transfer from the Re(I) center to the POM ligand.