Metal-to-Metal Electron Transfer in Co/Fe Prussian Blue Molecular Analogues: The Ultimate Miniaturization

Koumousi, Evangelia S.; Jeon, Ie‐Rang; Gao, Qian; Dechambenoit, Pierre; Woodruff, Daniel N.; Merzeau, Pascal; Buisson, L.; Jia, Xiaojun; Li, Dongfeng; Volatron, François; Mathonière, Corine; Clérac, Rodolphe

doi:10.1021/ja508094h

Cited by 168 publications

(207 citation statements)

References 32 publications

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“…3 days versus 10 years). Subsequent work by us and also several other research groups has shown that di-, 9 tri-, 10 tetra-, 11 penta, 6 hexa-, 12 tetradecanuclear 13 complexes and 1-D coordination polymers 14 also display comparable photophysical properties, which are highly sensitive to chosen ancillary ligands and their solid state intermolecular environments.…”

Section: ■ Introductionmentioning

confidence: 92%

Thermochromic and Photoresponsive Cyanometalate Fe/Co Squares: Toward Control of the Electron Transfer Temperature

Zhang¹,

Ferko²,

et al. 2014

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Two structurally related and photoresponsive cyanide-bridged Fe/Co square complexes, {Fe2Co2}, are reported: {[(Tp(Me))Fe(CN)3]2[Co(bpy)2]2[(Tp(Me))Fe(CN)3]2}·12H2O (2) and {[(Tp(Me))Fe(CN)3]2[Co(bpy)2]2[BPh4]2}·6MeCN (3), where Tp(Me) and bpy are hydridotris(3-methylpyrazol-1-yl)borate and 2,2'-bipyridine, respectively. Through electrochemical and spectroscopic studies, the Tp(Me) ligand appears to be a moderate σ donor in comparison to others in the [NEt4][(Tp(R))Fe(III)(CN)3] series [where Tp(R) = Tp, hydridotris(pyrazol-1-yl)borate; Tp(Me) = hydridotris(3-methylpyrazol-1-yl)borate; pzTp = tetrakis(pyrazol-1-yl)borate; Tp* = hydridotris(3,5-dimethylpyrazol-1-yl)borate; Tp*(Me) = hydridotris(3,4,5-trimethylpyrazol-1-yl)borate]. The spectroscopic, structural, and magnetic data of the {Fe2Co2} squares indicate that thermally-induced intramolecular electron transfer reversibly converts {Fe(II)LS(μ-CN)Co(III)LS} pairs into {Fe(III)LS(μ-CN)Co(II)HS} units near ca. 230 and 244 K (T1/2) for 2 and 3, respectively (LS: low spin; HS: high spin). These experimental results show that 2 and 3 display light-induced {Fe(III)LS(μ-CN)Co(II)HS} metastable states that relax to thermodynamic {Fe(II)LS(μ-CN)Co(III)LS} ones at ca. 90 K. Ancillary Tp(R) ligand donor strength appears to be the dominant factor for tuning electron transfer properties in these {Fe2Co2} complexes.

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Section: ■ Introductionmentioning

confidence: 92%

Thermochromic and Photoresponsive Cyanometalate Fe/Co Squares: Toward Control of the Electron Transfer Temperature

Zhang¹,

Ferko²,

et al. 2014

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“…Recently various multinuclear cyanide-bridged FeCo clusters exhibiting thermal and photoinduced charge transfers have also been synthesized [73][74][75][76][77][78] . The charge transfer process of FeCo compounds is expressed through a reversible phase transition between low-temperature phase with Fe II LS(S=0) -CN-Co III LS(S=0) and a high-temperature phase with Fe III LS(S=1/2) -CN-Co II HS(S=3/2) (Fig.…”

Section: Coupled Charge Transfer and Spin Transitionmentioning

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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“…22 Alternatively, spin transitions can also be induced by metal-to-ligand charge transfer, which is well-known in cobalt/dioxolene chemistry for example (eq 2; cat = catecholate, sq  = semiquinonate):…”

Section: Spin-state Switches In Molecular Materials Chemistrymentioning

confidence: 99%