Transition Metal Substitution Effects on Metal-to-Polyoxometalate Charge Transfer

Glass, Elliot, Fielden, John ORCID:, Huang, Zhuangqun, Xiang, Xu, Musaev, Djamaladdin, Lian, Tianquan and Hill, Craig (2016) Transition Metal Substitution Effects on Metal-to-Polyoxometalate Charge Transfer. Inorganic Chemistry, 55 (9). pp. 4308-4319. ISSN 0020-1669

[thumbnail of MMCT final SI ic-2016-00060v]
PDF (MMCT final SI ic-2016-00060v) - Accepted Version
Download (5MB) | Preview
[thumbnail of MMCT2 final text ic-2016-00060v]
PDF (MMCT2 final text ic-2016-00060v) - Accepted Version
Download (980kB) | Preview


A series of heterobimetallic transition metal substituted polyoxometalates (TMSPs) have been synthesized based on the CoII-centered ligand [CoIIW11O39]10-. The eight complex series, [CoII(MxOHy)W11O39](12-x-y)- (MxOHy = VIVO, CrIII(OH2), MnII(OH2), FeIII(OH2), CoII(OH2), NiII(OH2), CuII(OH2), ZnII(OH2)), of which six are reported for the first time, was synthesized starting from [CoIIIW11O39]9- and studied using spectroscopic, electrochemical, and computational techniques to evaluate the influence of substituted transition metals on the photodynamics of the metal-to-polyoxometalate charge transfer (MPCT) transition. The bimetallic complexes all show higher visible light absorption than the plenary [CoIIW12O40]6- and demonstrate the same MPCT transition as the plenary complex, but have shorter excited state lifetimes (sub-300 ps in aqueous media). The decreased lifetimes are rationalized on the basis of nonradiative relaxation due to coordinating aqua ligands, increased interaction with cations due to increased negative charge, and the energy gap law, with the strongest single factor appearing to be the charge on the anion. The most promising results are from the Cr- and Fe-substituted systems, which retain excited state lifetimes at least 50% of that of [CoIIW12O40]6- while more than tripling the absorbance at 400 nm.

Item Type: Article
Uncontrolled Keywords: polyoxometalates,charge transfer
Faculty \ School: Faculty of Science > School of Chemistry
Depositing User: Pure Connector
Date Deposited: 19 Apr 2016 12:00
Last Modified: 22 Oct 2022 01:00
DOI: 10.1021/acs.inorgchem.6b00060

Actions (login required)

View Item View Item