Mixed‐Ligand Copper Complexes with 8‐Methylthioquinoline and Triphenylphosphane or the<i>o</i>‐Semiquinone/Catecholate Redox System

Ye, Shengfa; Sarkar, Biprajit; Niemeyer, Mark; Kaim, Wolfgang

doi:10.1002/ejic.200500567

Cited by 19 publications

(14 citation statements)

References 40 publications

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“…The small magnitude of the thermodynamic parameters for [Cu Sal ] + in comparison to those reported for many metal–dioxolene systems10 is consistent with the relatively minor predicted change in bond lengths accompanying the shift in the locus of oxidation for [Cu Sal ] + . While temperature-dependent valence tautomerism between Cu(II)–catecholate and Cu(I)–semiquinonate species has been reported,70,72 this is the first account of a spin equilibrium involving a Cu–phenoxide complex. Interestingly, in the case of [Ni Sal ] + , the shift in the locus of oxidation from the ligand to the metal is due to large changes in the ligand field associated with axial ligation at low temperature 18.…”

Section: Discussionmentioning

confidence: 76%

Defining the Electronic and Geometric Structure of One-Electron Oxidized Copper−Bis-phenoxide Complexes

et al. 2008

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The geometric and electronic structure of an oxidized Cu complex ([CuSal] + ; Sal = N, N′-bis(3,5-di-tert-butylsalicylidene)-1,2-cyclohexane-(1R,2R)-diamine) with a non-innocent salen ligand has been investigated both in the solid state and in solution. Integration of information from UV-vis-NIR spectroscopy, magnetic susceptibility, electrochemistry, resonance Raman spectroscopy, X-ray crystallography, X-ray absorption spectroscopy, and density functional theory calculations provides critical insights into the nature of the localization/delocalization of the oxidation locus. In contrast to the analogous Ni derivative

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Section: Discussionmentioning

confidence: 76%

Defining the Electronic and Geometric Structure of One-Electron Oxidized Copper−Bis-phenoxide Complexes

et al. 2008

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“…On the other side, Kaim et al,570 have also reported the use of a weak π ‐acceptor thioether to induce sensitive valence tautomerism in paramagnetic copper complexes related to amine oxidase enzymes. In a more recent study, the comparison between two thioether ligands that differ on their π ‐acceptor capacity and structural rigidity has been used to have a comparative study of both effects 571…”

Section: Switching Materialsmentioning

confidence: 99%

Catechol‐Based Biomimetic Functional Materials

Saiz‐Poseu²,

et al. 2012

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Abstract.Catechols are found in nature taking part in a remarkably broad scope of biochemical processes and functions. Though not exclusively, such versatility may be traced back to several properties uniquely found together in the o -dihydroxyaryl chemical function; namely, its ability to establish reversible equilibria at moderate redox potentials and pHs and to irreversibly cross-link through complex oxidation mechanisms; its excellent chelating properties, greatly exemplifi ed by, but by no means exclusive, to the binding of Fe 3 + ; and the diverse modes of interaction of the vicinal hydroxyl groups with all kinds of surfaces of remarkably different chemical and physical nature. Thanks to this diversity, catechols can be found either as simple molecular systems, forming part of supramolacular structures, coordinated to different metal ions or as macromolecules mostly arising from polymerization mechanisms through covalent bonds. Such versatility has allowed catechols to participate in several natural processes and functions that range from the adhesive properties of marine organisms to the storage of some transition metal ions. As a result of such an astonishing range of functionalities, catechol-based systems have in recent years been subject to intense research, aimed at mimicking these natural systems in order to develop new functional materials and coatings. A comprehensive review of these studies is discussed in this paper.

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“…In contrast, above 250 K, the EPR signal of [Cu I (mmb)(3,5‐dbsq)] starts to appear, and it dominates above 350 K. The compounds [Cu I (dde)(3,5‐dbsq)]/[Cu II (dde)(3,5‐dbcat)] (dde=1‐diphenylphosphino‐2‐dimethylaminoethane) and [Cu I (mtq)(3,5‐dbsq)]/[Cu II (mtq)(3,5‐dbcat)] (mtq=8‐methylthioquinoline) also exhibit valence tautomerism 77. 78 Valence tautomerism of copper can also be observed in enzymes that play an important role in the oxidation of amines 79. Hence, the study of Cu valence‐tautomeric systems is important from biological and biomimetic viewpoints, as well as for basic science.…”

Section: Valence Tautomerismmentioning

confidence: 99%

Control of Magnetic Properties through External Stimuli

Sato¹,

Tao²,

Zhang³

2007

Angew Chem Int Ed

1,070

615

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The magnetic properties of many magnetic materials can be controlled by external stimuli. The principal focus here is on the thermal, photochemical, electrochemical, and chemical control of phase transitions that involve changes in magnetization. The molecular compounds described herein range from metal complexes, through pure organic compounds to composite materials. Most of the Review is devoted to the properties of valence-tautomeric compounds, molecular magnets, and spin-crossover complexes, which could find future application in memory devices or optical switches.

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Mixed‐Ligand Copper Complexes with 8‐Methylthioquinoline and Triphenylphosphane or theo‐Semiquinone/Catecholate Redox System

Cited by 19 publications

References 40 publications

Defining the Electronic and Geometric Structure of One-Electron Oxidized Copper−Bis-phenoxide Complexes

Defining the Electronic and Geometric Structure of One-Electron Oxidized Copper−Bis-phenoxide Complexes

Catechol‐Based Biomimetic Functional Materials

Control of Magnetic Properties through External Stimuli

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