掲載種別：研究論文（学術雑誌）   出版者・発行元：Dalton Transactions  

A novel 2D Hofmann-type framework was prepared with a bidentate co-ligand, 5,5′-dimethyl-2,2′-bipyridyl (dmbpy), which forces the curvature of the layer. X-ray diffraction analysis demonstrated that the coordination polymers, MnII(dmbpy)[MVN(CN)4] (MV = Mn (1) and Cr (2)), formed a considerably corrugated 2D cyanide-bridged network with a quasi C4v symmetric building unit, [CrVN(CN)4]2−, and trigonal prismatic coordination geometry around MnII. Compound 2 demonstrated a metamagnetic-like ordering at 14.4 K, caused by the intra- and inter-layer antiferromagnetic interactions between CrV (S = 1/2) and MnII (S = 5/2), and a weak ferromagnetic behaviour at 2 K reflecting the single-ion anisotropy of CrV and structural anisotropy.

DOI： 10.1039/d3dt03914e

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記述言語：その他   掲載種別：研究論文（学術雑誌）   出版者・発行元：Inorganic Chemistry  

The synthesis of Janus-type layers, which possess front and back sides that consist of different structures, remains a major challenge in the field of two-dimensional materials. In this study, two Janus-type layered coordination polymers, namely, CuII(NEtH2)(NMe2H·H2O)CuI(CN)3 (1) and CuII(NMe2H)(NMe2H·H2O)CuI(CN)3 (2), were synthesized via a simple one-pot procedure using copper(II) nitrate and sodium cyanido in mixed solutions of dimethylamine and ethylamine. Uniquely, 1 and 2 were composed of cyanido-bridged neutral layers and exhibited a CuICuII mixed-valent state. Meanwhile, using a solution of pure dimethylamine for the synthesis yielded the monovalent three-dimensional framework (NMe2H2)[CuI2(CN)3] (3). Results indicated that the simultaneous use of two mixed amines gave rise to the controlled reduction of CuII ions during the reaction. In addition, each face of the layers was coordinated by different amines on the axial positions of the CuII sites, resulting in anisotropic Janus layers. Furthermore, the thermal expansion behavior of 2 was investigated, demonstrating that the neutral [CuICuII(CN)3] layer was relatively rigid compared with the analogous anionic [CuI2(CN)3]− layer.

DOI： 10.1021/acs.inorgchem.3c03100

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出版者・発行元：Dalton Transactions  

An efficient water-based purification strategy for metal-organic polyhedra (MOPs) using commercially available centrifugal ultrafiltration membranes was developed. Having a diameter above 3 nm, MOPs were almost fully retained by the filters, while free ligands and other impurities were washed away. MOP retention also enabled efficient counter-ion exchange. This method paves the way for the application of MOPs with biological systems.

DOI： 10.1039/d3dt01644g

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：Angewandte Chemie - International Edition  

We synthesized a (1-propylpyridinium)2[ReN(CN)4]-type organic–inorganic hybrid exhibiting water-vapor-induced drastic structural changes of the [ReN(CN)4]2− assemblies. Specifically, upon exposure to water vapor, dehydrated nitrido-bridged chains were converted to hydrated cyanido-bridged tetranuclear clusters via rearrangements of large molecular building units in the crystals. These switchable assembly forms display substantially different photo-physical properties, although in both cases the emission is caused by a metal-centered d–d transition. The nitrido-bridged chain exhibited a near-infrared (749 nm) emission, which blue-shifted as the temperature increased, while a visible (561 nm) emission and its red shift was demonstrated by the cyanido-bridged cluster.

DOI： 10.1002/anie.202306853

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記述言語：日本語   出版者・発行元：錯体化学会  

<p>We have investigated cyanide-based metal complexes, which were synthesized by combining [M(CN)₄]^2- (M = Pt, Pd, Ni) or [MN(CN)₄]^2- (M = Mn, Re) with metal complex cations, metal ions, and organic cations, by focusing on their dynamic structures such as thermal expansion (TE) and phase transition. For example, FePd(CN)₄ is a three dimensional framework consisting of four-coordinate iron(II) nodes. This metal cyanide demonstrates large anisotropic TE involving negative TE (NTE) and colossal positive TE (PTE) during 100 K-500 K. Other examples are two-dimensional (2D) undulating layer-type coordination polymers of type [M(salen)]₂[Ḿ (CN)₄] (M = Mn, Fe; Ḿ = MnN, ReN, Pt, Pt(I₂)_x; x = 0.18, 0.45, 0.85, 1.0). Uniquely, they demonstrate composition-dependent anisotropic TE including 2D-PTE and 2D-NTE with wide range of linear TE coefficient values −45~+63 × 10^-6 K^-1. Furthermore, the combination of [MN(CN)₄]^2-(M = Mn, Re) with an ionic liquid cation, 1-ethyl-3-methylimidazolium (EmIm⁺), provided melting systems of (EmIm)₂[MN(CN)₄] involving cyanide-bridged architectures. Moreover, we also developing molecular probes incorporating the metal complex moieties, that can work in complex environments such as cell membranes, to investigate and promote membrane functions.</p>

DOI： 10.4019/bjscc.81.50

CiNii Research

記述言語：その他   掲載種別：研究論文（学術雑誌）   出版者・発行元：Journal of the American Chemical Society  

Metal-organic polyhedra (MOPs) can act as elementary structural units for the design of modular porous materials; however, their association with biological systems remains greatly restricted by their typically low stabilities and solubilities in water. Herein, we describe the preparation of novel MOPs bearing either anionic or cationic groups and exhibiting a high affinity for proteins. Simple mixing of the protein bovine serum albumin (BSA) and ionic MOP aqueous solutions resulted in the spontaneous formation of MOP-protein assemblies, in a colloidal state or as solid precipitates depending on the initial mixing ratio. The versatility of the method was further illustrated using two enzymes, catalase and cytochrome c, with different sizes and isoelectric points (pI's) below and above 7. This mode of assembly led to the high retention of catalytic activity and enabled recyclability. Furthermore, the co-immobilization of cytochrome c with highly charged MOPs resulted in a substantial 44-fold increase of its catalytic activity.

DOI： 10.1021/jacs.2c13798

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記述言語：その他   掲載種別：研究論文（学術雑誌）   出版者・発行元：Inorganic Chemistry  

The negative thermal expansion (NTE) of solid-state materials is of significance in various fields, but a very rare phenomenon. In this study, we carried out a meta-analysis for the anisotropic thermal expansion behavior of fifteen two-dimensional coordination polymers [M(salen)]2[M′(CN)4(solvent)] (M = Mn, Fe; M′ = MnN, ReN, Pt, Pt(I2)x; x = 0.18, 0.45, 0.85, 1.0; solvent = H2O, MeOH, MeCN) with a newly synthesized [Fe(salen)]2[MnN(CN)4(MeCN)]. Consequently, we successfully demonstrate the unusual NTE of the undulating coordination layers by an expansion deformation of the layers via strong interlayer interaction within the layer stacking. Notably, the layer volume of [Mn(salen)]2[ReN(CN)4] with its powder form decreases with a large NTE coefficient, αlayer-volume= -27 × 10-6K-1(100-500 K). This is a significantly large value despite the increase in layer thickness along the layer contraction based on the anisotropic transformation of undulating layers. Conversely, the analysis demonstrates that the chemical modification of the layers to enhance intralayer interaction rather than interlayer interaction switches a direction of the layer anisotropy, yielding positive thermal expansion materials with the coefficient of the layer volume reaching +92 × 10-6K-1

DOI： 10.1021/acs.inorgchem.2c03780

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記述言語：その他   掲載種別：研究論文（学術雑誌）   出版者・発行元：Nature Communications  

Abstract

Prussian blue analogues (PBAs) are archetypes of microporous coordination polymers/metal–organic frameworks whose versatile composition allows for diverse functionalities. However, developments in PBAs have centred solely on their crystalline state, and the glassy state of PBAs has not been explored. Here we describe the preparation of the glassy state of PBAs via a mechanically induced crystal-to-glass transformation and explore their properties. The preservation of short-range metal–ligand–metal connectivity is confirmed, enabling the framework-based functionality and semiconductivity in the glass. The transformation also generates unconventional CN⁻ vacancies, followed by the reduction of metal sites. This leads to significant porosity enhancement in recrystallised PBA, enabled by further accessibility of isolated micropores. Finally, mechanical stability under stress for successful vitrification is correlated to defect contents and interstitial water. Our results demonstrate how mechanochemistry provides opportunities to explore glassy states of molecular framework materials in which the stable liquid state is absent.

DOI： 10.1038/s41467-022-31658-w

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その他リンク： https://www.nature.com/articles/s41467-022-31658-w

記述言語：その他   掲載種別：研究論文（学術雑誌）   出版者・発行元：Inorganic Chemistry  

Chemical responsivity in materials is essential to build systems with switchable functionalities. However, polarity-switchable materials are still rare because inducing a symmetry breaking of the crystal structure by adsorbing chemical species is difficult. In this study, we demonstrate that a molecular organic-inorganic hybrid crystal of (NEt4)2[MnN(CN)4] (1) undergoes polarity switching induced by water vapor and transforms into a rare example of proton-conducting second-harmonic-generation-active material. Centrosymmetric 1 transforms into noncentrosymmetric polar 1·3H2O and 1·MeOH by accommodating water and methanol molecules, respectively. However, only water vapor causes a spontaneous single-crystal-to-single-crystal transition. Moreover, 1·3H2O shows proton conduction with 2.3 × 10-6S/cm at 298 K and a relative humidity of 80%.

DOI： 10.1021/acs.inorgchem.2c02555

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記述言語：その他   掲載種別：研究論文（学術雑誌）   出版者・発行元：CrystEngComm  

The zero area TE of cyanide-bridged honeycomb layers occurs by complementary structural changes in the cation and anion counterparts.

DOI： 10.1039/d2ce00878e

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記述言語：その他   掲載種別：研究論文（学術雑誌）   出版者・発行元：Physical Chemistry Chemical Physics  

Soft X-ray absorption study for low-crystallinity metal organic frameworks to investigate the ligand field.

DOI： 10.1039/d2cp01415g

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記述言語：その他   掲載種別：研究論文（学術雑誌）  

DOI： 10.1002/chem.202103404

記述言語：その他   掲載種別：研究論文（学術雑誌）  

DOI： 10.1246/cl.210244

記述言語：英語   掲載種別：研究論文（学術雑誌）  

A novel porous magnet consisting of cationic two-dimensional (2-D) layers extended by Fe-III-CN-Ni-II linkages and pseudo-pillar dianions was synthesized. The size-selective guest adsorption behaviour of water and methanol molecules originates from the narrow bottle-neck-type pores in the flexible pseudo-pillared-layer structure, which results in the switching of the magnetic phases from antiferromagnetic to ferromagnetic, involving significant changes in the interlayer distance.

DOI： 10.1039/d1cc01526e

記述言語：その他   掲載種別：研究論文（学術雑誌）  

DOI： 10.1002/cnma.202100026

記述言語：その他   掲載種別：研究論文（学術雑誌）  

DOI： 10.1021/acs.inorgchem.1c00702

記述言語：その他   掲載種別：研究論文（学術雑誌）  

<p>A series of crystalline porous materials was prepared by self-assembly of cationic metal–organic polyhedra with polyoxometalates.</p>

DOI： 10.1039/d1cc01185e

記述言語：その他   掲載種別：研究論文（学術雑誌）  

DOI： 10.1021/acs.inorgchem.0c03742

記述言語：その他   掲載種別：研究論文（学術雑誌）  

DOI： 10.1002/anie.202102774

記述言語：その他   掲載種別：研究論文（学術雑誌）  

<p>This review presents a discussion of soft metal complexes with a focus on spin crossover behaviours that are associated with structural phase transition, including liquid crystal LC transition.</p>

DOI： 10.1039/d1dt00004g

記述言語：その他   掲載種別：研究論文（学術雑誌）  

<p>The Jahn–Teller-like effect on the tetrahedral geometry of d⁶ iron(<sc>ii</sc>) is caused by its unequally occupied e orbitals with non-bonding nature.</p>

DOI： 10.1039/d0dt04155f

記述言語：その他   掲載種別：研究論文（学術雑誌）  

<p>This review discusses the correlation of the local and whole molecular structure of iron(<sc>iii</sc>) complexes with the magnetic properties including the light-induced excited spin-state trapping (LIESST) effect.</p>

DOI： 10.1039/d0qi01188f

記述言語：その他  

© 2020 Wiley-VCH GmbH Recently, “host–guest chemistry” aspects of material science have received much attention, particularly in relation to moderating the functions of materials. In particular, magnetic properties involving the “magnetic ordering” and “spin crossover” of host–guest metal complex systems have been actively investigated in terms of their host–guest chemistry. That is, systems in which the magnetic properties are sensitive to perturbation by the uptake of guests (which thus act as chemical stimuli). Such guests (solvents, gases and organic molecules) very often influence the structures of both discrete metallosupramolecular assemblies as well as those of coordination polymers/metal-organic frameworks (CPs/MOFs), providing a means for fine-tuning their magnetic behavior, including the switching of their spin states. In this minireview, we report recent progress in the development and investigation of magnetic materials of both the CP and MOF categories as well as of discrete complexes whose properties are modulated by guests.

DOI： 10.1002/ejic.202000553

記述言語：その他   掲載種別：研究論文（学術雑誌）  

DOI： 10.1002/anie.202008187

記述言語：その他   掲載種別：研究論文（学術雑誌）  

DOI： 10.1002/anie.202006600

記述言語：その他   掲載種別：研究論文（学術雑誌）  

<p>A Re(<sc>v</sc>) mononuclear complex switches the characters of emissive states by methanol vapor <italic>via</italic> a single-crystal-to-single-crystal ligand exchange reaction.</p>

DOI： 10.1039/d0cc05462c

記述言語：その他   掲載種別：研究論文（学術雑誌）  

<p>Luminescent ionic liquids are formed by the melting of tetranuclear rhenium(<sc>v</sc>) clusters.</p>

DOI： 10.1039/d0cc02937h

記述言語：英語   掲載種別：研究論文（学術雑誌）  

A hexagonal cobalt(ii) metallacycle and its "lipid packaged" derivatives, [Co6(R-bisterpy)6]X12 (R = H, OC16H33, OC27H55; X = BF4, C12-Glu), have been synthesized and characterized. The compounds incorporating BF4- anions formed sphere-like aggregates while the compounds with C12-Glu lipid anions gave double-layered honeycomb architectures composed of hexagonal stacked tubular structures, which exhibit spin crossover behaviour.

DOI： 10.1039/d0cc02628j

記述言語：英語   掲載種別：研究論文（学術雑誌）  

The ortho-isomer of molecular hydrogen (o-H₂) was converted to the para-isomer (p-H₂) within 600 s by using Prussian blue analogs, {M^II ₃[Cr^III(CN)₆]₂} (MCr; M = Mn and Ni), as nuclear-spin conversion catalysts. The swift conversion was confirmed by in-situ Raman micro-spectroscopy under an H₂ gas atmosphere (100 kPa) in a low temperature range (2090 K). The o-p ratio observed in MCr deviated from the theoretical value based on the Boltzmann distribution of H₂ in a free rotational state to the para-rich proportion, which suggested the promotion of the o-p conversion at higher temperature.

DOI： 10.1246/cl.190829

記述言語：英語   掲載種別：研究論文（学術雑誌）  

Two-dimensional Hofmann-type coordination polymers of type Mn(H₂O)₂[Pd(CN)₄]·xH₂O (1·xH₂O; x = 0, 1, and 4), Mn(H₂O)(MeOH)[Pd(CN)₄]·2MeOH (2·2MeOH), and Mn(MeOH)₂[Pd(CN)₄]·MeOH (3·MeOH) have been synthesized. The homosolvent-bound 1·4H₂O, 1·H₂O, and 3·MeOH polymers consist of undulating layer structures, whereas the structure of heterosolvent-bound 2·2MeOH consists of "Janus-like" flat layers in which water-bound and MeOH-bound-sides are present. 1·4H₂O and 1·H₂O exhibited anisotropic two-dimensional thermal expansions involving structural transformations of the undulating layers; one layer axis expands while the other contracts. 2·2MeOH exhibits anisotropic thermal expansion in which the flat layers shift sideways as the temperature is increased, with colossal interlayer expansion occurring (α_c = +200 MK^-1 over 140-180 K, α_c = +165 MK^-1 over 200-280 K). 3·MeOH also showed colossal interlayer expansion (α_c = +216 MK^-1) together with expansion of the undulating layers.

DOI： 10.1021/acs.inorgchem.9b01660

記述言語：その他  

Triply methoxo-bridged tetranuclear nickel cubane complexes with salicylate esters

DOI： 10.1007/s10847-018-0798-9

記述言語：その他  

Structure and magnetic property of mu-oxo bridged dinuclear iron(III) complex with trialkylated tridentated ligands

DOI： 10.1007/s10847-018-0810-4

記述言語：その他  

Morphology and magnetic properties of synthesized lipid packaged iron(II) complex

DOI： 10.1007/s10847-018-0815-z

記述言語：英語   掲載種別：研究論文（学術雑誌）  

The behavior of single-ion magnets (SIMs) that reflects large distortions of their coordination environments caused by the packing of long alkyl chains for two Co(II) complexes of the type [Co(C_n-terpy)₂](BF₄)₂ (C_n-terpy = 4′-alkoxy-2,2':6′,2″-terpyridine; n = 10 (1), 16 (2)) is reported. 1·2MeOH, which features a highly distorted octahedral high-spin Co(II) center, exhibits field-induced slow magnetic relaxation under an applied dc field of 1000 Oe. Further detailed analysis of the relaxation process indicated the prevalence of the Raman process at low temperature. Surprisingly, 2 shows a reverse spin transition (rST) and also exhibits remarkable field-induced SIM behavior, revealing the presence of magnetic anisotropy for this high-spin Co(II) species that is triggered by a structural phase transition. We present here the first examples of the coexistence of field-induced slow magnetic relaxation and rST associated with structural phase transitions involving long-alkyl-chain conformational changes from gauche to anti. These results indicate the prospect of inducing SIM properties in other distorted high-spin Co(II) species bearing long alkyl chains.

DOI： 10.1021/acs.inorgchem.9b00543

記述言語：英語   掲載種別：研究論文（学術雑誌）  

Luminescent Zn
^II
clusters [Zn
₄
L
₄
(μ
₃
-OMe)
₂
X
₂
] (X=SCN (1), Cl (2), Br (3)) and [Zn
₇
L
₆
(μ
₃
-OMe)
₂
(μ
₃
-OH)
₄
]Y
₂
(Y=I
⁻
(4), ClO
₄

⁻
(5)), HL=methyl-3-methoxysalicylate, exhibiting blue fluorescence at room temperature (λ
_max
=416≈429 nm, Φ
_em
=0.09–0.36) have been synthesised and investigated in detail. In one case the external heavy-atom effect (EHE) arising the presence of iodide counter anions yielded phosphorescence with a long emission lifetime (λ
_max
=520 nm, τ=95.3 ms) at 77 K. Single-crystal X-ray structural analysis and time-dependent density-functional theory (TD-DFT) calculations revealed that their emission origin was attributed to the fluorescence from the singlet ligand-centred (
¹
LC) excited state, and the phosphorescence observed in 4 was caused by the EHE of counter anions having strong CH−I interactions.

DOI： 10.1002/chem.201900343

記述言語：英語   掲載種別：研究論文（学術雑誌）  

Control of ion arrangements in ionic liquids represents a major challenge owing to the presence of the predominant coulombic interactions between cationic and anionic ion species that forms the coulombic ordering. Here, water-induced ion rearrangement in a room-temperature ionic liquid (RT-IL) metal complex, (1-ethyl-3-methylimidazolium)
₂
[MnN(CN)
₄
], is demonstrated through coordinative interactions between anions. Solidification occurred, which was associated with the formation of a “separated” structure consisting of cation columns and anionic cyanide-bridged one-dimensional coordination polymers. The energy diagram is in accord with the resultant RT-IL incorporating mononuclear [MnN(CN)
₄
]
²⁻
molecules being a kinetic phase stabilized by inter-ion repulsions of the anionic divalent metal complex moieties. Water acts to decrease the coulombic interactions, including repulsion, giving rise to breaking of the coulombic ordering arising from coordination bond formation in the IL phase.

DOI： 10.1002/chem.201900069

記述言語：英語   掲載種別：研究論文（学術雑誌）  

A homochiral one-dimensional (1D) Mn(iii) coordination polymer [MnL]_n (1) was synthesised employing the N₃O-donor tetradentate ligand (L = 2-hydroxy-N-[2-[[(2-aminophenyl)methylene]amino]-2-methylpropyl]-benzamide). The X-ray structure of 1 and its magnetic properties were investigated in detail. The crystal structure of 1 shows a homochiral helical arrangement in which spontaneous resolution has occurred, despite the ligand being achiral. Magnetic characterization revealed an antiferromagnetic interaction between manganese(iii) ions (J = -2.48 cm^-1, g = 1.96) that leads to an antiferromagnetic spin-ordering phase transition at T_N ≈ 7 K. Noteworthily, 1 exhibits weak ferromagnetism with a relatively large coercive field of 3.0 kOe based on the spin canting, indicating the formation of a homochiral weak ferromagnet.

DOI： 10.1039/c9dt00593e

記述言語：英語   掲載種別：研究論文（学術雑誌）  

The 2D coordination polymers, [Mn(salen)]₂[Pt^II(CN)₄]_1-x[Pt^IV(CN)₄(I₂)]_x (salen = N,N'-ethylenebis(salicylideneaminato), x = 0.18 (1), 0.45 (2), 0.85 (3)), have been synthesized via consecutive oxidative additions of iodine to the 2D undulating layers in [Mn(salen)]₂[Pt^II(CN)₄]. The presence of I-Pt-I chains perpendicular to the layers and the inhomogeneity of individual I-Pt-I sites were demonstrated. The I-Pt-I chains in 3 give rise to an absorption band involving the excitation that arises from an antibonding nature orbital to the corresponding bonding nature orbital between iodides in the I-Pt-I bridging units. Moreover, variable-temperature X-ray powder diffraction patterns and Raman spectra for 1 and 2 indicate that some I-Pt-I sites display different vibrational energies that are associated with the contraction of the zigzag 2D layers.

DOI： 10.1039/c8dt04624g

記述言語：英語   掲載種別：研究論文（学術雑誌）  

The ability to tune physical properties is attractive for the development of new materials for myriad applications. Understanding and controlling the structural dynamics in complicated network structures like coordination polymers (CPs) is particularly challenging. We report a series of two-dimensional CPs [Mn(salen)]₂[M(CN)₄]·xH₂O (M = Pt (1), PtI₂ (2), and MnN (3)) incorporating zigzag cyano-network layers that display composition-dependent anisotropic thermal expansion properties. Variable-temperature single-crystal X-ray structural analyses demonstrated that the thermal expansion behavior is caused by double structural distortions involving [Mn(salen)]⁺ units incorporated into the zigzag layers. Thermal relaxations produce structural transformations resulting in positive thermal expansion for 2·H₂O and negative thermal expansion for 3. In the case of 1·H₂O, the relaxation does not occur and zero thermal expansion results in the plane between 200 to 380 K. The present study proposes a new strategy based on structural distortions in coordination networks to control thermal responsivities of frameworks.

DOI： 10.1021/acs.inorgchem.8b01617

記述言語：英語   掲載種別：研究論文（学術雑誌）  

The dinuclear iron(III) complex [Fe(salten)₂(bipytz)](BPh₄)₂·EtOH (1) was synthesized and its post-synthesis modification yielded [Fe(salten)₂(bipydz)](BPh₄)₂·EtOH (2). The crystal structures and magnetic behaviors of 1 and 2 were investigated by variable temperature XRD, magnetic susceptibility, and Mössbauer spectra measurements, with each of these dinuclear iron(III) complexes exhibiting gradual spin crossover behavior.

DOI： 10.1002/zaac.201800087

記述言語：英語   掲載種別：研究論文（学術雑誌）  

Iron(III) spin-crossover (SCO) complexes [Fe(qsal)
₂
]BS·MeOH·H
₂
O (1), [Fe(qsal)
₂
](NS)·MeOH (2), [Fe(qnal)
₂
](NS) (3), and [Fe(qnal)
₂
]PS·MeOH·CH
₂
Cl
₂
(4) (Hqsal, N-(8-quinolinyl)salicylaldimine; Hqnal, N-(8-quinolinyl)-2-hydroxy-1-naphthaldimine; BS, benzenesulfonate; NS, 1-naphthalenesulfonate; PS, 1-pyrenesulfonate) have been synthesized and characterized by X-ray structure determinations and temperature-dependent magnetic susceptibility measurements. The aromatic counteranions BS, NS, and PS can be used for the tuning of intermolecular coupling through a variety of weak interactions. All of the complexes show temperature-dependent SCO behavior. but the light-induced excited spin-state trapping (LIESST) effect was observed only for 1, 3, and 4 when the samples were illuminated (λ 808 nm) for 1 h at 5 K. In particular, 59% of the LS form of 1 was converted to the metastable HS state by illumination, equal to the highest degree of conversion yet known for LIESST in [Fe(qsal)
₂
]
⁺
derivatives. The lack of a LIESST effect for 2 may be due to the relatively limited degree of interaction between the cations and anions in the lattice, reflected in a much longer minimum Fe···Fe separation in this complex in comparison to the others.

DOI： 10.1021/acs.inorgchem.7b03126

記述言語：英語   掲載種別：研究論文（学術雑誌）  

High dielectric constants (e_r) were observed in two-dimensional composites obtained from stacking of reduced graphene oxide (RGO) with Ca₂Nb₃O₁₀ and with TiO₂ nanosheets. The relative dielectric permittivity values of the composites were found to be higher than 10⁵, an amazingly high value compared to that of similar GO composites and other common dielectric materials. As a consequence, we considered application of the hybrids as super dielectric materials in high capacitance supercapacitors. The route to high capacitance involves the variation of oxygen vacancies within the surface and in the closest bulk interior of the hybrids. The effective charges generated throughout the metal oxide and carbon-oxygen polar bonding systems within the graphene skeleton appear to highly influence dielectric polarization. Moreover, the replenishment of oxygen vacancies at the RGO and metal oxide interface also contributes to polarizability.

DOI： 10.1021/acsomega.7b01764

記述言語：英語   掲載種別：研究論文（学術雑誌）  

The cobalt(ii) complex incorporating π-conjugated substituent, [Co(Naph-C2-terpy)₂](BF₄)₂ (1; Naph-C2-terpy = 4′-(2-naphthoxy(ethoxy))-2,2′:6′,2′′-terpyridine), exhibits an abrupt spin transition (ST) behavior (cooperative factor C = 0.91) while its solvated product, 1·2MeOH, shows gradual spin crossover (SCO) behavior (C = 0.49). Single crystal X-ray structural analyses demonstrated that the octahedral coordination core [CoN₆] in 1 shows larger distortion in both high-spin and low-spin states than solvated 1·2MeOH or another two derivatives, [Co(R-terpy)₂](BF₄)₂ (R = 2-naphthyl (2), 9-anthracenyl (3)). The respective distortion parameters (Σ) are compared with those for previously reported SCO cobalt(ii) compounds. The highly-distorted [CoN₆] core in 1 (Σ = 126 in the HS state and 101.6 in the LS state) was stabilized by strong intermolecular interactions and observed an abrupt ST behaviour.

DOI： 10.1039/c8dt02367k

記述言語：英語   掲載種別：研究論文（学術雑誌）  

Wheel-type heptanuclear heterometallic clusters of stoichiometry [Ni_7−xM_x(HL)₆(μ₃-OMe)₄(μ₃-OH)₂]Cl₂ (L = 1-(2-hydroxy-3-methoxybenzamido)-2-(benzylideneamino)ethane; M = Zn²⁺, Co²⁺, Mn²⁺; x = 1, 3) were synthesized, and their metal ion dependent ferromagnetic properties were investigated. It was demonstrated that the central position of each cluster was occupied by a Ni²⁺ ion while other metal ions (Zn²⁺, Co²⁺ or Mn²⁺) were accommodated in peripheral positions. The magnetic interactions, anisotropy and magnetization of the resultant clusters were all influenced by the combinations of metal ions present.

DOI： 10.1039/c8dt03275k

記述言語：英語   掲載種別：研究論文（学術雑誌）  

Water dispersible metal complex nanoparticles were synthesized using the polyethylene glycol (PEG) coating method. The χ_mT values at room temperature for the NPs 1-3 were calculated using the Evans method, and the proton relaxation times, T1 and T2, were measured employing MRI. Both relaxation times were observed to decrease with increasing χ_mT value.

DOI： 10.1246/cl.180038

記述言語：英語   掲載種別：研究論文（学術雑誌）  

π-π stacking between GO and benzene sulfonic acid (BS), naphthalene sulfonic acid (NS), pyrene sulfonic acid (PS), and naphthalene disulfonic acid (ND) results in the formation of respective GO-BS, GO-NS, GO-PS and GO-ND hybrid materials. The proton conductivities of these materials follow the trend as GO-NS>GO-BS>GO-PS>GO>GO-ND. GO-NS, possessing the highest interlayer distance, exhibits the optimum proton conductivity. Evidently, GO-sulfonic acid hybrids reveal excellent superionic conductivity.

DOI： 10.1002/celc.201701026

記述言語：英語   掲載種別：研究論文（学術雑誌）  

Zinc(ii) and platinum(ii) complexes [M(X-4-C₁₈-salmmen)] (M = Zn (1) and Pt (2), X = R, S (optical isomer) and rac (racemate), salmmen = N,N′-monomethylenebis-salicylideneimine) were synthesized and investigated. The series of compounds represented by 1 (R, S and rac forms) display liquid crystalline state behaviour at 413 K, and exhibit both ferroelectric and fluorescence properties, while the compounds represented by 2 (R and S, and rac forms) do not display liquid crystal behaviour but do exhibit ferroelectric and fluorescence properties. The ferroelectric behaviour was confirmed by second harmonic generation (SHG) experiments. It is considered that the motion and fluctuation of the long alkyl chains in these complexes results in the observed ferroelectric properties.

DOI： 10.1039/c8dt01100a

記述言語：英語   掲載種別：研究論文（学術雑誌）  

A sextuply linked capsule incorporating two Ni(ii) cubane units is formed when Ni(ii) salts are reacted with N-aminoalkyl salicylamidato ligands in a 4:3 ratio in methanol. With a short (propyl) alkyl substituent, additional chloride counter ions are included in the cavity by occupation of one apex of each of the linked cubanes, while with a longer (pentyl) substituent, perchlorate and tetrafluoroborate anions are included, probably by H-bonding involving hydroxyl groups on the inner apices of the cubanes, indicating that the cavity can be regarded as suited to binding of hydrophilic units despite the lipophilic character of its links. The dicubane capsules show ferromagnetic behaviour typical of Ni(ii) cubanes in general, with coupling constants dependent upon the nature of the salt-derived counter anions.

DOI： 10.1039/c8dt01911h

記述言語：英語   掲載種別：研究論文（学術雑誌）  

Ca_2-αL_aαNb_3-βX_βO₁₀ nanosheets ((α, β=0-0.14), X= Rh(LaRh), Mn(LaMn), Fe(LaFe), Ni(LaNi)) were synthesized by exfoliation using the surfactant aided sonication method. These nanosheets demonstrated superior photocatalytic activities for water splitting into hydrogen at room temperature. SEM-EDX images and spectra confirmed the morphology and composition of the materials where doped metal precursors inserted into the heterogeneous structure aided the photocatalytic activity.

DOI： 10.1557/adv.2018.461

記述言語：英語   掲載種別：研究論文（学術雑誌）  

Tuneable pressure effects associated with changing interlayer distances in two-dimensional graphene oxide (GO)/reduced GO (rGO) layers are demonstrated through monitoring the changes in the spin-crossover (SCO) temperature (T
_1/2
) of [Fe(Htrz)
₂
(trz)](BF
₄
) nanoparticles (NPs) incorporated in the interlayer spaces of the GO/rGO layers. The interlayer separation along the GO to GO/rGO-NP composites to rGO series decreases smoothly from 9.00 Å (for GO) to 3.50 Å (for rGO) as the temperature employed for the thermal reduction treatments of the GO-NP composites is increased. At the same time, T
_1/2
increases from 351 K to 362 K along the series. This T
_1/2
increment of 11 K corresponds to that observed for pristine [Fe(Htrz)
₂
(trz)](BF
₄
) NPs under a hydrostatic pressure of 38 MPa. The influence of the stacked layer structures on the pseudo-pressure effects has been further probed by investigating the differences in T
_1/2
for [Fe(Htrz)
₂
(trz)](BF
₄
) that is present in the composite as larger bulk particles rather than as NPs.

DOI： 10.1038/s41598-017-12444-x

記述言語：英語  

Graphene oxide (GO) shows high proton conductivity (≈10-4 Scm-1), excellent mechanical stability, and electrical insulation property, which makes it an ideal candidate for use as a proton conducting solid state electrolyte. The prospects of using GO as single phase solid electrolyte in an all solid battery is presented herein. A battery with the cell configuration: Zn + ZnSO4•7H2O + graphite (anode) || GO (electrolyte) || MnO2 + graphite (cathode) is fabricated. Cyclic voltammetry confirms its rechargeable nature. The respective discharge capacity and power density of the cell are 360 μAh and 19.5 mW kg-1 at a constant current drain of 3 μA under the experimental conditions employed. GO based proton conductors are cleaner and cheaper than other solid electrolytes. The current study strongly suggests that GO can be used as a practical and beneficial component in solid state battery applications with low energy feedback.

DOI： 10.1002/gch2.201700054

記述言語：英語   掲載種別：研究論文（学術雑誌）  

Zero in-plane thermal expansion (TE) in a two-dimensional (2D) coordination polymer is demonstrated. The combination of components that expand and those that shrink into zigzag layers results in no net area change in the 2D materials with temperature. Single crystals of [Mn(salen)]
₂
[Mn(N)(CN)
₄
(guest)] (salen = N,N′-ethylenebis(salicylideneaminato), guest = MeOH and MeCN) were prepared, and variable-temperature single-crystal X-ray structural analyses demonstrated that these compounds exhibited both anisotropic positive and negative thermal expansion depending on the guest species. The TE behavior results from distortions of the octahedral coordination geometry of [Mn(salen)]
⁺
units in the zigzag layers. When both guests MeOH and MeCN were incorporated into one material, [Mn(salen)]
₂
[Mn(N)(CN)
₄
(MeOH)
_0.25
(MeCN)
_0.75
], zero in-plane TE resulted in a range of temperature between 380 and 440 K.

DOI： 10.1021/acs.inorgchem.7b00282

記述言語：英語   掲載種別：研究論文（学術雑誌）  

The nature of the molecular assemblies formed in the crystalline state by cobalt(II) terpyridine (terpy) complexes incorporating appended adenine (A) or thymine (T) bases was found to be controlled by which bases are present. Single-crystals of the cobalt(II) complexes [Co(A-C6-terpy)₂](BF₄)₂ (1) and [Co(T-C6-terpy)₂](BF₄)₂ (2) have needle and block habits, respectively. Subsequent mixing of 1 and 2 in MeOH resulted in isolation of [Co(A-C6-terpy)_1.5(T-C6-terpy)_0.5](BF₄)₂ (3) as plate-like crystals. A 3D network structure is present in 1 that incorporates 1D chains, whereas 2 adopts a 2D stacked structure constructed from ladder-type assemblies. For 3, “dimer-rings” consisting of [Co(A-C6-terpy)₂]²⁺ and [Co(A-C6-terpy)(T-C6-terpy)]²⁺ units are generated by means of base-pairing between A and T. Notably, 3 displays the first crystal structure of a heteroleptic cobalt(II) complex of [Co(A-C6-terpy)(T-C6-terpy)](BF₄)₂. These assembly differences involving the terpyridine cobalt(II) complex units in 1–3 affect the cooperativities influencing their spin crossover (SCO) behavior. The influence of the terminal nucleobases on the resulting assembly has been probed by investigating the co-crystallization of [Co(terpy)₂](BF₄)₂ (4) with [Co(C6-terpy)₂](BF₄)₂ (5) and 1 with 5.

DOI： 10.1002/chem.201700593

記述言語：英語   掲載種別：研究論文（学術雑誌）  

Invited for the cover of this issue is the group of Shinya Hayami at Kumamoto University, Japan. The cover image shows a Japanese New Year’s card symbolizing the dawn of a new era for chiral magnetism. Mt. Aso, which is the symbol of Kumamoto, was chosen for the background.

DOI： 10.1002/ejic.201700131

記述言語：英語   掲載種別：研究論文（学術雑誌）  

The host–guest composites of Hofmann-type iron(II) spin-transition (ST) porous coordination polymers incorporating guest molecules show guest-dependent ST behavior in accordance with the respective guest species, which may be a gas, solvent, halogen, or organic molecule. The guest also works as a chemical stimulant to switch the spin state of the host between high and low spin at room temperature. In this review, we discuss guest properties including size, shape, flexibility, chemical properties, and pore loading content, which impact the spin states of the host framework and the ST behavior exhibited by the host–guest composites.

DOI： 10.1002/chem.201601880

記述言語：英語   掲載種別：研究論文（学術雑誌）  

Chiral iron(II) complexes, [Fe{(R)-L}₂(NCS)₂] (1) and [Fe{(S)-L}₂(NCS)₂] (2), and racemic complex [Fe(rac)-L)₂(NCS)₂] (3) {L = α-methyl-N-(2-pyridinylmethylene)cyclohexanemethanamine} were synthesized. Their structures and magnetic properties were investigated by X-ray crystallography, magnetic susceptibility measurements, and Mössbauer spectroscopy. Complexes 1 and 2 crystallize in the trigonal system with space group P3₁21 and P3₂21, respectively. All complexes exhibit spin-crossover (SCO) behavior and light induced excited spin state trapping (LIESST) effects at 532 nm. Complexes 1 and 2 show similar gradual SCO behavior, and complex 3 shows more gradual SCO, which seems to be a result of the different crystal packing, as complex 3 is the symmetric isomer but 1 and 2 are asymmetric.

DOI： 10.1002/ejic.201601232

記述言語：英語   掲載種別：研究論文（学術雑誌）  

Trifunctional catalysts for simultaneously generating H₂, O₂ and H₂O provide a crucial means for improving the overall efficiency of H₂O electrolysis. A series of nonnoble metal [M = Fe(III), Co(II), Ni(II)]-nitrogen co-doped oxidized graphite rods (M-N/OGR) that function as in situ working electrodes for tri-functional oxygen evolution reaction, hydrogen evolution reaction, and oxygen reduction reaction electrocatalysis was prepared. The enhanced performance of the hybrid catalysts appear mostly associated with dual active site mechanisms originating from the synergic effects of M-N/Co-doped on the surface of the OGR. The development of multifunctional electrocatalysts with optimal catalytic activity using transition metals and nitrogen doped OGR opens new fields for in situ synthesized electrocatalysts for use in clean electrochemical energy storage and conversion technologies.

DOI： 10.1246/bcsj.20170102

記述言語：英語   掲載種別：研究論文（学術雑誌）  

A morphology transformation of hybrid liposomes was shown to occur from spherical vesicles to tubular micelles when increasing the ratio of the metal complex lipid present. Phase transition temperatures increased while viscosities decreased, indicating that the hybrids exhibit stronger interaction between heads but weaker interaction between alkyl chains than occurs in pristine liposomes.

DOI： 10.1039/c7cc07944c

記述言語：英語   掲載種別：研究論文（学術雑誌）  

Two ferromagnetic multinuclear Ni(ii) clusters, [Ni
₄
L
¹
₄
(μ
₃
-OMe)
₄
(CH
₃
OH)
₄
] (1) and [Ni
₇
(HL
²
)
₆
(μ
₃
-OMe)
₆
]Cl
₂
(2), and a mononuclear complex [NiL
³
]·2H
₂
O (3) (HL
¹
= benzyl 2-hydroxy-3-methoxybenzoate; H
₂
L
²
= 1-(2-hydroxy-3-methoxybenzamido)-2-(benzylideneamino)ethane; H
₂
L
³
= 1-(2-hydroxy-3-methoxybenzamido)-2-(pyridylmethyleneamino)ethane) were synthesised, and their structures and magnetic behaviours were investigated in detail. 1 has a [Ni
₄
O
₄
] cubane structure while 2 has a wheel-like [Ni@Ni
₆
] arrangement. The temperature-dependent magnetic susceptibilities for 1 and 2 are in accord with the presence of dominating intra-cluster ferromagnetic interactions between Ni(ii) ions. The best fits for their behaviours gave the following parameters: J
₁
= 11.06 cm
^-1
, J
₂
= 1.43 cm
^-1
, g = 2.29 for 1, and J
₁
= 6.87 cm
^-1
, J
₂
= -3.41 cm
^-1
, g = 2.24 for 2.

DOI： 10.1039/c7dt01757j

記述言語：英語   掲載種別：研究論文（学術雑誌）  

Self-assembled hybrid supramolecular architectures formed between amphiphilic anions and long alkylated cationic cobalt(ii) complexes of type [Co(C_n-terpy)₂](C₁₂-Glu)₂ (n = 15-20) have been synthesized and characterized by TEM, PXRD and magnetic susceptibility measurements. The hybrids display wire or rolled sheet supramolecular arrangements with odd and even alkyl chain dependence, with the cobalt(ii) centres exhibiting gradual spin-crossover behaviours.

DOI： 10.1039/c7cc01501a

記述言語：英語   掲載種別：研究論文（学術雑誌）  

Insertion of 3-hydroxypropanesulfonicacid (HPS) in the graphene oxide (GO) interlayer results in high proton conductivity (10⁻²–10⁻¹ S cm⁻¹), owing to an improvement in oxygen content, interlayer distance and water absorbing capacity. This result indicates that hydroxyalkylsulfonicacids can be perfect guest molecules for improving the proton conductivity of carbon materials.

DOI： 10.1002/asia.201601488

記述言語：英語   掲載種別：研究論文（学術雑誌）  

Hybrid materials that are obtained from intercalation of different polar and hydrophilic acid guest molecules within graphene oxide (GO) have been found to exhibit high proton conductivity. The accommodation of these guest precursors within the GO interlayer takes place through weak physical forces. PXRD patterns with enhanced interlayer distance confirmed successful intercalation processes. Raman and IR spectral data reveal the absence of any covalent bond between the functional groups of the guest and the GO host. TGA data confirms improved water adsorbing capacity of the hybrids. At ambient conditions and 90% relative humidity (RH), a RH dependent impedance study shows that intercalation of formic acid (FA) and phosphoric acid (PA) within GO results in ∼7 times higher proton conductivity compared with that for the pristine GO sample. The low activation energy values suggest that proton conduction in the samples is aided by the Grotthuss mechanism. Improvement in the water adsorbing capacity is primarily responsible for such high proton conductivity. The current study suggests that cheap and environmentally friendly GO-based intercalated hybrid materials, such as GO/PA and GO/FA with enhanced proton conductivity, can be appropriate replacements for the expensive Nafion-based solid electrolytes.

DOI： 10.1039/c7ra01634d

記述言語：英語   掲載種別：研究論文（学術雑誌）  

The aging effect on the proton conductivity of graphene oxide (GO) is investigated. Characterizations of oxygenated functional groups and measurement of the proton conductivity have been performed using freshly prepared GO and the same sample after preserving for three years under ambient conditions. Although GO retains its layered structure, a slight deviation in its powder X-ray diffraction (PXRD) pattern and Raman spectra upon aging implies some changes in the interlayer distance and functional groups. Decomposition of epoxy groups on aging has been recognised by X-ray photoelectron spectroscopy (XPS) analysis. The proton conductivity was found to be reduced by 25% after three years of aging.

DOI： 10.1071/CH16557

記述言語：英語   掲載種別：研究論文（学術雑誌）  

Both p- and n-type field effect transistors (FET) properties have been observed in undoped reduced graphene oxide (rGO). Short and long time exposure of GO during photo reduction results in the formation of respective p- and n-type rGO semiconductor. Achieving duel behavior of this type in an undoped material is exceedingly unusual. Herein we report the presence of such behavior in the reduced from of graphene oxide (rGO) for the first time.

DOI： 10.1002/slct.201701509

記述言語：英語   掲載種別：研究論文（学術雑誌）  

A stable single-phase mixed electron/proton conductor with excellent capacitance from oxygen-functionalized porous carbon (OPC) has been presented herein. Electrochemical study suggested that at room temperature and 90% RH the values of electronic and protonic conductivity of OPC are 1.68

DOI： 10.1246/cl.170677

記述言語：英語   掲載種別：研究論文（学術雑誌）  

We reported the proton conductivities of a series of oxidized fullerenes (fullerenols) having varied polarity and hydrophilicity. The samples were generated from the oxidation of fullerenes by using different oxidation techniques and oxidizing agents. XPS, IR and TGA data confirmed the successful oxidation of fullerenes. Electrochemical impedance showed that fullerenols can support proton conductivity. At room temperature and 90% RH, a maximum proton conductivity of 1.4 × 10^-2 S cm^-1 was observed in fullerenols obtained from the oxidation of fullerene (C₆₀) by caustic soda. We expect the use of fullerenols as solid electrolytes in fuel cells, sensors, chemical filters and so on.

DOI： 10.1039/c7nj02964k

記述言語：英語   掲載種別：研究論文（学術雑誌）  

Cobalt(ii) complexes with terpyridine-type ligands, [Co(n-pyterpy)₂](ClO₄)₂ (n=3 (1), 4 (2)), were prepared and characterised. Different positions of the nitrogen atom in the terpyridine ligands influenced their assembly properties in the crystal structures. Complex 1 showed a 2D network structure consisting of 1D chains connected by intermolecular NHC interactions. On the other hand, complex 2 consisted of two different cobalt ion sites (Co1 and Co2) with slightly different coordination environments. Complex 2 showed 1D chains with no interchain interactions. Such differences are discussed with the cooperativities estimated by their spin crossover behaviours.

DOI： 10.1071/CH16556

記述言語：英語   掲載種別：研究論文（学術雑誌）  

Slight changes in the coordination structure of the manganese(v)-nitrido anionic complex, [Mn^V(N)(CN)₄]²⁻, induced by using a “lipid package” approach markedly made an impact on the corresponding redox potentials. The single crystals of four lipid assemblies, [dabco-(CH₂)_n−1-CH₃]₂[Mn(N)(CN)₄(H₂O)]·xH₂O (n = 15, 16, 17 and 18; dabco = 1,4-diazabicyclo[2,2,2]octane), were synthesized and solid-state cyclic voltammetric studies demonstrated that the [Mn^V(N)(CN)₄]²⁻ anions with smaller “cross” NC-Mn-CN bond angles exhibit higher redox potentials. The observed trend reflects the energy change associated with the structural transformation from [Mn^V(N)(CN)₄]²⁻ to [Mn^VI(N)(CN)₄]²⁻ and is supported by the results of DFT calculations. The NC-Mn-CN bond angles in the flexible [Mn(N)(CN)₄]²⁻ structure exhibit excellent correlation with the redox potentials of the complexes in the solid state.

DOI： 10.1039/c7dt00233e

記述言語：英語   掲載種別：研究論文（学術雑誌）  

Within the nanopores, junctions and interlayer void space (IVS) in graphene oxide film (GOf), we report that IVS function as the key semipermeable site during sieving. The GOf could filter only dye molecules having nanometer-ranged dimensions. Tinier hydrated ions with angstrom-ranged dimensions couldn't be sieved by GOf. Nature and extent of this molecular sieving property have been justified by observing sieving efficacy and flow times for aqueous solutions of dyes, inorganic salts and their mixtures. GOf also could separate the dyes from mixtures with salts. The flow time followed the trend as: mixtures > salt solutions > dye solutions. PXRD data reveal entering of dye molecules at IVS during sieving. Obviously, a part of dye molecules leaking through the nanopores and junctions of GOf, finally become trapped at the IVS. IVS, therefore has been recognized as the key semipermeable site for molecular sieving in GO. With exploring the insight features of molecular sieving in GOf, this report clearly indicates that IVS needs to be tuned to adopt GOf for various analytical aspects including water purification, desalination and organic inorganic separation.

DOI： 10.1002/slct.201700503

記述言語：英語   掲載種別：研究論文（学術雑誌）  

The title complex, [Ni(C₂₀H₁₄ClN₃O)], with an asymmetrically chloride-appended Schiff base ligand has been synthesized and structurally characterized at 100K. In the compound, the central nickel(II) ion has a square-planar coordination geometry with N3O donors of the π-conjugated tetradentate Schiff base ligand. In the crystal, the complexes are connected into an inversion dimer via an Ni⋯Ni interaction [3.1753(5)Å] and a pair of π-π interactions [centroid-centroid distance = 3.8416(16)Å]. The dimers are linked via a C-H⋯Cl hydrogen bond, forming a chain along the c-axis direction. The dimer chains interact with each other through π-π interactions [centroid-centroid distance = 3.8736(16)Å], forming a layer expanding parallel to the ac plane.

DOI： 10.1107/S2056989017004613

記述言語：英語   掲載種別：研究論文（学術雑誌）  

The effect of interlayer distance and oxygen content on proton conductivity of graphite oxide is presented. Bulk-state proton conductivities were measured using coin-shaped pellets of three different graphite oxide samples, namely, H-GO, S-GO, and B-GO, generated respectively from the techniques of Hummers, Staudenmaier, and Brodie. The extent of oxidation, nature of functional groups, interlayer distances, and morphologies are studied through Raman spectroscopy, XPS, powder XRD pattern, and SEM images. The proton conductivities follow the trend H-GO > S-GO > B-GO. In the XPS study, the total oxygen contents were found to follow the trend H-GO > B-GO > S-GO, whereas the interlayer distances obtained from the powder XRD patterns show the trend H-GO > S-GO > B-GO. Beside the nature of the functional groups and extent of oxidation, the interlayer distance displays a significant effect on the proton conductivity values. The temperature-dependent Arrhenius plots reveal the activation energy (E_a) of the samples as 0.274, 0.291, and 0.296 eV. These low E_a values imply the Grotthuss mechanism for proton conduction. The high conductivity value and low activation energy of H-GO with a maximum interlayer distance indicate that hydronium ion's rotational movement and re-formation of hydrogen bonds by the Grotthuss mechanism are supported by a more flexible interlayer. We propose that this physical insight might be considered to improve the proton conductivity through modulating layer distances not only in carbon allotropes but also in other materials.

DOI： 10.1021/acs.jpcc.6b06301

記述言語：英語   掲載種別：研究論文（学術雑誌）  

A highly stable proton conductor has been developed from carbon sphere oxide (CSO). Carbon sphere (CS) generated from sucrose was oxidized successfully to CSO using Hummers’ graphite oxidation technique. At room temperature and 90 % relative humidity, the proton conductivity of thin layer CSO on microsized comb electrode was found to be 8.7×10⁻³ S cm⁻¹, which is higher than that for a similar graphene oxide (GO) sample (3.4×10⁻³ S cm⁻¹). The activation energy (E_a) of 0.258 eV suggests that the proton is conducted through the Grotthuss mechanism. The carboxyl functional groups on the CSO surface are primarily responsible for transporting protons. In contrast to conventional carbon-based proton conductors, in which the functional groups decompose around 80 °C, CSO has a stable morphology and functional groups with reproducible proton conductivity up to 400 °C. Even once annealed at different temperatures at high relative humidity, the proton conductivity of CSO remains almost unchanged, whereas significant change is seen with a similar GO sample. After annealing at 100 and 200 °C, the respective proton conductivity of CSO was almost the same, and was about ∼50 % of the proton conductivity at room temperature. Carbon-based solid electrolyte with such high thermal stability and reproducible proton conductivity is desired for practical applications. We expect that a CSO-based proton conductor would be applicable for fuel cells and sensing devices operating under high temperatures.

DOI： 10.1002/asia.201600835

記述言語：英語   掲載種別：研究論文（学術雑誌）  

Acetaldehyde gas sensing using hybrids of reduced graphene oxide (rGO) and transition metal elements, rGO-M (M = oxide/hydroxide of Mn, Fe, Co and Ni) has been investigated. Thin films of GO, rGO and rGO-M on conductive glass were deposited through simple and affordable techniques and characterized using Raman spectroscopy, powder X-ray diffraction patterns, field emission scanning electron microscopy and electrical conductivity measurements. Concentration dependent resistances during the oxidation of acetaldehyde gas in air (10 to 50%) were investigated by using a sensing probe devised from rGO, GO-M and the rGO-M hybrids, of which rGO-Ni exhibited the maximum sensitivity. In rGO-Ni, in combination with rGO the NiOOH precursor can capture electrons (generated from acetaldehyde oxidation) through the holes, while indicating rGO-Ni to be a p-type semiconductor. This report implies the possibility of developing inexpensive graphene based p-type semiconductors for sensing other gases as well.

DOI： 10.1039/c6qi00058d

記述言語：英語   掲載種別：研究論文（学術雑誌）  

Fe[((py)im-C16)
₃
](BF
₄
)
₂
(1) and Fe[((py)imH)
₃
](BF
₄
)
₂
(2), the Iron(II) compounds with C16 long alkyl chain appended (py)imH and unmodified (py)imH [(py)imH = 2-(2-pyridyl)imidazole] have been synthesized and characterized by NMR, IR spectra and elemental analysis. For containing C16 long alkyl chain, complex 1 exhibits the liquid crystalline property around room temperature. The magnetic study suggests that 1 exists only in low spin state but 2 exhibits gradual spin crossover behavior. These observation suggests the possibility for synchronizing liquid crystallinity and spin crossover behavior of (py)imH complex in near future.

DOI： 10.1016/j.jorganchem.2016.02.014

記述言語：英語   掲載種別：研究論文（学術雑誌）  

Metal dilution effects on reverse spin transition (rST) in mixed crystals of type [Co_1-xZn_x(C₁₆-terpy)₂](BF₄)₂ (x = 0.1-0.7) were investigated by comparison with behavior of [Co_1-xFe_x(C₁₆-terpy)₂](BF₄)₂ (x = 0.1-0.4). In the mixed crystals, the Zn complexes increased rST temperatures linearly with increasing values of x, without changing the hysteresis width, while the Fe complexes decreased rST temperatures. Moreover, the strength of the metal dilution effects in the CoZn mixed crystals is weaker than what occurs in the CoFe mixed crystals.

DOI： 10.1021/acs.inorgchem.5b02582

記述言語：英語   掲載種別：研究論文（学術雑誌）  

A graphene oxide (GO) and ruthenium(II) complex with bromine-substituted terpyridine ligand, [Ru(Br-terpy)(2)]Cl-2 (Br-terpy: 4'-bromo-2,2':6',2 ''-terpyridine), reacts to form a GO-[Ru(Br-terpy)(2)](2+) hybrid, which after photoreduction turns to the reduced graphene oxide (rGO)-based hybrid rGO-[Ru(Br-terpy)(2)](2+). The hybrids were characterized by UV, IR, and XPS spectra. rGO-[Ru(Br-terpy)(2)](2+) exhibits excellent photocurrent generation through the cathodic photoreduction process. This observation indicates the possibility of designing an rGO-based energy generating material.

DOI： 10.1246/cl.151123

記述言語：英語   掲載種別：研究論文（学術雑誌）  

A highly stable composite from in situ growth of silicon oxycarbide phases (SiOC) within reduced graphene oxide (rGO) has been synthesized. The resulted SiOC/rGO anode exhibits high porosity, reversible Li intercalation capacity and a cycling stability of 507 mAhg
⁻¹
at 100 mAg
⁻¹
(50 cycles).

DOI： 10.1002/slct.201601363

記述言語：英語   掲載種別：研究論文（学術雑誌）  

Cobalt-iron Prussian blue analogues are magnetic functional compounds that exhibit charge-transfer-induced spin transition (CTIST), however, the role of guest species such as water in influencing the magnetic behaviour has remained unclear. Here, we report the water-dependent CTIST behaviour of Na_0.46Co[Fe(CN)₆]_0.78(H₂O)_1.31 together with its single crystal X-ray structural analysis, for the first time.

DOI： 10.1039/c6dt03474h

記述言語：英語   掲載種別：研究論文（学術雑誌）  

An antimalarial drug artesunate (ATS) was encapsulated in both functionalized MCM-41 and ordinary MCM-41 with an excellent loading capacity and sustained release behavior for possible biomedical applications.

DOI： 10.1039/c5tb02200b

記述言語：英語   掲載種別：研究論文（学術雑誌）  

The racemic oxovanadium(IV) salmmen complexes, [VO((rac)-(4-X-salmmen))] (X=C₁₂C₁₀C₅ (1), C₁₆ (2), and C₁₈ (3); salmmen=N,N′-monomethylenebis-salicylideneimine) with "banana shaped" molecular structures were synthesized, and their ferroelectric properties were investigated. These complexes exhibit well-defined hysteresis loops in their viscous phases, moreover, 1 also displays liquid crystal behaviour. We observed a synergetic effect influenced by three structural aspects; the methyl substituents on the ethylene backbone, the banana shaped structure and the square pyramidal metal cores all play an important role in generating the observed ferroelectricity, pointing the way to a useful strategy for the creation of advanced ferroelectric soft materials.

DOI： 10.1038/srep16606

記述言語：英語   掲載種別：研究論文（学術雑誌）  

Graphene (rGO) based hybrid materials exhibiting electrical conductivity and spin crossover (SCO) behavior are reported. The non-conductive [Fe(qnal)₂]_nGO (1·GO) and [Fe(qsal)₂]_nGO (2·GO) hybrids have been prepared by employing the electrostatic interaction between the negatively charged graphene oxide (GO) nanosheet and the respective iron(iii) complex cations in [Fe(qnal)₂]⁺Cl^- and [Fe(qsal)₂]⁺Cl^-. The conductive [Fe(qnal)₂]_nrGO (1·rGO) and [Fe(qsal)₂]_nrGO (2·rGO) hybrids were obtained by thermal reduction of 1·GO and 2·GO. 1·GO and 1·rGO exhibit SCO behavior, and 1·rGO also shows a light-induced excited spin state trapping (LIESST) effect. Thus, in 1·rGO the electrical conductivity of rGO and the SCO behavior of [Fe(qnal)₂]⁺ coexist in a single structure. We propose that the observed cooperativity for the rGO nanosheet-bound iron(iii) [Fe(qnal)₂]⁺ SCO material occurs through formation of large domains via π-π stacking between the graphene skeleton and the [Fe(qnal)₂]⁺ cations.

DOI： 10.1039/c5qi00097a

記述言語：英語   掲載種別：研究論文（学術雑誌）  

Discrete Co(II) spin crossover (SCO) compounds have attracted much attention for constructing highly sensitive molecular devices; however, the use of Co(II) SCO-coordination polymers (CPs) in such applications is extremely limited. The syntheses of the one-dimensional Co(II) SCO-CPs, [CoX₂(pyterpy)] (pyterpy = 4′-(4-pyridyl)-2,2′:6′,2′′-terpyridine; X = Cl (1), Br (2)), are presented. The structure of 1 shows a 'closed' packing arrangement that exhibits gate-type water adsorption at room temperature while 2 has an 'open' packing arrangement that shows type I water adsorption behaviour at room temperature. In addition, both 1 and 2 adsorb CO₂ at 201 K. Following water adsorption, 1·H₂O and 2·H₂O showed cooperative SCO at 226 K and 299 K, respectively.

DOI： 10.1039/c5tc00864f

記述言語：英語   掲載種別：研究論文（学術雑誌）  

Manganese(III) complexes [MnL ₂ ¹ ]BPh₄ (1) and [MnL ₂ ² (MeOH)₂]BPh₄ (2) were synthesized (HL¹ = 2-{N-[2-(2-pyridyl)ethyl]iminomethyl}-6-methoxyphenol and HL² = 2-{N-[2-(2-pyridyl)ethyl]iminomethyl}-4-methylphenol) and characterized. The crystal structures were determined by single crystal X-ray crystallography for 1 and 2 and magnetic properties were characterized by magnetic susceptibility. Compounds 1 and 2 crystallized in the triclinic system with space groups P-1. The crystal structure of 1 showed that the central manganese(III) ions were coordinated by four nitrogen and two oxygen atoms of two ligands in trans positions, exhibiting a pseudo-octahedral geometry. On the other hand, the crystal structure of 2 showed that the manganese(III) ions were coordinated by the two nitrogen and two oxygen atoms of two ligands and two methanol solvent molecules. The variable temperature-dependence magnetic susceptibilities have shown that the compounds 1 and 2 manganese(III) oxidation state; there is no magnetic interaction between complexes.

DOI： 10.1007/s10847-015-0492-0

記述言語：英語   掲載種別：研究論文（学術雑誌）  

Temperature dependent dielectric constant changes for salicylideneaniline (SA) were observed before and after light irradiation. The dielectric constant for a non-illuminated sample is higher than that for an illuminated one. It was considered that this fascinating observation might reflect dynamic chromophoric structural changes within the tautomers of SA.

DOI： 10.1007/s10847-015-0524-9

記述言語：英語   掲載種別：研究論文（学術雑誌）  

Iron(III) Schiff base compound [Fe(pap)₂]ClO₄·H₂O (1, and Hpap = (2-(2-pyridylmethyleneamino)phenol)) shows abrupt spin crossover (SCO) with a hysteresis (T_1/2↓ = 165 K, T_1/2↑ = 180 K) and anomalous light induced excited spin state trapping. In the complex 1, the existence of the interaction between molecules by π electrons is suggested from single crystal structure. An anomalous LS → HS conversion, aberrant increase of HS molar fraction, was observed at low-temperature (50 K) in 1 after rapid cooling, and interpreted in terms of bistability resulted from strong cooperative interactions.

DOI： 10.1007/s10847-015-0521-z

記述言語：英語   掲載種別：研究論文（学術雑誌）  

Two solvated cobalt(ii) terpyridine complexes, [Co(MeO-terpy)₂](BF₄)₂·H₂O (1·H₂O) and [Co(MeO-terpy)₂](BF₄)₂·acetone (1·acetone) were prepared. Annealing each of these complexes resulted in the formation of two desolvated species, 1 and 1′, respectively. 1·H₂O and 1 exhibited two-step and gradual SCO. The compound 1·acetone has high-spin at all temperatures and 1′ undergoes a reverse spin transition due to a phase change.

DOI： 10.1039/c4dt03743j

記述言語：英語   掲載種別：研究論文（学術雑誌）  

The coexistence of electrical conductivity and ferromagnetism has been achieved in a reduced graphene oxide/manganese oxide hybrid (rGO-Mn) synthesized by chemical reduction of a graphene oxide and Mn²⁺ (as its GO-Mn²⁺ complex) using hydrazine. The rGO-Mn and GO-Mn²⁺ complexes were characterized by Fourier transform infrared spectroscopy (FT-IR), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM). In rGO-Mn the Mn was present as manganese oxide nanoparticles located on the rGO nanosheets. This rGO-Mn exhibits both electrical conductivity and ferromagnetism. The synthesis of hybrids incorporating rGO and metal oxides is proposed as a useful strategy for generation of new multifunctional nano-composite materials.

DOI： 10.1039/c5dt00299k

記述言語：英語   掲載種別：研究論文（学術雑誌）  

In the title compound, [Co(C₂₅H₃₀N₄O₄)₂](ClO₄)₃·CH₃OH·H₂O, the metal atom is coordinated by two tridentate crown ether terpyridine ligands, forming a distorted CoN₆ octahedron. The three pyridine rings in each crown-terpyridine ligand are approximately coplanar [maximum deviations = 0.088 (12) and 0.102 (15) Å] and the mean planes through the three pyridine rings are perpendicular to each other, making a dihedral angle of 89.95 (17)°. An intramolecular C-H···π interaction is observed between the two terpyridine ligands. In the crystal, O-H···O and C-H···O hydrogen bonds, a π-π stacking interaction [centroid-centroid distance = 3.923 (7) Å] and a C-H···π interaction connect the complex cation, the perchlorate anions and the two types of solvent molecules, forming a three-dimensional network.

DOI： 10.1107/S2056989015014164

記述言語：英語   掲載種別：研究論文（学術雑誌）  

Novel organic-inorganic hybrid liposomes, socalled coordination polymersomes (CPsomes), with artificial domains that exhibit strong lateral cohesion were prepared by a three-step procedure that formed a coordinative interaction leading to a lipid bilayer. First, the lipophilic complex (dabco-C₁₈)[Mn(N)(CN)₄(dabco-C₁₈)] (1; dabco-C₁₈ ⁺ = 1,4-diazabicyclo[2,2,2]octane-(CH₂)₁₇-CH₃ cation), was synthesized. 1 has a lipophilic alkyl tail part and a tetracyanometallate head group, which can be used for an expansion to two-dimensional coordination networks. Second, 1 and 1,2-dipal-mitoyl-sn-glycero-3-phosphocholine were mixed to prepare the liposomes. Finally, CPsomes were obtained by the addition of transition-metal ions (M) to form unilamellar faceted liposomes with plain CP raft domains with Mn-CN-M linkages. The concentration of 1 influences the size of the CP raft domains and the shape of the CPsomes. The synthesis of coordination polymers in lipid bilayers is a novel approach for the construction of artificial architectures as raft domains, for example, in cell membranes.

DOI： 10.1002/anie.201408101

記述言語：英語   掲載種別：研究論文（学術雑誌）  

The hetero-metal complexes [Co^II(Fctpy)₂]X₂ (Fctpy = 4′-ferrocenyl-2,2′;6′2′′-terpyridine, X = PF₆ (1), BF₄ (2), ClO₄ (3), BPh₄ (4)) were prepared and their structures and properties were investigated by single crystal X-ray structural analysis, cyclic voltammetry, Mössbauer spectroscopy, UV-vis spectroscopy measurements and DFT calculations. These compounds show reversible redox behaviour in the solid state and switching of the colour between red-violet and blue in response to the change of the oxidation state of the cobalt ion centres. [Co^II(Fctpy)₂](PF₆)₂ (1) and [Co^III(Fctpy)₂](PF₆)₃ (5) were isolated as the red and blue crystalline products, and the crystal structures were determined. From the results of UV-vis spectroscopy and the DFT calculations, we assigned the respective colours as resulting from MLCT involving the ferrocenyl substituents, with the shift in the wavelength of the MLCT reflecting the respective HOMO/LUMO stabilizations induced by the change in the oxidation state of the cobalt centres. Furthermore, these compounds 1-4 also showed counter anion-dependent spin crossover behaviours.

DOI： 10.1039/c5dt02592c

記述言語：英語   掲載種別：研究論文（学術雑誌）  

The synthesis, structure, and magnetic properties of three clathrate derivatives of the spin-crossover porous coordination polymer {Fe(pyrazine)[Pt(CN)₄]} (1) with five-membered aromatic molecules furan, pyrrole, and thiophene is reported. The three derivatives have a cooperative spin-crossover transition with hysteresis loops 14-29?K wide and average critical temperatures T_c=201?K (1fur), 167?K (1pyr), and 114.6?K (1thio) well below that of the parent compound 1 (T_c=295?K), confirming stabilization of the HS state. The transition is complete and takes place in two steps for 1fur, while 1pyr and 1thio show 50?% spin transition. For 1fur the transformation between the HS and IS (middle of the plateau) phases occurs concomitantly with a crystallographic phase transition between the tetragonal space groups P4/mmm and I4/mmm, respectively. The latter space group is retained in the subsequent transformation involving the IS and the LS phases. 1pyr and 1thio display the tetragonal P4/mmm and orthorhombic Fmmm space groups, respectively, in both HS and IM phases. Periodic calculations using density functional methods for 1fur, 1pyr, 1thio, and previously reported derivatives 1CS₂, 1I, 1bz(benzene), and 1pz(pyrazine) have been carried out to investigate the electronic structure and nature of the host-guest interactions as well as their relationship with the changes in the LS-HS transition temperatures of 1Guest. Geometry-optimized lattice parameters and bond distances in the empty host 1 and 1Guest clathrates are in general agreement with the X-ray diffraction data. The concordance between the theoretical results and the experimental data also comprises the guest molecule orientation inside the host and intermolecular distances. Furthermore, a general correlation between experimental T_c and calculated LS-HS electronic energy gap was observed. Finally, specific host-guest interactions were studied through interaction energy calculations and crystal orbital displacement (COD) curve analysis.

DOI： 10.1002/chem.201402292

記述言語：英語   掲載種別：研究論文（学術雑誌）  

To implement specific guest responsivity, a hydrophobic cholesterol-based co-ligand, cholest-5-en-3-yl-4-isonicotinate (Cholpy), was incorporated into a two-dimensional Hofmann-type Co(ii)Ni(ii) coordination polymer. The chemically programmed structure successfully demonstrated the unique guest response with remarkable chromatic changes.

DOI： 10.1039/c3dt51465j

記述言語：英語   掲載種別：研究論文（学術雑誌）  

Coordination pillared layers (CPLs) are among the most attractive framework compounds displaying unique porous properties depending on their components. Three-dimensional Hofmann-type porous coordination polymers consisting of pillared cyanide-bridged layers with a tetracyanometallate anion [M ^II(CN)₄]^2- (M = Ni, Pd, Pt) as a secondary building unit (SBU) are the representative functional CPLs. In this paper, we report a new synthetic strategy for constructing CPLs using a new SBU linking two tetracyanometallate complexes, [{Mn^V(N)(CN)₄} ₂(bpy)]^4- (bpy = 4,4′-bipyridyl). The [Mn ^V(N)(CN)₄]^2- part in the SBU permits expansion of the 2-D cyanide-bridged layers and the pillar part bpy simultaneously links the layers. Two CPLs, [M^II(bpy){Mn^V(N)(CN) ₄(bpy)_1/2}]·MeCN·H₂O (M = Zn, Cd), were synthesized by applying the SBU and characterized by X-ray single-crystal structural analysis and gas adsorption measurements.

DOI： 10.1016/j.poly.2012.08.006

記述言語：英語   掲載種別：研究論文（学術雑誌）  

Two 2D Hofmann-type spin-crossover coordination polymers, [Fe(stpy) ₂Pt(CN) ₄]·0.5MeOH (stpy = 4-styrylpyridine; 1) and [Fe(pep) ₂Pt(CN) ₄] {pep = 4-(2-phenylethyl)pyridine; 2}, have been prepared by using long co-ligands with different flexibilities. These compounds form 3D interdigitate structures based on 2D layers extended by Pt-CN-Fe linkages with different interlayer structures depending on the nature of the axial co-ligand. The stpy co-ligand forms one-directional π-π networks between the layers, whereas pep forms twodirectional π-π networks as a result of its perpendicularly twisted structure. Coordination polymer 1 exhibits a half-spin transition with Tc ↓ = 106 K and Tc ↑ = 110 K. In contrast, coordination polymer 2 shows a sharp, two-step spin transition in the temperature range 184-236 K. The difference in spintransition behavior is discussed in terms of the interlayer packing structure.

DOI： 10.1002/ejic.201201204

記述言語：英語   掲載種別：研究論文（学術雑誌）  

Three porous coordination polymers {Fe(dpa)[Pt(CN)₄]·G·nH₂O} (1-G; dpa = 1,2-di(4-pyridyl)ethane, G = dpa, bibenzyl (bbz) and stilbene (stb)) have been prepared by using a long and flexible ligand dpa. These compounds formed analogous 3-D elongated Hofmann-type frameworks based on 2-D planar layers extended by Pt-CN-Fe linkages with dpa as flexible pillar ligands. 1-dpa showed a characteristic three-step spin transition (ST) in the temperature range 180-240 K. The ST behavior was reversibly modulated by dehydration and hydration processes in keeping with the three steps. 1-bbz and 1-stb exhibited a gradual three-step ST over the range 80-200 K and an abrupt ST with T_c = 163 K. The guest-dependent cooperativity of the ST behavior is discussed by considering the flexibility of the framework and guest molecules.

DOI： 10.1007/s10904-012-9747-z

記述言語：英語   掲載種別：研究論文（学術雑誌）  

Inclusion of thiourea guest molecules in the tridimensional spin crossover porous coordination polymers {[Fe(pyrazine)[M(CN) ₄]} (M = Pd, Pt) leads to novel clathrates exhibiting unprecedented large thermal hysteresis loops of ca. 60 K wide centered near room temperature.

DOI： 10.1039/c2cc31048a

記述言語：英語   掲載種別：研究論文（学術雑誌）  

A quasielastic neutron scattering and solid-state ²H NMR spectroscopy study of the polymeric spin-crossover compound {Fe(pyrazine)[Pt(CN) ₄]} shows that the switching of the rotation of a molecular fragment-the pyrazine ligand-occurs in association with the change of spin state. The rotation switching was examined on a wide time scale (10 ^-13-10 ^-3 s) by both techniques, which clearly demonstrated the combination between molecular rotation and spin-crossover transition under external stimuli (temperature and chemical). The pyrazine rings are seen to perform a 4-fold jump motion about the coordinating nitrogen axis in the high-spin state. In the low-spin state, however, the motion is suppressed, while when the system incorporates benzene guest molecules, the movements of the system are even more restricted.

DOI： 10.1021/ja206228n

記述言語：英語   掲載種別：研究論文（学術雑誌）  

A facile route has been found to prepare Prussian blue (PB) hollow particles with a cubic shape (see picture). With PB mesocrystals used as a starting material, hollow interiors were created through controlled chemical etching in the presence of poly(vinylpyrrolidone). The hollow cavities and particle sizes could be tuned by changing the synthetic conditions, and the original PB crystallinity was preserved even after formation of interior hollows.

DOI： 10.1002/anie.201105190

記述言語：英語   掲載種別：研究論文（学術雑誌）  

Precise control of spin transition temperature (T_c) is one of the most important challenges in molecular magnetism. A Hofmann-type porous coordination polymer {Fe(pz)[Pt^II(CN)₄]} (1; pz = pyrazine) exhibited cooperative spin transition near room temperature (T _c^up = 304 K and T_c^down = 284 K) and its iodine adduct {Fe(pz)[Pt^II/IV(CN)₄(I)]} (1-I), prepared by oxidative addition of iodine to the open metal sites of Pt ^II, raised the T_c by 100 K. DSC and microscopic Raman spectra of a solid mixture of 1-I and 1 revealed that iodine migrated from 1-I to 1 through the grain boundary after heating above 398 K. We have succeeded in precisely controlling the iodine content of {Fe(pz)[Pt(CN)₄(I) _n]} (1-In; n = 0.0-1.0), which resulted in consecutive modulation of T_c in the range 300-400 K while maintaining the hysteresis width. Furthermore, it was demonstrated that iodine migration in the solid mixture was triggered by the spin transition of 1-I. The magnetically bistable porous framework decorating guest interactive open-metal-site in the pore surface makes it possible to modulate T_c ad arbitrium through unique postsynthetic method using iodine migration.

DOI： 10.1021/ja111674c

記述言語：英語   掲載種別：研究論文（学術雑誌）  

Mixing with the guests: Exposure of the porous spin-crossover framework {Fe(pz)[Ptll(CN)4]}to X2(pz=pyrazine; X2=Cl2, Br2, and 12) leads to incorporation of the halides in the coordi natively unsaturated [Ptll(CN)4]2- moieties through oxidative addition, thus affording the mixed-valence series {Fe(pz)[Ptll/IV(CN)4(X)]], which features quite distinct cooperative spin-transition properties.

DOI： 10.1002/anie.200904379

開催年月日： 2024年3月

記述言語：英語   会議種別：口頭発表（一般）  

開催地：西船橋   国名：日本国  

開催年月日： 2024年3月

記述言語：日本語   会議種別：口頭発表（一般）  

開催地：西船橋   国名：日本国  

開催年月日： 2024年3月

記述言語：日本語   会議種別：口頭発表（一般）  

開催地：西船橋   国名：日本国  

開催年月日： 2024年3月

記述言語：日本語   会議種別：口頭発表（一般）  

開催地：西船橋   国名：日本国  

開催年月日： 2024年3月

記述言語：日本語   会議種別：口頭発表（一般）  

開催地：西船橋   国名：日本国  

開催年月日： 2023年9月

記述言語：日本語   会議種別：シンポジウム・ワークショップ パネル（公募）  

開催地：水戸   国名：日本国  

開催年月日： 2023年9月

記述言語：英語   会議種別：シンポジウム・ワークショップ パネル（公募）  

開催地：水戸   国名：日本国  

開催年月日： 2023年9月

記述言語：日本語   会議種別：口頭発表（一般）  

開催地：水戸   国名：日本国  

開催年月日： 2023年9月

記述言語：日本語   会議種別：口頭発表（一般）  

開催地：水戸   国名：日本国  

開催年月日： 2023年9月

記述言語：日本語   会議種別：シンポジウム・ワークショップ パネル（公募）  

開催地：水戸   国名：日本国  

開催年月日： 2023年9月

記述言語：日本語   会議種別：シンポジウム・ワークショップ パネル（公募）  

開催地：水戸   国名：日本国  

開催年月日： 2023年9月

記述言語：日本語   会議種別：シンポジウム・ワークショップ パネル（公募）  

開催地：水戸   国名：日本国  

開催年月日： 2023年9月

記述言語：英語   会議種別：口頭発表（一般）  

開催地：水戸   国名：日本国  

開催年月日： 2023年9月

記述言語：英語   会議種別：口頭発表（一般）  

開催地：水戸   国名：日本国  

開催年月日： 2023年9月

記述言語：英語   会議種別：シンポジウム・ワークショップ パネル（公募）  

開催地：水戸   国名：日本国  

開催年月日： 2023年9月

記述言語：英語   会議種別：口頭発表（一般）  

開催地：水戸   国名：日本国  

開催年月日： 2023年9月

記述言語：日本語   会議種別：シンポジウム・ワークショップ パネル（公募）  

開催地：水戸   国名：日本国  

開催年月日： 2023年9月

記述言語：日本語   会議種別：シンポジウム・ワークショップ パネル（公募）  

開催地：水戸   国名：日本国  

開催年月日： 2023年9月

記述言語：日本語   会議種別：口頭発表（一般）  

開催地：大阪   国名：日本国  

開催年月日： 2023年7月

記述言語：日本語   会議種別：シンポジウム・ワークショップ パネル（公募）  

開催地：北九州   国名：日本国  

開催年月日： 2023年7月

記述言語：日本語   会議種別：シンポジウム・ワークショップ パネル（公募）  

開催地：北九州   国名：日本国  

開催年月日： 2023年7月

記述言語：日本語   会議種別：シンポジウム・ワークショップ パネル（公募）  

開催地：北九州   国名：日本国  

開催年月日： 2023年7月

記述言語：日本語   会議種別：シンポジウム・ワークショップ パネル（公募）  

開催地：北九州   国名：日本国  

開催年月日： 2023年7月

記述言語：日本語   会議種別：シンポジウム・ワークショップ パネル（公募）  

開催地：北九州   国名：日本国  

開催年月日： 2023年7月

記述言語：日本語   会議種別：シンポジウム・ワークショップ パネル（公募）  

開催地：北九州   国名：日本国  

開催年月日： 2023年7月

記述言語：日本語   会議種別：シンポジウム・ワークショップ パネル（公募）  

開催地：北九州   国名：日本国  

開催年月日： 2023年7月

記述言語：日本語   会議種別：シンポジウム・ワークショップ パネル（公募）  

開催地：北九州   国名：日本国  

開催年月日： 2023年7月

記述言語：日本語   会議種別：シンポジウム・ワークショップ パネル（公募）  

開催地：北九州   国名：日本国  

開催年月日： 2023年7月

記述言語：日本語   会議種別：シンポジウム・ワークショップ パネル（公募）  

開催地：北九州   国名：日本国  

開催年月日： 2023年7月

記述言語：日本語   会議種別：シンポジウム・ワークショップ パネル（公募）  

開催地：北九州   国名：日本国  

開催年月日： 2023年3月

記述言語：英語   会議種別：口頭発表（一般）  

開催地：千葉   国名：日本国  

開催年月日： 2023年3月

記述言語：日本語   会議種別：口頭発表（一般）  

開催地：千葉   国名：日本国  

開催年月日： 2022年10月

記述言語：英語   会議種別：口頭発表（一般）  

開催地：仙台   国名：日本国  

開催年月日： 2022年9月

記述言語：日本語   会議種別：シンポジウム・ワークショップ パネル（公募）  

開催地：福岡   国名：日本国  

開催年月日： 2022年9月

記述言語：日本語   会議種別：口頭発表（招待・特別）  

開催地：福岡   国名：日本国  

開催年月日： 2022年9月

記述言語：英語   会議種別：口頭発表（一般）  

開催地：福岡   国名：日本国  

開催年月日： 2022年9月

記述言語：英語   会議種別：口頭発表（一般）  

開催地：福岡   国名：日本国  

開催年月日： 2022年9月

記述言語：英語   会議種別：口頭発表（一般）  

開催地：福岡   国名：日本国  

開催年月日： 2022年9月

記述言語：日本語   会議種別：シンポジウム・ワークショップ パネル（公募）  

開催地：福岡   国名：日本国  

開催年月日： 2022年9月

記述言語：日本語   会議種別：シンポジウム・ワークショップ パネル（公募）  

開催地：福岡   国名：日本国  

開催年月日： 2022年9月

記述言語：日本語   会議種別：シンポジウム・ワークショップ パネル（公募）  

開催地：福岡   国名：日本国  

開催年月日： 2022年9月

記述言語：日本語   会議種別：シンポジウム・ワークショップ パネル（公募）  

開催地：福岡   国名：日本国  

開催年月日： 2022年9月

記述言語：日本語   会議種別：シンポジウム・ワークショップ パネル（公募）  

開催地：福岡   国名：日本国  

開催年月日： 2022年9月

記述言語：日本語   会議種別：シンポジウム・ワークショップ パネル（公募）  

開催地：福岡   国名：日本国  

開催年月日： 2022年9月

記述言語：日本語   会議種別：シンポジウム・ワークショップ パネル（公募）  

開催地：福岡   国名：日本国  

開催年月日： 2022年9月

記述言語：日本語   会議種別：シンポジウム・ワークショップ パネル（公募）  

開催地：福岡   国名：日本国  

開催年月日： 2022年9月

記述言語：日本語   会議種別：シンポジウム・ワークショップ パネル（公募）  

開催地：福岡   国名：日本国  

開催年月日： 2022年9月

記述言語：日本語   会議種別：シンポジウム・ワークショップ パネル（公募）  

開催地：福岡   国名：日本国  

開催年月日： 2022年9月

記述言語：日本語   会議種別：シンポジウム・ワークショップ パネル（公募）  

開催地：福岡   国名：日本国  

開催年月日： 2022年9月

記述言語：日本語   会議種別：シンポジウム・ワークショップ パネル（公募）  

開催地：福岡   国名：日本国  

開催年月日： 2022年7月

記述言語：日本語   会議種別：シンポジウム・ワークショップ パネル（公募）  

開催地：北九州   国名：日本国  

開催年月日： 2022年7月

記述言語：日本語   会議種別：シンポジウム・ワークショップ パネル（公募）  

開催地：北九州   国名：日本国  

開催年月日： 2022年7月

記述言語：日本語   会議種別：シンポジウム・ワークショップ パネル（公募）  

開催地：北九州   国名：日本国  

開催年月日： 2022年7月

記述言語：日本語   会議種別：シンポジウム・ワークショップ パネル（公募）  

開催地：北九州   国名：日本国  

開催年月日： 2022年7月

記述言語：日本語   会議種別：シンポジウム・ワークショップ パネル（公募）  

開催地：北九州   国名：日本国  

開催年月日： 2022年7月

記述言語：日本語   会議種別：シンポジウム・ワークショップ パネル（公募）  

開催地：北九州   国名：日本国  

開催年月日： 2022年7月

記述言語：日本語   会議種別：シンポジウム・ワークショップ パネル（公募）  

開催地：北九州   国名：日本国  

開催年月日： 2022年7月

記述言語：日本語   会議種別：シンポジウム・ワークショップ パネル（公募）  

開催地：北九州   国名：日本国  

開催年月日： 2022年7月

記述言語：日本語   会議種別：シンポジウム・ワークショップ パネル（公募）  

開催地：北九州   国名：日本国  

開催年月日： 2022年3月

記述言語：英語   会議種別：口頭発表（一般）  

開催地：オンライン   国名：日本国  

開催年月日： 2022年3月

記述言語：日本語   会議種別：口頭発表（一般）  

開催地：オンライン   国名：日本国  

開催年月日： 2022年3月

記述言語：日本語   会議種別：口頭発表（一般）  

開催地：オンライン   国名：日本国  

開催年月日： 2022年3月

記述言語：日本語   会議種別：口頭発表（一般）  

開催地：オンライン   国名：日本国  

開催年月日： 2022年3月

記述言語：日本語   会議種別：口頭発表（一般）  

開催地：オンライン   国名：日本国  

開催年月日： 2022年3月

記述言語：日本語   会議種別：口頭発表（一般）  

開催地：オンライン   国名：日本国  

開催年月日： 2022年3月

記述言語：日本語   会議種別：口頭発表（一般）  

開催地：オンライン   国名：日本国  

開催年月日： 2022年3月

記述言語：日本語   会議種別：口頭発表（一般）  

開催地：オンライン   国名：日本国  

開催年月日： 2021年12月

記述言語：英語   会議種別：口頭発表（一般）  

開催地：オンライン   国名：日本国  

開催年月日： 2021年12月

記述言語：英語   会議種別：口頭発表（一般）  

開催地：オンライン   国名：日本国  

開催年月日： 2021年12月

記述言語：英語   会議種別：シンポジウム・ワークショップ パネル（公募）  

開催地：オンライン   国名：日本国  

開催年月日： 2021年12月

記述言語：英語   会議種別：シンポジウム・ワークショップ パネル（公募）  

開催地：オンライン   国名：日本国  

開催年月日： 2021年12月

記述言語：英語   会議種別：シンポジウム・ワークショップ パネル（公募）  

開催地：オンライン   国名：日本国  

開催年月日： 2021年12月

記述言語：英語   会議種別：シンポジウム・ワークショップ パネル（公募）  

開催地：オンライン   国名：日本国  

開催年月日： 2021年12月

記述言語：英語   会議種別：口頭発表（一般）  

開催地：オンライン   国名：日本国  

開催年月日： 2021年12月

記述言語：英語   会議種別：口頭発表（一般）  

開催地：オンライン   国名：日本国  

開催年月日： 2021年9月

記述言語：日本語   会議種別：シンポジウム・ワークショップ パネル（公募）  

開催地：オンライン   国名：日本国  

開催年月日： 2021年9月

記述言語：英語   会議種別：口頭発表（一般）  

開催地：オンライン   国名：日本国  

開催年月日： 2021年9月

記述言語：英語   会議種別：口頭発表（一般）  

開催地：オンライン   国名：日本国  

開催年月日： 2021年9月

記述言語：英語   会議種別：口頭発表（一般）  

開催地：オンライン   国名：日本国  

開催年月日： 2021年9月

記述言語：日本語   会議種別：シンポジウム・ワークショップ パネル（公募）  

開催地：オンライン   国名：日本国  

開催年月日： 2021年9月

記述言語：日本語   会議種別：シンポジウム・ワークショップ パネル（公募）  

開催地：オンライン   国名：日本国  

開催年月日： 2021年9月

記述言語：日本語   会議種別：シンポジウム・ワークショップ パネル（公募）  

開催地：オンライン   国名：日本国  

開催年月日： 2021年9月

記述言語：日本語   会議種別：シンポジウム・ワークショップ パネル（公募）  

開催地：オンライン   国名：日本国  

開催年月日： 2021年9月

記述言語：日本語   会議種別：シンポジウム・ワークショップ パネル（公募）  

開催地：オンライン   国名：日本国  

開催年月日： 2021年9月

記述言語：日本語   会議種別：シンポジウム・ワークショップ パネル（公募）  

開催地：オンライン   国名：日本国  

開催年月日： 2021年7月

記述言語：日本語   会議種別：シンポジウム・ワークショップ パネル（公募）  

開催地：オンライン   国名：日本国  

開催年月日： 2021年7月

記述言語：日本語   会議種別：シンポジウム・ワークショップ パネル（公募）  

開催地：オンライン   国名：日本国  

開催年月日： 2021年7月

記述言語：日本語   会議種別：シンポジウム・ワークショップ パネル（公募）  

開催地：オンライン   国名：日本国  

開催年月日： 2021年7月

記述言語：日本語   会議種別：シンポジウム・ワークショップ パネル（公募）  

開催地：オンライン   国名：日本国  

開催年月日： 2021年7月

記述言語：日本語   会議種別：シンポジウム・ワークショップ パネル（公募）  

開催地：オンライン   国名：日本国  

開催年月日： 2021年3月

記述言語：日本語   会議種別：口頭発表（一般）  

開催地：オンライン   国名：日本国  

開催年月日： 2021年3月

記述言語：日本語   会議種別：口頭発表（一般）  

開催地：オンライン   国名：日本国  

開催年月日： 2021年3月

記述言語：日本語   会議種別：口頭発表（一般）  

開催地：オンライン   国名：日本国  

開催年月日： 2021年3月

記述言語：日本語   会議種別：口頭発表（一般）  

開催地：オンライン   国名：日本国  

開催年月日： 2021年3月

記述言語：日本語   会議種別：口頭発表（一般）  

開催地：オンライン   国名：日本国  

開催年月日： 2021年3月

記述言語：日本語   会議種別：口頭発表（一般）  

開催地：オンライン   国名：日本国  

開催年月日： 2021年3月

記述言語：英語   会議種別：シンポジウム・ワークショップ パネル（公募）  

開催地：オンライン   国名：日本国  

開催年月日： 2021年3月

記述言語：英語   会議種別：シンポジウム・ワークショップ パネル（公募）  

開催地：オンライン   国名：日本国  

開催年月日： 2021年3月

記述言語：英語   会議種別：シンポジウム・ワークショップ パネル（公募）  

開催地：オンライン   国名：日本国  

開催年月日： 2021年3月

記述言語：英語   会議種別：シンポジウム・ワークショップ パネル（公募）  

開催地：オンライン   国名：日本国  

開催年月日： 2020年10月

記述言語：日本語   会議種別：シンポジウム・ワークショップ パネル（公募）  

開催地：オンライン   国名：日本国  

開催年月日： 2020年10月

記述言語：日本語   会議種別：シンポジウム・ワークショップ パネル（公募）  

開催地：オンライン   国名：日本国  

開催年月日： 2020年10月

記述言語：日本語   会議種別：シンポジウム・ワークショップ パネル（公募）  

開催地：オンライン   国名：日本国  

開催年月日： 2020年10月

記述言語：日本語   会議種別：シンポジウム・ワークショップ パネル（公募）  

開催地：オンライン   国名：日本国  

開催年月日： 2020年9月

記述言語：日本語   会議種別：口頭発表（一般）  

開催地：オンライン   国名：日本国  

開催年月日： 2020年9月

記述言語：日本語   会議種別：シンポジウム・ワークショップ パネル（公募）  

開催地：オンライン   国名：日本国  

開催年月日： 2020年9月

記述言語：日本語   会議種別：シンポジウム・ワークショップ パネル（公募）  

開催地：オンライン   国名：日本国  

開催年月日： 2020年9月

記述言語：日本語   会議種別：シンポジウム・ワークショップ パネル（公募）  

開催地：オンライン   国名：日本国  

開催年月日： 2020年9月

記述言語：日本語   会議種別：シンポジウム・ワークショップ パネル（公募）  

開催地：オンライン   国名：日本国  

開催年月日： 2020年9月

記述言語：日本語   会議種別：シンポジウム・ワークショップ パネル（公募）  

開催地：オンライン   国名：日本国  

開催年月日： 2020年9月

記述言語：英語   会議種別：口頭発表（一般）  

開催地：オンライン   国名：日本国  

開催年月日： 2020年9月

記述言語：英語   会議種別：口頭発表（一般）  

開催地：オンライン   国名：日本国  

開催年月日： 2020年9月

記述言語：日本語   会議種別：シンポジウム・ワークショップ パネル（公募）  

開催地：オンライン   国名：日本国  

開催年月日： 2020年9月

記述言語：英語   会議種別：口頭発表（一般）  

開催地：オンライン   国名：日本国  

開催年月日： 2020年9月

記述言語：英語   会議種別：口頭発表（一般）  

開催地：オンライン   国名：日本国  

開催年月日： 2020年7月

記述言語：日本語   会議種別：口頭発表（一般）  

開催地：オンライン   国名：日本国  

開催年月日： 2020年7月

記述言語：日本語   会議種別：シンポジウム・ワークショップ パネル（公募）  

開催地：オンライン   国名：日本国  

開催年月日： 2020年7月

記述言語：日本語   会議種別：シンポジウム・ワークショップ パネル（公募）  

開催地：オンライン   国名：日本国  

開催年月日： 2020年7月

記述言語：日本語   会議種別：シンポジウム・ワークショップ パネル（公募）  

開催地：オンライン   国名：日本国  

開催年月日： 2020年7月

記述言語：日本語   会議種別：シンポジウム・ワークショップ パネル（公募）  

開催地：オンライン   国名：日本国  

開催年月日： 2020年3月

記述言語：日本語   会議種別：口頭発表（一般）  

開催地：野田   国名：日本国  

開催年月日： 2020年3月

記述言語：日本語   会議種別：口頭発表（一般）  

開催地：野田   国名：日本国  

開催年月日： 2020年3月

記述言語：日本語   会議種別：口頭発表（一般）  

開催地：野田   国名：日本国  

開催年月日： 2020年3月

記述言語：日本語   会議種別：口頭発表（一般）  

開催地：野田   国名：日本国  

開催年月日： 2020年3月

記述言語：日本語   会議種別：シンポジウム・ワークショップ パネル（公募）  

開催地：野田   国名：日本国  

開催年月日： 2020年3月

記述言語：日本語   会議種別：口頭発表（一般）  

開催地：野田   国名：日本国  

開催年月日： 2020年3月

記述言語：英語   会議種別：口頭発表（一般）  

開催地：野田   国名：日本国  

開催年月日： 2019年12月

記述言語：英語   会議種別：口頭発表（一般）  

開催地：Dairen   国名：中華人民共和国  

開催年月日： 2019年11月

記述言語：英語   会議種別：口頭発表（一般）  

開催地：Bhopal   国名：インド  

開催年月日： 2019年10月

記述言語：英語   会議種別：口頭発表（一般）  

開催地：Suzhou   国名：中華人民共和国  

開催年月日： 2019年10月

記述言語：英語   会議種別：口頭発表（一般）  

開催地：Kuala Lumpur   国名：マレーシア  

開催年月日： 2019年10月

記述言語：英語   会議種別：口頭発表（一般）  

開催地：Kuala Lumpur   国名：マレーシア  

開催年月日： 2019年10月

記述言語：英語   会議種別：シンポジウム・ワークショップ パネル（公募）  

開催地：Kuala Lumpur   国名：マレーシア  

開催年月日： 2019年10月

記述言語：英語   会議種別：シンポジウム・ワークショップ パネル（公募）  

開催地：Kuala Lumpur   国名：マレーシア  

開催年月日： 2019年10月

記述言語：英語   会議種別：シンポジウム・ワークショップ パネル（公募）  

開催地：Kuala Lumpur   国名：マレーシア  

開催年月日： 2019年10月

記述言語：英語   会議種別：シンポジウム・ワークショップ パネル（公募）  

開催地：Kuala Lumpur   国名：マレーシア  

開催年月日： 2019年9月

記述言語：英語   会議種別：口頭発表（一般）  

開催地：名古屋   国名：日本国  

開催年月日： 2019年9月

記述言語：英語   会議種別：口頭発表（一般）  

開催地：名古屋   国名：日本国  

開催年月日： 2019年9月

記述言語：英語   会議種別：口頭発表（一般）  

開催地：名古屋   国名：日本国  

開催年月日： 2019年9月

記述言語：英語   会議種別：口頭発表（一般）  

開催地：名古屋   国名：日本国  

開催年月日： 2019年9月

記述言語：日本語   会議種別：シンポジウム・ワークショップ パネル（公募）  

開催地：名古屋   国名：日本国  

開催年月日： 2019年9月

記述言語：日本語   会議種別：シンポジウム・ワークショップ パネル（公募）  

開催地：名古屋   国名：日本国  

開催年月日： 2019年9月

記述言語：日本語   会議種別：シンポジウム・ワークショップ パネル（公募）  

開催地：名古屋   国名：日本国  

開催年月日： 2019年9月

記述言語：日本語   会議種別：シンポジウム・ワークショップ パネル（公募）  

開催地：名古屋   国名：日本国  

開催年月日： 2019年9月

記述言語：日本語   会議種別：シンポジウム・ワークショップ パネル（公募）  

開催地：名古屋   国名：日本国  

開催年月日： 2019年9月

記述言語：日本語   会議種別：シンポジウム・ワークショップ パネル（公募）  

開催地：名古屋   国名：日本国  

開催年月日： 2019年9月

記述言語：英語   会議種別：シンポジウム・ワークショップ パネル（公募）  

開催地：名古屋   国名：日本国  

開催年月日： 2019年9月

記述言語：日本語   会議種別：シンポジウム・ワークショップ パネル（公募）  

開催地：名古屋   国名：日本国  

開催年月日： 2019年9月

記述言語：英語   会議種別：口頭発表（一般）  

開催地：名古屋   国名：日本国