Layered Metal Phosphonates as Potential Materials for the Design and Construction of Molecular Photosynthetic Systems

Vermeulen, Lori A.

doi:10.1002/9780470166451.ch3

“…Redox-active multinuclear metal–oxo cluster compounds such as polyoxometalates are interesting materials with relevance for different application fields such as materials science, catalysis, medicine, and biochemistry. − The attractive properties of these materials, e.g. in catalytic processes, are based on the fact that they can change the valence state of the active sites with only minor or even without any change in their cluster framework.…”

Section: Introductionmentioning

confidence: 99%

Control of Bridging Ligands in [(V₂O₃)₂(RXO₃)₄⊂F]⁻Cage Complexes: A Unique Way To Tune Their Chemical Properties

Rabeah

¹

,

Dimitrov

²

,

Surkus

³

et al. 2014

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In this work, the new organic–inorganic hybrid compound Ph4P[(V2O3)2(PhAsO3)4⊂F] (VAsF) has been prepared and characterized by single-crystal XRD and multinuclear magnetic resonance (1H, 19F, 31P, and 51V). Redox properties and thermal stability have been investigated by EPR, cyclic voltammetry, and thermal analysis in comparison to its Ph4P[(V2O3)2(PhPO3)4⊂F] (VPF) analogue. The VAsF cluster has a lower redox potential and higher electrochemical stability in solution, while it is thermally less stable in the solid state. Density functional theory (DFT) calculations showed that the difference in the redox potential is due to the different electron affinities of VPF and VAsF. With this approach of modifying the type of the ligand of the molecular vanadium cage, we hope to enhance the utility of such compounds as building blocks for the design of new hybrid materials with desirable properties.

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Electron Transfer in Coordination Compounds

Endicott

¹

2005

Encyclopedia of Inorganic Chemistry

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The transfer of an electron between a transition metal donor and a transition metal acceptor can be promoted by the absorption of either thermal or light energy. The thermal processes have been experimentally determined to span a range of about 10 20 in their ambient rates of electron transfer. The same molecular properties that determine the electron‐transfer reactivity also determine the correlated electron‐transfer absorption or emission band energy, band shape, and absorptivity. The relationships between the thermal‐kinetic and the spectroscopic observations are relatively simple when there is very little electron delocalization between the donor and acceptor, the weak‐coupling limit. This limit applies to most bimolecular electron‐transfer reactions of transition metals and to the spectroscopy of transition metal ion pairs; this is the limit treated well by Marcus theory. When the donor and acceptor are covalently linked, interactions of the donor and acceptor with the linker often increase the coupling in such a way as to enhance the reactivity and to alter the spectroscopy. Most of these linker‐induced changes of reactivity and spectroscopy can be treated in terms of perturbation theory‐based alterations of the behavior in the weak‐coupling limit. Reactivity in some very strongly coupled complexes seems to fall outside the standard theoretical framework; many such systems seem to implicate nuclear motions of the linker in facilitating the donor–acceptor electronic coupling. Extensions to biological, multicentered, and heterogeneous systems containing transition metal complexes are briefly considered.

show abstract

Electron Transfer in Coordination Compounds

Endicott¹

2005

Encyclopedia of Inorganic and Bioinorganic Chemistry

0

View full text Add to dashboard Cite

The transfer of an electron between a transition metal donor and a transition metal acceptor can be promoted by the absorption of either thermal or light energy. The thermal processes have been experimentally determined to span a range of about 10 20 in their ambient rates of electron transfer. The same molecular properties that determine the electron‐transfer reactivity also determine the correlated electron‐transfer absorption or emission band energy, band shape, and absorptivity. The relationships between the thermal‐kinetic and the spectroscopic observations are relatively simple when there is very little electron delocalization between the donor and acceptor, the weak‐coupling limit. This limit applies to most bimolecular electron‐transfer reactions of transition metals and to the spectroscopy of transition metal ion pairs; this is the limit treated well by Marcus theory. When the donor and acceptor are covalently linked, interactions of the donor and acceptor with the linker often increase the coupling in such a way as to enhance the reactivity and to alter the spectroscopy. Most of these linker‐induced changes of reactivity and spectroscopy can be treated in terms of perturbation theory‐based alterations of the behavior in the weak‐coupling limit. Reactivity in some very strongly coupled complexes seems to fall outside the standard theoretical framework; many such systems seem to implicate nuclear motions of the linker in facilitating the donor–acceptor electronic coupling. Extensions to biological, multicentered, and heterogeneous systems containing transition metal complexes are briefly considered.

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Layered Metal Phosphonates as Potential Materials for the Design and Construction of Molecular Photosynthetic Systems

Cited by 22 publications

References 95 publications

Control of Bridging Ligands in [(V₂O₃)₂(RXO₃)₄⊂F]⁻Cage Complexes: A Unique Way To Tune Their Chemical Properties

Control of Bridging Ligands in [(V₂O₃)₂(RXO₃)₄⊂F]⁻Cage Complexes: A Unique Way To Tune Their Chemical Properties

Electron Transfer in Coordination Compounds

Electron Transfer in Coordination Compounds

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Layered Metal Phosphonates as Potential Materials for the Design and Construction of Molecular Photosynthetic Systems

Cited by 22 publications

References 95 publications

Control of Bridging Ligands in [(V2O3)2(RXO3)4⊂F]−Cage Complexes: A Unique Way To Tune Their Chemical Properties

Control of Bridging Ligands in [(V2O3)2(RXO3)4⊂F]−Cage Complexes: A Unique Way To Tune Their Chemical Properties

Electron Transfer in Coordination Compounds

Electron Transfer in Coordination Compounds

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Product

Resources

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Control of Bridging Ligands in [(V₂O₃)₂(RXO₃)₄⊂F]⁻Cage Complexes: A Unique Way To Tune Their Chemical Properties

Control of Bridging Ligands in [(V₂O₃)₂(RXO₃)₄⊂F]⁻Cage Complexes: A Unique Way To Tune Their Chemical Properties