Theoretical Studies on Magnetic Interactions in Prussian Blue Analogs and Active Controls of Spin States by External Fields

Nishino, Masamichi; Kubo, Shigehiro; Yoshioka, Yasunori; Nakamura, Akira; Yamaguchi, Kizashi

doi:10.1080/10587259708045050

Cited by 27 publications

(6 citation statements)

References 35 publications

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“…Recently, there has been tremendous interest in functional as well as synthetic design of coordination polymers based on crystal engineering. , In particular, the development of cyano-bridged bimetallic assemblies has been widely employed for multidimensional organic−inorganic coordination polymers as molecule-based magnets. , This fact has created important expectations in the search for new materials that possess not only expected properties with conventional dimensionality but also multifunctionality, for instance, photomagnets , and chiral magnets. − Some of the most famous photomagnets may be Fe−Co Prussian blue analogues, which are three-dimensional arrays of cyano-bridged inorganic solids showing photoinduced electron transfer , and lattice strain to weaken the ligand field of cyanide ligands . In addition, new photomagnets of Nd−Fe/Co 3d−4f bimetallic assemblies , do not exhibit photoinduced electron transfer but structural changes around cyano bridges after light irradiation.…”

Section: Introductionmentioning

confidence: 99%

Extremely Long Axial Cu−N Bonds in Chiral One-Dimensional Zigzag Cyanide-Bridged Cu^II^-Ni^II and Cu^II^-Pt^II Bimetallic Assemblies

Akitsu

Einaga

2006

Inorg. Chem.

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Preparations, crystal structures, and spectral and magnetic properties of two new chiral one-dimensional cyano-bridged coordination polymers, [Cu(II)L2]M(II)(CN)].2H2O (M(II) = Ni(II) (1) and Pt(II) (2), L = trans-cyclohexane-(1R,2R)-diamine) have been presented. Complex 1 crystallizes in the monoclinic P2(1) space group with a = 9.864(4) A, b = 15.393(8) A, c = 7.995(4) A, beta = 110.32(3) degrees , V = 1138.4(10) A3, and Z = 2, while 2 crystallizes in the monoclinic P2(1) space group with a = 9.899(3) A, b = 15.541(4) A, c = 8.102(2) A, beta = 111.02(2) degrees , V = 1163.6(5) A3, and Z = 2. The unique zigzag cyano-bridged chains along the crystallographic b axis consist of alternate chiral [CuL(2)]2+ cations and square-planar [M(CN)4]2- anions. One side of the axial Cu-N(triple bond C) bond distances are 2.324(6) and 2.34(1) A with Cu-N[triple bond]C angles of 137.8(6) degrees and 138.2(9) degrees for 1 and 2, respectively. On the other hand, the opposite side of the axial Cu-N(triple bond C) bond distances are 3.120(8) and 3.09(1) A with significantly large bent Cu-N[triple bond]C angles of 97.9(5) degrees and 96.8(7) degrees for 1 and 2, respectively. The novel axial bonding features of extremely long semi-coordination Cu-N bonds are attributed to coexistence of pseudo-Jahn-Teller elongation and electrostatic interaction in the unique zigzag cyano-bridged chains. The characteristic bonding features with overlap between small 3d (Ni(II)) or large 5d (Pt(II)) and 3d (Cu(II)) orbitals results in larger shifts in XPS peaks of not only Cu2p(1/2) and Cu2p(3/2) but also Ni2p(1/2) and Ni2p(3/2) for 1 than those of 2, which is also consistent with weak antiferromagnetic interactions with Weiss constants of -5.31 and -5.94 K for 1 and 2, respectively. The d-d, pi-pi*, and CT bands in the electronic, CD, and MCD spectra for 1 and 2 in the solid state at room temperature are discussed from the viewpoint of magneto-optical properties.

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Section: Introductionmentioning

confidence: 99%

Extremely Long Axial Cu−N Bonds in Chiral One-Dimensional Zigzag Cyanide-Bridged Cu^II^-Ni^II and Cu^II^-Pt^II Bimetallic Assemblies

Akitsu

Einaga

2006

Inorg. Chem.

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“…The model in our previous study can qualitatively explain the fundamental aspects of the interesting photoinduced magnetic properties. Yamaguchi et al have systematically analyzed the magnetic interactions in various Prussian blue analogues from ab initio UHF (unrestricted Hartree−Fock) and DFT (density functional theory) calculations, using binuclear transition metal cyanide models. A DFT band structural analysis for the (Mn, Cr) and (Ni, Cr) Prussian blue complexes was recently reported by Eyert et al However, since the actual Prussian blue complexes include crystal water, interstitial potassium ions, vacancies, and lattice defects, we should take these features into account for an extended analysis in this paper.…”

Section: Introductionmentioning

confidence: 99%

Analysis of Photoinduced Magnetization in a (Co, Fe) Prussian Blue Model

et al. 1998

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The electronic properties of a modified (Co, Fe) Prussian blue compound, which exhibits interesting photoinduced magnetic properties, are analyzed. For band structure calculations we set realistic models (for the ground and excited states) that involve interstitial potassium ions, crystal water, and lattice defects. The top of the “t2g” block consists mainly of Fe 3d orbitals, the low-lying “eg(1)” block Co 3d, and the high-lying “eg(2)” block Fe 3d. Because of the influence of crystal water coordinating to the Co ion, the “eg(1)”-block bands split into two parts; one is the “eg(1)(N)” block originating from the Co−NC fragment and another the “eg(1)(O)” block from the Co−OH2 fragment. The energy of visible light causing the magnetization enhancement is close to the computed “t2g(Fe-based)−eg(1)(N)” and “t2g(Fe-based)−eg(1)(O)” separations in the ground-state model. It is reasonable from DOS (density of states) analyses that irradiation with visible light causes an electron transfer from the Fe(II) to the Co(III) ions, through which the magnetization is effectively enhanced. Such an electron transfer is not a d−d transition on the same metal ion so that the Laporte rule may not be applied, or if applied, this rule may be relaxed in the (Co, Fe) Prussian blue.

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“…All Na 2 PR(CN) 6 were initialized with P and R in the 2+ oxidation state, whereas different initializations of oxidation states (P 3+ R 3+ , P 4+ R 2+ , P 2+ R 4+ ) for PR(CN) 6 were evaluated to identify the lowest-energy configuration. PBAs have been shown to exhibit various spin-ordering configurations with temperatures, compositions, and photoinduction. − For all polymorphs, we calculated the total energies of all possible spin-ordering configurations, and the lowest-energy one was used for the property calculations (Table S1). In this work, only ferromagnetic configurations were considered based on previous results from Nishino et al All crystal structure manipulations and data analyses were performed using the Python Materials Genomics (pymatgen) package …”

Section: Theoretical Approachmentioning

confidence: 99%

“…25−27 For all polymorphs, we calculated the total energies of all possible spin-ordering configurations, and the lowest-energy one was used for the property calculations (Table S1). In this work, only ferromagnetic configurations were considered based on previous results from Nishino et al 27 All crystal structure manipulations and data analyses were performed using the Python Materials Genomics (pymatgen) package. 28 Average Voltage.…”

Section: ■ Introductionmentioning

confidence: 99%

Water Contributes to Higher Energy Density and Cycling Stability of Prussian Blue Analogue Cathodes for Aqueous Sodium-Ion Batteries

et al. 2019

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In this work, we performed a comprehensive study of Prussian blue and its analogues (PBAs), one of the most promising cathode materials for aqueous sodium-ion batteries for large-scale energy-storage systems, using first-principles calculations. It is confirmed that dry PBAs generally undergo a phase transition from a rhombohedral Na2PR(CN)6 (where P and R are transition metals) to a tetragonal/cubic PR(CN)6 during Na extraction, in agreement with experimental observations. Using a grand potential phase diagram construction, we show that water and Na co-intercalation result in fundamentally different phase transition behavior and, hence, electrochemical voltage profiles in wet versus dry electrolytes. Lattice water increases the average voltage and reduces the volume change during electrochemical cycling, resulting in both higher energy density and better cycling stability. Finally, we identified four new PBA compositions, Na2CoMn(CN)6, Na2NiMn(CN)6, Na2CuMn(CN)6, and Na2ZnMn(CN)6, that show great promise as cathodes for aqueous rechargeable Na-ion batteries.

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Theoretical Studies on Magnetic Interactions in Prussian Blue Analogs and Active Controls of Spin States by External Fields

Cited by 27 publications

References 35 publications

Extremely Long Axial Cu−N Bonds in Chiral One-Dimensional Zigzag Cyanide-Bridged Cu^II^-Ni^II and Cu^II^-Pt^II Bimetallic Assemblies

Extremely Long Axial Cu−N Bonds in Chiral One-Dimensional Zigzag Cyanide-Bridged Cu^II^-Ni^II and Cu^II^-Pt^II Bimetallic Assemblies

Analysis of Photoinduced Magnetization in a (Co, Fe) Prussian Blue Model

Water Contributes to Higher Energy Density and Cycling Stability of Prussian Blue Analogue Cathodes for Aqueous Sodium-Ion Batteries

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Theoretical Studies on Magnetic Interactions in Prussian Blue Analogs and Active Controls of Spin States by External Fields

Cited by 27 publications

References 35 publications

Extremely Long Axial Cu−N Bonds in Chiral One-Dimensional Zigzag Cyanide-Bridged CuII-NiII and CuII-PtII Bimetallic Assemblies

Extremely Long Axial Cu−N Bonds in Chiral One-Dimensional Zigzag Cyanide-Bridged CuII-NiII and CuII-PtII Bimetallic Assemblies

Analysis of Photoinduced Magnetization in a (Co, Fe) Prussian Blue Model

Water Contributes to Higher Energy Density and Cycling Stability of Prussian Blue Analogue Cathodes for Aqueous Sodium-Ion Batteries

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Product

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Extremely Long Axial Cu−N Bonds in Chiral One-Dimensional Zigzag Cyanide-Bridged Cu^II^-Ni^II and Cu^II^-Pt^II Bimetallic Assemblies

Extremely Long Axial Cu−N Bonds in Chiral One-Dimensional Zigzag Cyanide-Bridged Cu^II^-Ni^II and Cu^II^-Pt^II Bimetallic Assemblies