Synthesis of the Single‐Crystalline Form and First‐Principles Calculations of Photomagnetic Copper(II) Octacyanidomolybdate(IV)

Umeta, Yoshikazu; Chorąży, Szymon; Nakabayashi, Koji; Ohkoshi, Shin‐ichi

doi:10.1002/ejic.201500823

Cited by 20 publications

(11 citation statements)

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“…Molybdenum‐copper complexes have attracted great attention over the past decade due to the interesting photomagnetic phenomena that have been reported for these systems . Most of the compounds display a reversible photoinduced magnetic bistability that has been developed into various forms: three‐dimensional networks, molecular complexes, high nuclearity clusters,, chains,, nanoparticles, and films . In addition, the integration of Mo‐Cu complexes viewed as magnetic switches into sophisticated architectures, has been performed with success as well as their transformation into promising materials with various properties , .…”

Section: Introductionmentioning

confidence: 99%

Direct Evidence of a Photoinduced Electron Transfer in Diluted “Molybdenum‐Copper” Molecular Compounds

et al. 2017

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Section: Introductionmentioning

confidence: 99%

Direct Evidence of a Photoinduced Electron Transfer in Diluted “Molybdenum‐Copper” Molecular Compounds

et al. 2017

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“…Prompted by these discoveries, we continue our intensive research on photoinduced magnetization in heterometallic systems based on photoactive [Mo IV (CN) 8 ] 4– and [W IV (CN) 8 ] 4– ions. The related Cu II –Mo IV networks were proved to reveal a photoinduced singlet–triplet spin transition in [Mo IV (CN) 8 ] 4– ions and concurrent MMCT transitions, − the last one also supported by ab initio calculations. Thus, it is expected that for the specific coordination geometries of these octacyanidometalates both processes, spin transition and charge transfer, could be induced by light irradiation. , …”

Section: Introductionmentioning

confidence: 58%

Chiral Photomagnets Based on Copper(II) complexes of 1,2-Diaminocyclohexane and Octacyanidomolybdate(IV) Ions

et al. 2020

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Chiral photomagnets compose a class of multifunctional molecule-based materials with light-induced alteration of magnetization and chiral properties. The rational design and synthesis of such assemblies is a challenge, and only few such systems are known. Herein, the remarkable octacyanide-bridged enantiomeric pair of 1-D chains [Cu((R,R)-chxn)2]2[Mo(CN)8]·H2O (1R) and [Cu((S,S)-chxn)2]2[Mo(CN)8]·H2O (1S) exhibiting enantiopure structural helicity, which results in optical activity in the 350–800 nm range as confirmed by natural circular dichroism (NCD) spectra, is reported. The photomagnetic effects of 1R, 1S, and 1rac result from the blue light excitation (436 nm) of the photomagnetically active octacyanidomolybdate(IV) ions. In the excited state MoIV HS centers with S = 1 couple antiferromagnetically with the neighboring CuII centers with J CuMo values of −1.3, −1.0, and −1.1 cm–1 for 1R, 1S, and 1rac, respectively. The values of thermal relaxation energy barriers have been estimated as 142 and 356 K for 1R and 1S, being comparable with the energy range of the thermal bath. The value for 1rac reveals a significantly lower value of 75 K. On the basis of these results the value of g Mo HS has been estimated to be in the range 4.8–5.8.

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“…450 nm (Figure a). This UV–vis absorption is connected mainly with the charge-transfer transitions within [Mo IV (CN) 8 ] 4– . However, the band at ca.…”

Section: Resultsmentioning

confidence: 99%

In Situ Ligand Transformation for Two-Step Spin Crossover in Fe^II[M^IV(CN)₈]^4– (M = Mo, Nb) Cyanido-Bridged Frameworks

et al. 2019

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We report a unique synthetic route toward the multistep spin crossover (SCO) effect induced by utilizing the partial ligand transformation during the crystallization process, which leads to the incorporation of three different Fe II complexes into a single coordination framework. The 3acetoxypyridine (3-OAcpy) molecules were introduced to the self-assembled Fe II −[M IV (CN) 8 ] 4− (M = Mo, Nb) system in the aqueous solution which results in the partial hydrolysis of the ligand into 3-hydroxypyridine (3-OHpy). It gives two novelThey exhibit an unprecedented cyanido-bridged skeleton composed of {Fe 3 M 2 } n coordination nanotubes bonded by additional Fe complexes. These frameworks contain three types of Fe sites differing in the attached organic ligands, [Fe1(3-OAcpy) 4 (μ-NC) 2 ], [Fe2(3-OHpy) 4 (μ-NC) 2 ], and [Fe3(3-OAcpy) 3 (3-OHpy)(μ-NC) 2 ], which lead to the thermal two-step Fe II SCO, as proven by X-ray diffraction, magnetic susceptibility, UV− vis−NIR optical absorption, and 57 Fe Mossbauer spectroscopy studies. The first step of SCO, going from room temperature to the 150−170 K range with transition temperatures of 245(5) and 283(5) K for FeMo and FeNb, respectively, is related to Fe1 sites, while the second step, occurring at the 50−140 K range with transition temperatures of 70(5) and 80(5) K for FeMo and FeNb, respectively, is related to Fe2 sites. The Fe3 site with both 3-OAcpy and 3-OHpy ligands does not undergo the SCO at all. The observed two-step SCO phenomenon is explained by the differences in the ligand field strength of the Fe complexes and the role of their alignment in the coordination framework. The simultaneous application of two related pyridine derivatives is the efficient synthetic route for the multistep Fe II SCO in the cyanido-bridged framework which is a promising step toward rational design of advanced spin transition molecular switches.

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Synthesis of the Single‐Crystalline Form and First‐Principles Calculations of Photomagnetic Copper(II) Octacyanidomolybdate(IV)

Abstract: A gel crystallization technique was successfully applied in the pioneering preparation of a single-crystalline form of the three-dimensional copper(II) octacyanidomolybdate(IV) network, which is a photomagnetic material. This assembly crystallizes with the formula {[Cu II

Cited by 20 publications

References 45 publications

Direct Evidence of a Photoinduced Electron Transfer in Diluted “Molybdenum‐Copper” Molecular Compounds

Direct Evidence of a Photoinduced Electron Transfer in Diluted “Molybdenum‐Copper” Molecular Compounds

Chiral Photomagnets Based on Copper(II) complexes of 1,2-Diaminocyclohexane and Octacyanidomolybdate(IV) Ions

In Situ Ligand Transformation for Two-Step Spin Crossover in Fe^II[M^IV(CN)₈]^4– (M = Mo, Nb) Cyanido-Bridged Frameworks

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Synthesis of the Single‐Crystalline Form and First‐Principles Calculations of Photomagnetic Copper(II) Octacyanidomolybdate(IV)

Abstract: A gel crystallization technique was successfully applied in the pioneering preparation of a single-crystalline form of the three-dimensional copper(II) octacyanidomolybdate(IV) network, which is a photomagnetic material. This assembly crystallizes with the formula {[Cu II

Cited by 20 publications

References 45 publications

Direct Evidence of a Photoinduced Electron Transfer in Diluted “Molybdenum‐Copper” Molecular Compounds

Direct Evidence of a Photoinduced Electron Transfer in Diluted “Molybdenum‐Copper” Molecular Compounds

Chiral Photomagnets Based on Copper(II) complexes of 1,2-Diaminocyclohexane and Octacyanidomolybdate(IV) Ions

In Situ Ligand Transformation for Two-Step Spin Crossover in FeII[MIV(CN)8]4– (M = Mo, Nb) Cyanido-Bridged Frameworks

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In Situ Ligand Transformation for Two-Step Spin Crossover in Fe^II[M^IV(CN)₈]^4– (M = Mo, Nb) Cyanido-Bridged Frameworks