title: Synthesis and characterization of a metal-to-polyoxometalate charge transfer molecular chromophore.
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.
authors.affiliation: Department of Chemistry and Cherry L. Emerson Center for Scientific Computation, Emory University, Atlanta, Georgia 30322, USA.
authors.forename: Chongchao
authors.initials: C
authors.lastname: Zhao
authors.forename: Zhuangqun
authors.initials: Z
authors.lastname: Huang
authors.forename: William
authors.initials: W
authors.lastname: Rodríguez-Córdoba
authors.forename: Choon Sung
authors.initials: CS
authors.lastname: Kambara
authors.forename: Kevin P
authors.initials: KP
authors.lastname: O'Halloran
authors.forename: Ken I
authors.initials: KI
authors.lastname: Hardcastle
authors.forename: Djamaladdin G
authors.initials: DG
authors.lastname: Musaev
authors.forename: Tianquan
authors.initials: T
authors.lastname: Lian
authors.forename: Craig L
authors.initials: CL
authors.lastname: Hill