記述言語：英語   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：Journal of the American Chemical Society  

Ion conductors comprising noncentrosymmetric frameworks have emerged as new functional materials. However, strongly correlated polarity functionality and ion transport have not been achieved. Herein, we report a ferroelectric proton conductor, K2MnN(CN)4·H2O (1·H2O), exhibiting the strong correlation between its polar skeleton and conductive ions that generate anomalous ferroelectricity via the proton-bias phenomenon. The application of an electric field of ±1 kV/cm (0.1 Hz) on 1·H2O at 298 K produced the ferroelectricity (polarization = 1.5 × 104 μC/cm2), which was enhanced by the ferroelectric-skeleton-trapped conductive protons. Furthermore, the strong polarity-proton transport coupling of 1·H2O induced a proton-rectification-like directional ion-conductive behavior that could be adjusted by the magnitude and direction of DC electric fields. Moreover, 1·H2O exhibited reversible polarity switching between the polar 1·H2O and its dehydrated form, 1, with a centrosymmetric structure comprising an order-disorder-type transition of the nitrido-bridged chains.

DOI： 10.1021/jacs.3c10841

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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：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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出版者・発行元：Chemical Engineering Journal  

Despite their extreme toxicity for human and the environment, Cr(VI) species are widely used in multiple industrial processes. This brings the need of potent strategies for detection at trace level and for remediation of contaminated effluents. In this article, we present a novel composite containing Fe3O4 quantum dots (QDs) immobilized on polydopamine-functionalized graphene obtained by a simple and cost-effective hydrothermal process. The high affinity of the composite for Cr(VI) ions resulted in an efficient chemical coupling with the Fe3O4 QDs, offering a powerful platform for multimodal reactivity. First, the composite acted both as a fluorescence as well as nanozymatic sensing platform for detecting toxic Cr(VI) ions in aqueous solution with a limit of detection (LOD) of 18 nM and 47 nM, respectively. In addition, the composite proved to be a very efficient catalyst for the visible-light photoreduction of Cr(VI) to non-toxic Cr(III), showing an outstanding reduction by 99% in 20 min under natural sunlight and a good recyclability. This study is the first of its kind where metal oxide QDs anchored functionalized graphene has been explored both as fluorescence and colorimetric sensing platform for Cr(VI) detection as well as an efficient photocatalyst for reduction of toxic Cr(VI) to non-toxic Cr(III) ions.

DOI： 10.1016/j.cej.2023.145797

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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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DOI： 10.1002/anie.202307093

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

Mechanically interlocked architecture has inspired the fabrication of numerous molecular systems, such as rotaxanes, catenanes, molecular knots, and their polymeric analogues. However, to date, the studies in this field have only focused on the molecular-scale integrity and topology of its unique penetrating structure. Thus, the topological material design of such architectures has not been fully explored from the nano- to the macroscopic scale. Here, we propose a supramolecular interlocked system, MOFaxane, comprised of long chain molecules penetrating a microcrystal of metal–organic framework (MOF). In this study, we describe the synthesis of polypseudoMOFaxane that is one of the MOFaxane family. This has a polythreaded structure in which multiple polymer chains thread a single MOF microcrystal, forming a topological network in the bulk state. The topological crosslinking architecture is obtained by simply mixing polymers and MOFs, and displays characteristics distinct from those of conventional polyrotaxane materials, including suppression of unthreading reactions.

DOI： 10.1038/s41467-023-38835-5

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その他リンク： https://www.nature.com/articles/s41467-023-38835-5

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：ACS Applied Nano Materials  

Accurate detection of trace analytes in biological samples is essential for medical diagnostics but usually requires complex and expensive instruments. Nanozymes, a series of nanosized systems with a catalytic activity mimicking that of peroxidase enzymes, offer a useful alternative for the design of sensing devices. In this article, we describe the synthesis of porous 3D nitrogen-doped crumpled graphene nanoparticles (CGNPs) and their use as a platform for the sensitive detection of dopamine (DA) in complex biological media such as blood serum. CGNPs were prepared by doping graphene oxide (GO) using ammonium hydroxide in a hydrothermal treatment. This procedure leads to the crumpling of GO sheets into porous sphere-like nanoparticles, with a diameter of 34 ± 10 nm. These nanoparticles with high surface area and improved electronic properties proved very active for the oxidation of the peroxidase substrate 3,3′,5,5′- tetramethylbenzidine (TMB). Our sensing device relied on the scavenging of hydroxyl radicals by DA, resulting in a turn-off effect for TMB oxidation. The system selectively detected DA with a limit of detection of 1.15 μM and a linearity range of 1 to 20 μM. The system also possessed good selectivity for DA in the presence of various interfering species, as well as in human blood serum.

DOI： 10.1021/acsanm.2c04582

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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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掲載種別：研究論文（学術雑誌）  

DOI： 10.26434/chemrxiv-2022-bhgjl

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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  

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

The zero area thermal expansion (TE) of a cyanide-bridged honeycomb layer was demonstrated by (PPh4)[Cu2(CN)3] (PPh4+ = tetraphenyl phosphonium) via double distortion relaxation. This characteristic TE behaviour involves in-plane anisotropy of the distorted layer with positive and negative TE. The conformation change in distorted PPh4+ tetrahedrons also occurred between the layers. This was coupled with the anisotropic TE of the layers in accordance with complementary structural changes in the cation and anion counterparts.

DOI： 10.1039/d2ce00878e

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記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1002/chem.202103404

記述言語：英語   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）  

<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：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1021/acs.inorgchem.1c00702

記述言語：英語   掲載種別：研究論文（学術雑誌）  

Anisotropic negative thermal expansion is a valuable property of solid-state materials, influencing their micromechanical and functional response. Two flexible two-dimensional (2D) cyanide-bridged coordination polymers (CPs) of type [Fe(salen)](2)[M(CN)(4)] (M=MnN (FeMnN) and Pt (FePt)) were synthesized. Their anisotropic negative thermal expansions was strongly linked to relaxations of node distortions in [Fe(salen)](+) units. Comparison with the [Mn(salen)](+) analogues indicated shorter bond lengths around iron(III), due to the different electronic states. These changes of node structures resulted in FeMnN and FePt exhibiting lower and higher degrees of anisotropic thermal expansion behavior, respectively, than their Mn analogues.

DOI： 10.1002/cnma.202100026

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1039/d1cc01526e

記述言語：英語   掲載種別：研究論文（学術雑誌）  

Amorphous coordination polymers and metal-organic frameworks (MOFs) have attracted much attention owing to their various functionalities. Here, we demonstrate the tunable water adsorption behavior of a series of amorphous cyanide-bridged MOFs with different metals (M[Ni(CN)(4)]: MNi; M = Mn, Fe, and Co). All three compounds adsorb up to six water molecules at a certain vapor pressure (P-ads) and undergo conversion to crystalline Hofmann-type MOFs, M(H2O)(2)[Ni(CN)(4)]center dot 4H(2)O (MNi-H2O; M = Mn, Fe, and Co). The P-ads of MnNi, FeNi, and CoNi for water adsorption is P/P-0 = 0.4, 0.6, and 0.9, respectively. Although the amorphous nature of these materials prevented structural elucidation using X-ray crystallography techniques, the local-scale structure around the N-coordinated M(2+ )centers was analyzed using L-2,L-3-, K-edge X-ray absorption fine structure, and magnetic measurements. Upon hydration, the coordination geometry of these metal centers changed from tetrahedral to octahedral, resulting in significant reorganization of the MOF local structure. On the other hand, Ni[Ni(CN)(4)] (NiNi) containing square-planar Ni2+ centers did not undergo significant structural transformation and therefore abruptly adsorbed H2O in the low-pressure region. We could thus define how changes in the bond lengths and coordination geometry are related to the adsorption properties of amorphous MOF systems.

DOI： 10.1021/acs.inorgchem.0c03742

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1016/j.eurpolymj.2020.109855

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1021/jacs.9b13568

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1021/jacs.9b07563

記述言語：英語  

DOI： 10.1002/ijch.201800074

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1038/s41467-018-06099-z

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1021/acsami.7b13929

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1039/c7py00309a

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1021/jacs.7b02402

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1002/anie.201700962

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1038/NNANO.2016.233

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1107/S2053273317085412

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1002/admi.201600191

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1021/jacs.6b05552

記述言語：英語  

DOI： 10.1016/j.nantod.2015.04.002

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1039/c2tb00312k

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1021/jp403990m

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1021/jp2115669

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1016/j.jssc.2010.05.002

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1021/ja9092715

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1021/jp907785t

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：英語   会議種別：口頭発表（一般）  

開催地：Mito   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：英語   会議種別：口頭発表（一般）  

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）  

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）  

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：Mito   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：Mito   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：Mito   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：Mito   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）  

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）  

国名：日本国  

開催年月日： 2023年6月

記述言語：英語  

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）  

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）  

国名：日本国  

その他リンク： https://confit.atlas.jp/guide/event/csj102nd/top

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）  

国名：日本国  

その他リンク： https://confit.atlas.jp/guide/event/csj102nd/top

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）  

国名：日本国  

その他リンク： http://www.sakutai.jp/conference_en/the-71st-conference-of-japan-society-of-coordination-chemistry

開催年月日： 2021年7月

記述言語：英語   会議種別：口頭発表（一般）  

国名：インド  

その他リンク： http://www.epormat.com/