Valence tautomerism in metal complexes: Stimulated and reversible intramolecular electron transfer between metal centers and organic ligands

Tezgerevska, Tina; Alley, Kerwyn G.; Boskovic, Colette

doi:10.1016/j.ccr.2014.01.014

Cited by 394 publications

(311 citation statements)

References 120 publications

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“…In the past, several transition-metal complexes with, for example, odioxolene ligands have demonstrated valence tautomerism. [2][3][4][5][6] The electronic structure is often influenced by a number of parameters, such as temperature, pressure, modifications of the coligands, the environment (solid state or solution), the solvent, and for charged complexes, even the counterions. [7][8][9][10] Most studied valence tautomeric transition-metal complexes are based on cobalt, [11] for which the change from the Co II high-spin to Co III low-spin state is associated with a relative high barrier.…”

Section: Introductionmentioning

confidence: 99%

A Valence Tautomeric Dinuclear Copper Tetrakisguanidine Complex

Wiesner

Wagner

Kaifer

et al. 2016

Chemistry A European J

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We report on the first valence tautomeric dinuclear copper complex, featuring 2,3,5,6-tetrakis(tetramethylguanidino)pyridine as a bridging redox-active GFA (guanidino-functionalized aromatic) ligand. The preferred electronic structure of the complex is massively influenced by the environment. In the solid state and in nonpolar solvents a paramagnetic, dinuclear Cu(II) complex with a neutral GFA ligand is present. In polar solvents, the electronic structure changes to a diamagnetic, dinuclear Cu(I) complex with a twofold-oxidized GFA ligand. Using acetone as a solvent, both electronic structures are accessible due to a temperature-dependent equilibrium between the two valence tautomeric complexes. Our results pave the way for a broader use of valence tautomeric transition-metal complexes in catalytic reactions since anionic coligands can now be tolerated owing to the neutral/positively charged GFA ligand.

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Section: Introductionmentioning

confidence: 99%

A Valence Tautomeric Dinuclear Copper Tetrakisguanidine Complex

Wiesner

Wagner

Kaifer

et al. 2016

Chemistry A European J

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“…These complexes are of interest as models for active sites of metal containing enzymes in bio-inorganic chemistry [4] or as potential electron reservoirs serving as efficient homogeneous catalysts [5]. We are also interested in the magnetic properties of complexes containing redox active ligands, in particular, semiquinone or iminosemiquinone-based ligands, where temperature dependent electron transfer reactions are often observed with cobalt (in so-called valence tautomerism) [6]. There are fewer examples of iminosemiquinone complexes relative to the parent semiquinone but iminosemiquinone systems are easy to prepare and can present a wide variety of structural types by variation of the amine in the synthesis [7][8][9][10].…”

Section: Introductionmentioning

confidence: 99%

Structure, magnetic properties and electronic structure of a nickel(II) complex with redox-active 6-(8-quinolylamino)-2,4-bis(tert-butyl)phenol

et al. 2016

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“…A n important challenge in molecular materials science is the design of functional compounds whose physical properties can be controlled by external stimuli -making them promising for a range of practical applications [1][2][3][4][5][6][7][8][9][10][11][12][13] . Numerous molecular materials exhibiting various switching effects in their electronic, magnetic, optical and mechanical properties -controlled through a variety of phenomena -have recently been reported, and are herein called dynamic molecular crystals (Fig.…”

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confidence: 99%

Dynamic molecular crystals with switchable physical properties

2016

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The development of molecular materials whose physical properties can be controlled by external stimuli - such as light, electric field, temperature, and pressure - has recently attracted much attention owing to their potential applications in molecular devices. There are a number of ways to alter the physical properties of crystalline materials. These include the modulation of the spin and redox states of the crystal's components, or the incorporation within the crystalline lattice of tunable molecules that exhibit stimuli-induced changes in their molecular structure. A switching behaviour can also be induced by changing the molecular orientation of the crystal's components, even in cases where the overall molecular structure is not affected. Controlling intermolecular interactions within a molecular material is also an effective tool to modulate its physical properties. This Review discusses recent advances in the development of such stimuli-responsive, switchable crystalline compounds - referred to here as dynamic molecular crystals - and suggests how different approaches can serve to prepare functional materials.

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Valence tautomerism in metal complexes: Stimulated and reversible intramolecular electron transfer between metal centers and organic ligands

Cited by 394 publications

References 120 publications

A Valence Tautomeric Dinuclear Copper Tetrakisguanidine Complex

A Valence Tautomeric Dinuclear Copper Tetrakisguanidine Complex

Structure, magnetic properties and electronic structure of a nickel(II) complex with redox-active 6-(8-quinolylamino)-2,4-bis(tert-butyl)phenol

Dynamic molecular crystals with switchable physical properties

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