Two‐Step Spin Conversion in a Cyanide‐Bridged Ferrous Square

Nihei, Masayuki; Ui, Mayumi; Yokota, Mizuho; Han, Lingqin; Maeda, Atsushi; Kishida, Hideo; Okamoto, Hiroshi; Oshio, Hiroki

doi:10.1002/anie.200502216

Cited by 191 publications

(102 citation statements)

References 43 publications

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“…There are two distinct situations that account for stepwise transitions. One is observed when different SCO sites, characterized by distinct transition temperatures (T 1/2 or T c ), are present in the solid [10][11][12][13][14][15][16][17]. The other arises from subtle balances between different elastic interactions in the crystal lattice, which spontaneously generate two or more The crystal structures of the anhydrous and the hydrate species (x = 0, 1/3) were investigated at 200 K, 130 K and 90 K. At 200 K, the crystals are monoclinic (space group C2/c, (Z = 8)) and contain one crystallographically independent Fe II site, which is HS.…”

Section: Introductionmentioning

confidence: 99%

Symmetry Breaking in Iron(II) Spin-Crossover Molecular Crystals

2016

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Abstract:This review provides an up to date survey of a singular class of iron(II) spin crossover (SCO) molecular materials that undergo high-spin (HS) Ø low-spin (LS) phase transitions accompanied by crystallographic symmetry breaking (CSB). Particular interest has been focused on a variety of complexes that exhibit one-step or stepwise SCO behavior and CSB. Most of them afford excellent examples of well-ordered 1HS-1LS, 2HS-1LS or 1HS-2LS intermediate phases (IP) and represent an important platform to disclose microscopic mechanisms responsible for cooperativity and ordering in such multistable materials.

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Section: Introductionmentioning

confidence: 99%

Symmetry Breaking in Iron(II) Spin-Crossover Molecular Crystals

2016

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“…[2][3][4][5][6][7][8] Mono-or multinuclear systems that have more than one crystallographically distinct SCO site prior to a stepped transition may be merely interpreted in terms of the individual sites having different chemical environments and/or intermolecular interactions and hence different ligand field and/or interaction parameters. That such metal sites may undergo SCO at somewhat different temperatures is certainly no surprise.…”

Section: Introductionmentioning

confidence: 99%

Pressure-induced two-step spin transition with structural symmetry breaking: X-ray diffraction, magnetic, and Raman studies

et al. 2011

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We have used single-crystal x-ray diffraction, Raman spectroscopy, and magnetometry to investigate the effect of hydrostatic pressures up to 16 kbar on the molecular spin crossover complex [Fe II (bapbpy)(NCS) 2 ]. A stepped first-order transition from the high-spin (HS) to low-spin (LS) phase was observed upon compression of single-crystal samples. The intermediate phase (IP) is stable between 4 and 11 kbar at room temperature. This phase is characterized by supercell reflections and tripling of the c-axis of the unit cell (C2/c) due to the formation of a periodic [HS-LS-LS] structural motif, as seen in the thermal stepped transition. The pressure-temperature phase diagram reveals an anomalous increase of the thermal hysteresis widths with increasing pressure and the stabilization of the IP across the investigated P-T space.

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“…Approaches to the generation of multi-bistable systems include the crystallization of mononuclear SCO complexes in asymmetric packing environments 21 , the co-crystallization of different bistable molecules 22 and the linkage of two or more bistable building blocks in a molecular system, in which the stabilization of an intermediate state depends on the degree to which neighbouring chromophores are electronically coupled 23 . Cooperative SCO behaviour, mediated by the steric and electronic stress applied to neighbouring metal centres by multidentate or bridging ligands, has been reported in dinuclear complexes 23 , tetranuclear squares 24,25 and grid-like complexes [26][27][28] . Indeed, the study of grid-type clusters is of particular interest, as their tunable electronic states 29,30 have seen them proposed as quantum cellular automata; molecular binary logic devices that function through coulombic interactions between metal centres on neighbouring cells 31 .…”

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Programmable spin-state switching in a mixed-valence spin-crossover iron grid

et al. 2014

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Photo-switchable systems, such as discrete spin-crossover complexes and bulk iron-cobalt Prussian blue analogues, exhibit, at a given temperature, a bistability between low-and high-spin states, allowing the storage of binary data. Grouping different bistable chromophores in a molecular framework was postulated to generate a complex that could be site-selectively excited to access multiple electronic states under identical conditions. Here we report the synthesis and the thermal and light-induced phase transitions of a tetranuclear iron(II) grid-like complex and its two-electron oxidized equivalent. The heterovalent grid is thermally inactive but the spin states of its constituent metal ions are selectively switched using different laser stimuli, allowing the molecule to exist in three discrete phases. Site-selective photo-excitation, herein enabling one molecule to process ternary data, may have major ramifications in the development of future molecular memory storage technologies.

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Two‐Step Spin Conversion in a Cyanide‐Bridged Ferrous Square

Cited by 191 publications

References 43 publications

Symmetry Breaking in Iron(II) Spin-Crossover Molecular Crystals

Symmetry Breaking in Iron(II) Spin-Crossover Molecular Crystals

Pressure-induced two-step spin transition with structural symmetry breaking: X-ray diffraction, magnetic, and Raman studies

Programmable spin-state switching in a mixed-valence spin-crossover iron grid

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