FeII Spin‐Crossover Phenomenon in the Pentadecanuclear {Fe9[Re(CN)8]6} Spherical Cluster

Chorąży, Szymon; Podgajny, Robert; Nakabayashi, Koji; Staněk, J.; Rams, Michał; Sieklucka, Barbara; Ohkoshi, Shin‐ichi

doi:10.1002/anie.201500288

Cited by 63 publications

(50 citation statements)

References 69 publications

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“…[12] Therefore,w ef ocused our attention on the underexplored [Re V (CN) 8 ] 3À analogue,w hich can stabilize Fe II centers favoring the SCO effect over the CT pathway,a ss hown in {Fe II 9 [Re V (CN) 8 ] 6 }c lusters. [13] Therefore,w ed ecided to employ [Re V (CN) 8 ] 3À ions for the construction of Fe-Re coordination networks to generate stepwise and hysteretic features of the SCO effect. Our direct inspiration was the report of a2 DC s{…”

Section: Introductionmentioning

confidence: 99%

Octacyanidorhenate(V) Ion as an Efficient Linker for Hysteretic Two‐Step Iron(II) Spin Crossover Switchable by Temperature, Light, and Pressure

et al. 2020

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A two‐step hysteretic FeII spin crossover (SCO) effect was achieved in programmed layered Cs{[Fe(3‐CNpy)2][Re(CN)8]}⋅H2O (1) (3‐CNpy=3‐cyanopyridine) assembly consisting of cyanido‐bridged FeII‐ReV square grid sheets bonded by Cs+ ions. The presence of two non‐equivalent FeII sites and the conjunction of 2D bimetallic coordination network with non‐covalent interlayer interactions involving Cs+, [ReV(CN)8]3− ions, and 3‐CNpy ligands, leads to the occurrence of two steps of thermal SCO with strong cooperativity giving a double thermal hysteresis loop. The resulting spin‐transition phenomenon could be tuned by an external pressure giving the room‐temperature range of SCO, as well as by visible‐light irradiation, inducing an efficient recovery of the high‐spin FeII state at low temperatures. We prove that octacyanidorhenate(V) ion is an outstanding metalloligand for induction of a cooperative multistep, multiswitchable FeII SCO effect.

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Section: Introductionmentioning

confidence: 99%

Octacyanidorhenate(V) Ion as an Efficient Linker for Hysteretic Two‐Step Iron(II) Spin Crossover Switchable by Temperature, Light, and Pressure

et al. 2020

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“…With such as till increasing library of coordination systems at hand, one can retrospectively select the groups that appear reproducibly at the specific experimental conditions;s uch molecular platforms can be further exploited in the construction of molecular networks with properties tuned by the buildingb locks of similars hapea nd molecular structure, yet differing in their electronic structure. [6][7][8][9][10][11] In light of the above solutions,t he formation of multi-metallic coordination compounds [12] is expected to multiply the opportunities to achieve not only simple, but also combined or even interacting functions. Along this line, very elegante xamples in the field of coordination chemistry were shown using the "simple"m ixings trategy, [2d, 13] solid-solution strategy [14] and modulars trategy, [14e,f, 15] yieldingn ovel specieso ft unable magnetic properties, for example, magnetic sponge-like behaviour, slow relaxation of the magnetization and spin-crossover,a s well as negative thermale xpansion and luminescence.…”

Section: Introductionmentioning

confidence: 99%

Tuning of High Spin Ground State and Slow Magnetic Relaxation within Trimetallic Cyanide‐Bridged {Ni^II_xCo^II_9−x[W^V(CN)₈]₆} and {Mn^II_xCo^II_9−x[W^V(CN)₈]₆} Clusters

Chorąży

Majcher

Kozieł

et al. 2018

Chemistry A European J

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Two series of trimetallic {Ni Co [W (CN) ] } (NiCoW) and {Mn Co [W (CN) ] } (MnCoW) (x=1-8) crystalline solid-solutions were constructed and systematically studied by SEM EDX, single-crystal X-ray diffraction (SC XRD), and magnetic measurements. The atomic Ni:Co:W and Mn:Co:W ratios in the solid state follow the stoichiometric concentration in the mother MeOH solutions fairly well. The structural studies revealed a definite strong tendency of smaller 3d ions to locate in the central [M(μ-NC) ] moiety of the skeleton: Ni over the Co and Co over Mn . In contrast, the external fac-[M(μ-NC) (MeOH) ] are consecutively occupied by the mixture of 3d metal ions, accessible according to the stoichiometry of the mother solutions. The DC magnetic χT(T) and M(H) curves illustrate the continuous tendency of change with x along both series, nicely reproducing the changes of the theoretical high spin in the ground state S , assuming the ferromagnetic Co -NC-W and antiferromagnetic Mn -NC-W interactions established by numerous literature reports. The AC magnetic measurements indicate the occurrence of slow magnetic relaxation, with the highest energy barrier ΔE/k of 26 K for the Ni Co W congener and of 17 K for the Mn Co W congener, and relatively large values of distribution parameter α. The values of ΔE are correlated with possible anisotropy of distribution of fac-[Co (μ-NC) (MeOH) ] moieties at the external corners of the cube substructure.

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“…Primarily, these properties were investigated within the classical group of three-dimensional bimetallic coordination frameworks based on hexacyanidometallates, called Prussian Blue Analogues (PBAs) [43]. However, the last several years brought the increasing attention pointed to the heterometallic coordination architectures based on other polycyanidometallates, including the homoligand tetracyanido- metallates of Pt II /Pd II , heptacyanidometallates of Mo III /Re IV , and octacyanidometallates of Mo IV/V , W IV/V , Re V , Nb IV , and the heteroligand [M(L) x (CN) y ] n − cyanide complexes with blocking organic ligand, L [44,45,46,47,48,49]. As a result, a variety of the [M(CN) x ] n − -based heterometallic coordination networks were reported, and many extraordinary magnetic, optical, and magneto-optical effects have been presented [50,51,52,53,54].…”

Section: Introductionmentioning

confidence: 99%

Lanthanide Photoluminescence in Heterometallic Polycyanidometallate-Based Coordination Networks

2017

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Solid-state functional luminescent materials arouse an enormous scientific interest due to their diverse applications in lighting, display devices, photonics, optical communication, low energy scintillation, optical storage, light conversion, or photovoltaics. Among all types of solid luminophors, the emissive coordination polymers, especially those based on luminescent trivalent lanthanide ions, exhibit a particularly large scope of light-emitting functionalities, fruitfully investigated in the aspects of chemical sensing, display devices, and bioimaging. Here, we present the complete overview of one of the promising families of photoluminescent coordination compounds, that are heterometallic d–f cyanido-bridged networks composed of lanthanide(3+) ions connected through cyanide bridges with polycyanidometallates of d-block metal ions. We are showing that the combination of cationic lanthanide complexes of selected inorganic and organic ligands with anionic homoligand [M(CN)x]n− (x = 2, 4, 6 and 8) or heteroligand [M(L)(CN)4]2− (L = bidentate organic ligand, M = transition metal ions) anions is the efficient route towards the emissive coordination networks revealing important optical properties, including 4f-metal-centred visible and near-infrared emission sensitized through metal-to-metal and/or ligand-to-metal energy transfer processes, and multi-coloured photoluminescence switchable by external stimuli such as excitation wavelength, temperature, or pressure.

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Fe^II Spin‐Crossover Phenomenon in the Pentadecanuclear {Fe₉[Re(CN)₈]₆} Spherical Cluster

Cited by 63 publications

References 69 publications

Octacyanidorhenate(V) Ion as an Efficient Linker for Hysteretic Two‐Step Iron(II) Spin Crossover Switchable by Temperature, Light, and Pressure

Octacyanidorhenate(V) Ion as an Efficient Linker for Hysteretic Two‐Step Iron(II) Spin Crossover Switchable by Temperature, Light, and Pressure

Tuning of High Spin Ground State and Slow Magnetic Relaxation within Trimetallic Cyanide‐Bridged {Ni^II_xCo^II_9−x[W^V(CN)₈]₆} and {Mn^II_xCo^II_9−x[W^V(CN)₈]₆} Clusters

Lanthanide Photoluminescence in Heterometallic Polycyanidometallate-Based Coordination Networks

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FeII Spin‐Crossover Phenomenon in the Pentadecanuclear {Fe9[Re(CN)8]6} Spherical Cluster

Cited by 63 publications

References 69 publications

Octacyanidorhenate(V) Ion as an Efficient Linker for Hysteretic Two‐Step Iron(II) Spin Crossover Switchable by Temperature, Light, and Pressure

Octacyanidorhenate(V) Ion as an Efficient Linker for Hysteretic Two‐Step Iron(II) Spin Crossover Switchable by Temperature, Light, and Pressure

Tuning of High Spin Ground State and Slow Magnetic Relaxation within Trimetallic Cyanide‐Bridged {NiIIxCoII9−x[WV(CN)8]6} and {MnIIxCoII9−x[WV(CN)8]6} Clusters

Lanthanide Photoluminescence in Heterometallic Polycyanidometallate-Based Coordination Networks

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Fe^II Spin‐Crossover Phenomenon in the Pentadecanuclear {Fe₉[Re(CN)₈]₆} Spherical Cluster

Tuning of High Spin Ground State and Slow Magnetic Relaxation within Trimetallic Cyanide‐Bridged {Ni^II_xCo^II_9−x[W^V(CN)₈]₆} and {Mn^II_xCo^II_9−x[W^V(CN)₈]₆} Clusters