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

Research output: Contribution to Journal/Magazine › Journal article › peer-review

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Transition Metal Substitution Effects on Metal-to-Polyoxometalate Charge Transfer. / Glass, Elliot; Fielden, John; Huang, Zhuangqun et al.
In: Inorganic Chemistry, Vol. 55, No. 9, 02.05.2016, p. 4308-4319.

Research output: Contribution to Journal/Magazine › Journal article › peer-review

Harvard

Glass, E, Fielden, J, Huang, Z, Xiang, X, Musaev, D, Lian, T & Hill, C 2016, 'Transition Metal Substitution Effects on Metal-to-Polyoxometalate Charge Transfer', Inorganic Chemistry, vol. 55, no. 9, pp. 4308-4319. https://doi.org/10.1021/acs.inorgchem.6b00060

APA

Glass, E., Fielden, J., Huang, Z., Xiang, X., Musaev, D., Lian, T., & Hill, C. (2016). Transition Metal Substitution Effects on Metal-to-Polyoxometalate Charge Transfer. Inorganic Chemistry, 55(9), 4308-4319. https://doi.org/10.1021/acs.inorgchem.6b00060

Vancouver

Glass E, Fielden J, Huang Z, Xiang X, Musaev D, Lian T et al. Transition Metal Substitution Effects on Metal-to-Polyoxometalate Charge Transfer. Inorganic Chemistry. 2016 May 2;55(9):4308-4319. doi: 10.1021/acs.inorgchem.6b00060

Author

Glass, Elliot ; Fielden, John ; Huang, Zhuangqun et al. / Transition Metal Substitution Effects on Metal-to-Polyoxometalate Charge Transfer. In: Inorganic Chemistry. 2016 ; Vol. 55, No. 9. pp. 4308-4319.

Bibtex

@article{daaa512d62da43a681ea694910fe96cc,
title = "Transition Metal Substitution Effects on Metal-to-Polyoxometalate Charge Transfer",
abstract = "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.",
keywords = "polyoxometalates, charge transfer",
author = "Elliot Glass and John Fielden and Zhuangqun Huang and Xu Xiang and Djamaladdin Musaev and Tianquan Lian and Craig Hill",
year = "2016",
month = may,
day = "2",
doi = "10.1021/acs.inorgchem.6b00060",
language = "English",
volume = "55",
pages = "4308--4319",
journal = "Inorganic Chemistry",
issn = "0020-1669",
publisher = "American Chemical Society",
number = "9",

}

RIS

TY - JOUR

T1 - Transition Metal Substitution Effects on Metal-to-Polyoxometalate Charge Transfer

AU - Glass, Elliot

AU - Fielden, John

AU - Huang, Zhuangqun

AU - Xiang, Xu

AU - Musaev, Djamaladdin

AU - Lian, Tianquan

AU - Hill, Craig

PY - 2016/5/2

Y1 - 2016/5/2

N2 - 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.

AB - 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.

KW - polyoxometalates

KW - charge transfer

U2 - 10.1021/acs.inorgchem.6b00060

DO - 10.1021/acs.inorgchem.6b00060

M3 - Journal article

VL - 55

SP - 4308

EP - 4319

JO - Inorganic Chemistry

JF - Inorganic Chemistry

SN - 0020-1669

IS - 9

ER -