記述言語：英語   出版者・発行元：Elsevier  

Mechano-responsive luminescence, or mechanochromic luminescence (MCL), is a type of luminescence that can be reversibly controlled by the addition of mechanical stimuli. Organic materials exhibiting MCL have been an ongoing area of development since the early 2000s, and the number of reports into such materials has been steadily increasing. While the majority of MCL systems rely on the brittle nature of organic crystalline solids, there is a growing interest in "flexible" organic crystals that exhibit mechanical bending or shape deformation owing to their elasticity/plasticity. Such non-destructive deformed crystals may exhibit a new type of MCL that can be controlled by the magnitude of the force stress. In this review, we describe MCL systems capable of the spontaneous recovery of changes in their luminescent properties in response to the loading/unloading of mechanical stress. We particularly focus on the MCL of flexible crystals based on the density gradient of molecular packing (i.e., elastic and plastic crystals) and an emerging system known as "superelastochromism," which is based on spontaneously reversible crystal polymorphism. This emerging research area has the potential to play an important role in the promotion of next-generation soft crystals.

DOI： 10.1016/j.jphotochemrev.2021.100479

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担当区分：責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：Amer Chemical Soc  

A ferroic property such as ferroelasticity in an organic molecular crystal is a lucrative and crucial area to explore and investigate, owing to its potentiality in developing mechanical materials. Direction-dependent mechanical deformations are probable in organic compounds; however, isotropic deformation seems improbable due to their anisotropic structural nature. In this work, we report two-dimensional ferroelasticity in 4-iodoaniline undergoing deformation on two mutually orthogonal planes on the application of external stress, which was investigated by force measurement and single-crystal X-ray diffraction techniques at macroscopic and microscopic levels.

DOI： 10.1021/acs.cgd.1c01394

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担当区分：責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：Amer Chemical Soc  

For ferroelastic deformation, twinning facilitates the plastic shape change, leaving spontaneous strain. The twinning is common in metal solids in their microstructures and, recently, has been found in organic solids under a single-crystal state. To actualize multiferroicity in organic molecular materials, the crystals consisting of organic free radicals can be candidates, bringing magnetic properties in organoferroelastic solids. Herein, we demonstrated the organoferroelastic deformation of organic radical crystals of (2,2,6,6-tetramethylpiperidin-1-yl)oxyl (TEMPO) characterized by force measurements and single-crystal X-ray diffraction analysis.

DOI： 10.1021/acs.cgd.1c01141

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担当区分：責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）  

Chromism-color changes by external stimuli-has been intensively studied to develop smart materials because of easily detectability of the stimuli by eye or common spectroscopy as color changes. Luminescent chromism has particularly attracted research interest because of its high sensitivity. The color changes typically proceed in a one-way, two-state cycle, i.e. a stimulus-induced state will restore the initial state by another stimuli. Chromic systems showing instant, biphasic color switching and spontaneous reversibility will have wider practical applicability. Here we report luminescent chromism having such characteristics shown by mechanically controllable phase transitions in a luminescent organosuperelastic crystal. In mechanochromic luminescence, superelasticity-diffusion-less plastic deformation with spontaneous shape recoverability-enables real-time, reversible, and stepless control of the abundance ratio of biphasic color emissions via a single-crystal-to-single-crystal transformation by controlling a single stimulus, force stress. The unique chromic system, referred to as superelastochromism, holds potential for realizing informative molecule-based mechanical sensing.

DOI： 10.1038/s41467-020-15663-5

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担当区分：責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：WILEY-V C H VERLAG GMBH  

As altering permanent shapes without loss of material function is of practical importance for material molding, especially for elastic materials, shape-rememorization ability would enhance the utility of elastic crystalline materials. Since diffusionless plastic deformability can preserve the crystallinity of materials, the interconversion of diffusionless mechanical deformability between superelasticity and ferroelasticity could enable shape rememorization of superelastic single crystals. This study demonstrates the shape rememorization of an organosuperelastic single crystal of 1,4-dicyanobenzene through time-reversible interconversion of superelasticity-ferroelasticity relaxation by holding the mechanically twinned crystal without heating. The shape-rememorization ability of the organosuperelastic crystal indicates the compatibility of superelasticity (antiferroelasticity) and ferroelasticity as well as the intrinsic workability of organic crystalline materials capable of recovering their crystal functions under mild conditions.

DOI： 10.1002/anie.201905769

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担当区分：筆頭著者,　責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：AMER CHEMICAL SOC  

Superelasticity, which has been known dominantly in association with a specific kind of alloy called shape-memory alloys, involves a peculiar recoverability after plastic deformation. However, metal superelasticity remains difficult in material applications requiring flexible and biocompatible usage. Herein we revealed the versatile recoverability including elasticity, superelasticity, ferroelasticity, and shape-memory effects of soft fatty acid crystals, which can be regarded as biological metabolites, providing new insights into organic materials for incredible shape recoverability.

DOI： 10.1021/acs.cgd.8b01890

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担当区分：責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）  

Ferroelasticity involves the generation of spontaneous strain in a solid by the application of mechanical stress. The phenomenon has been well-studied in metal alloys but relatively neglected in organic solid-state chemistry. Herein we present multiple discrete modes of mechanical twinning and a mechanistic analysis of ferroelasticity in 1,4-diethoxybenzene. Single crystals of the compound can be almost freely deformed, as multiple different twin domains are generated simultaneously. Within each domain, single-crystal character is preserved. Such extremely versatile, ferroelastic deformability is unprecedented in single crystals of any kind and defies the fragility and anisotropic mechanical behaviour of most organic crystals. The dissipated energy and critical stress associated with twinning deformation in 1,4-diethoxybenzene suggests that organic solids could be developed for absorbing weak mechanical shocks in such applications as mechanical damping and soft robotics.

DOI： 10.1002/anie.201803097

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担当区分：責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：Royal Society of Chemistry  

We demonstrate exceptional twinning deformation in a molecular crystal upon application of mechanical stress. Crystal integrity is preserved and the deformation is associated with a large bending angle (65.44°). This is a new strategy to increase the magnitude of the dissipated energy in an organic solid comparable to that seen in alloys. By X-ray crystallographic analysis it was determined that a large molecular rearrangement at the twinning interface preserves the crystal integrity. Drastic molecular rearrangement at the twinning interface helps to preserve hydrogen bonding in the molecular rotation, which facilitates the large bending angle. The maximum shear strain of 218.81% and dissipated energy density of 1 MJ m-3 can significantly enhance mechanical damping of vibrations.

DOI： 10.1039/c8ra02499e

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担当区分：筆頭著者,　責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：NATURE PUBLISHING GROUP  

Superplasticity, which enables processing on hard-to-work solids, has been recognized only in metallic solids. While metallic materials and plastics (polymer solids) essentially possess high plastic workability, functional crystalline solids present difficulties in molding. Organic crystals especially are fragile, in the common view, and they are far from the stage of materials development. From the viewpoint of practical application; however, organic crystals are especially attractive because they are composed of ubiquitous elements and often exhibit higher performance than metallic materials. Thus, finding superplastic deformation of organic crystals, especially in a single-crystal-to-single-crystal manner, will pave the way for their material applications. This study confirmed superplasticity in a crystal of a simple organic compound: N,N-dimethyl-4-nitroaniline. The crystal exhibits single-crystal-to-single-crystal superplastic deformation without heating. This finding of "organosuperplasticity" will contribute to the future design of functional solids that do not lose their crystalline quality in molding.

DOI： 10.1038/s41467-018-06431-7

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担当区分：責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）  

Evidence of ferroelasticity in a non-planar organic molecular crystal is presented for 4,4'-dicarboxydiphenyl ether. Ferroelasticity has been demonstrated by the micro- and macroscopic mechanical characterization of single crystals, including recording of a full hysteretic stress-strain cycle. The underlying mechanism involves the partial flipping of phenyl rings.

DOI： 10.1098/rsos.171146

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担当区分：責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）  

A single crystal of adipic acid shows twinning ferroelasticity by the reversible molecular conformational change. The flexible nature of components in molecular solids raises the efficiency of energy dissipation using organoferroelasticity.

DOI： 10.1039/c7cp07206f

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担当区分：責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）  

Ferroelasticity has been relatively well-studied in mechanically robust inorganic atomic solids but poorly investigated in organic crystals, which are typically inherently fragile. The absence of precise methods for the mechanical analysis of small crystals has, no doubt, impeded research on organic ferroelasticity. The first example of ferroelasticity in an organic molecular crystal of 5-chloro-2-nitroaniline is presented, with thorough characterization by macro- and microscopic methods. The observed cyclic stress-strain curve satisfies the requirements of ferroelasticity. Single-crystal X-ray structure analysis provides insight into lattice correspondence at the twining interface, which enables substantial crystal bending by a large molecular orientational shift. This deformation represents the highest maximum strain (115.9 %) among reported twinning materials, and the associated dissipated energy density of 216 kJ m-3 is relatively large, which suggests that this material is potentially useful as a mechanical damping agent.

DOI： 10.1002/anie.201707749

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担当区分：筆頭著者,　責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：ROYAL SOC CHEMISTRY  

Shape-memory materials, i.e., polymers (SMPs: shape-memory polymers) and alloys (SMAs: shape-memory alloys), have been developed in very different ways since they are historically far apart in material type as well as physical property. In the deformation process, SMPs require only a slight stress due to the properties of organic polymer solids, and they reveal a smaller recovery force during the thermoplastic process whereas SMAs require a relatively large stress due to metallic properties, and they thermally tighten to generate a larger recovery force via destabilization of the stress-induced phase. An investigation into the unexplored area of the material adjoining both ends of SMPs and SMAs would lead toward a better understanding of shape-memory materials and extend future applications and material types. Here, we report the discovery of a shape-memory effect in an organic crystal bearing a combination of crystal transformability like in SMAs with organic components like SMPs.

DOI： 10.1039/c5sc04057d

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担当区分：筆頭著者,　責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：WILEY-V C H VERLAG GMBH  

In solid-state science, most changing phenomena have been mysterious. Furthermore, the changes in chemical composition should be added to mere physical changes to also cover the chemical changes. Here, the first success in characterizing the nature of gas inclusion in a single crystal is reported. The gas inclusion process has been thoroughly investigated by in situ optical microscopy, single-crystal X-ray diffraction analyses, and gas adsorption measurements. The results demonstrated an inclusion action of a first-order transition behavior induced by a critical concentration on the phase boundary. The transfer of phase boundary and included gas are strongly related. This relationship can generate the dynamic features hidden in the inclusion phenomena, which can lead to the guest capturing and transfer mechanism that can apply to spatiotemporal inclusion applications by using host solids.

DOI： 10.1002/anie.201500884

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担当区分：責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：NATURE PUBLISHING GROUP  

Fluidic control is an essential technology widely found in processes such as flood control in land irrigation and cell metabolism in biological tissues. In any fluidic control system, valve function is the key mechanism used to actively regulate flow and miniaturization of fluidic regulation with precise workability will be particularly vital in the development of microfluidic control. The concept of crystal engineering is alternative to processing technology in microstructure construction, as the ultimate microfluidic devices must provide molecular level control. Consequently, microporous crystals can instantly be converted to microfluidic devices if introduced in an active transformability of porous structure and geometry. Here we show that the introduction of a stress-induced martensitic transition mechanism converts a microporous molecular crystal into an active fluidic device with spatiotemporal molecular flow controllability through mechanical reorientation of subnanometre channels.

DOI： 10.1038/ncomms9934

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担当区分：筆頭著者,　責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：WILEY-V C H VERLAG GMBH  

Superelastic materials (crystal-to-crystal transformation pseudo elasticity) that consist of organic components have not been observed since superelasticity was discovered in a Au-Cd alloy in 1932. Superelastic materials have been exclusively developed in metallic or inorganic covalent solids, as represented by Ti-Ni alloys. Organosuperelasticity is now revealed in a pure organic crystal of terephthalamide, which precisely produces a large motion with high repetition and high energy storage efficiency. This process is driven by a small shear stress owing to the low density of strain energy related to the low lattice energy.

DOI： 10.1002/anie.201311014

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担当区分：責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：AMER CHEMICAL SOC  

A novel single-crystal membrane [Cu(II)2(4-F-bza)4(2-mpyz)]n (4-F-bza = 4-fluorobenzoate; 2-mpyz = 2-methylpyrazine) was synthesized and its identical permeability in any crystal direction in the correction for tortuosity proved that gas diffuses inside the channels without detour. H2 permeated by 1.18 × 10(-12) mol m m(-2) s(-1) Pa(-1) with a high selectivity (Fα: 23.5 for H2/CO and 48.0 for H2/CH4) through its 2D-channels having a minimum diameter of 2.6 Å, which is narrower than the Lennard-Jones diameter of H2 (2.827 Å), CO (3.690 Å), and CH4 (3.758 Å). The high rate of permeation was well explained by a modified Knudsen diffusion model based on the space expansion effect, which agrees with the observed permselectivity enhanced for smaller gases in considering the expansion of a channel resulting from the collision of gas molecules or atoms onto the channel wall. An analysis of single-crystal X-ray data showed the expansion order to be H2 > Ar > CH4, which was expected from the permeation analysis. The permselectivity of a porous solid depends on the elasticity of the pores as well as on the diameter of the vacant channel and the size of the target gas.

DOI： 10.1021/ja501045u

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担当区分：筆頭著者,　責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1021/ja9091598

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担当区分：筆頭著者,　責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：AMER CHEMICAL SOC  

Development of gas separation materials has been one of the basic requirements of industry. Microporous materials have adequate pores for gas separation and have contributed to the advancement of gas purification techniques. because the simplest and most economical method would be membrane separation, various microporous membranes have been prepared and explored for their separation properties. However, a key issue remains as to how to generate defect-free membranes with practical gas permeance. Here we report the preparation of a well-oriented single-crystal membrane with high permeance by using a flexible single crystal of [Cu(2)(bza)(4)(pyz)](n) possessing one-dimensional (1D) penetration channels; this membrane exhibits anisotropic gas permeation through the 1D channels with high permselectivity for H(2) and CO(2). Although the diameter of the neck of the narrow channels is smaller than the kinetic diameters of the sample gases, various gases pass through the 1D channels. This report provides a new way of developing gas permeation membranes as sophisticated crystal devices for gas purification techniques.

DOI： 10.1021/ja910492d

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担当区分：筆頭著者,　責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：WILEY-V C H VERLAG GMBH  

To develop the application of the adsorption ability of our flexible single-crystal host [Cu(2)(bza)(4)(pyz)](n) (1) (bza=benzoate; pyz=pyrazine) possessing a I D channel, we study the separation ability of a 1 packed column for various organic vapors and inorganic gases. A 1 packed column can detect various organic molecules with sharp signals although steric or nonpolar molecules give broad signals. Interestingly, 1 separates various organic mixtures even if the mixture contains nonpolar molecules. Comparing the separation properties with columns of other separation media, including zeolite, activated carbon, activated alumina, and silica gel, suggests that a 1 packed column separates various gaseous molecules under moderate conditions. Additionally, the eluted order of similar molecules, such as N(2)/O(2) and methanol/ethanol using the I packed column is different from the others (zeolite, activated carbon, activated alumina, and silica gel), which suggests a difference in the separation mechanism of 1. From GC measurements, the estimated changes in Gibbs free energy by gas adsorption, under diluted gas conditions, exhibits a large entropy dependence caused by regularity in the generated adsorption state, which enables the dynamic control of gas adsorption selectivity. Therefore, it is suggested that single-crystal host 1, because of its flexibility, can separate various gases by adjusting its channel structure according to the features of the guest gaseous molecules. This generates active controllability of the adsorption potential in addition to the intrinsic adsorption interaction.

DOI： 10.1002/asia.200800435

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記述言語：英語   出版者・発行元：ELSEVIER SCIENCE BV  

A new series of microporous materials containing infinite chains of mononuclear metal (Cu(II), Zn(II), Ni(II))-pyridine unit bridged by dicarboxylates, copper(II) terephthalate-pyridine, [Cu-II(OOCC6H4COO)(C5H5N)(2)(H2O)] (.) C5H5N (.) H2O (1), copper(II) terephthalate-4-phenylpyridine, [Cu-II(OOCC6H4COO)(C11H9N)(2)(H2O)] (.) (MeOH)(2) (2), zinc(II) fumarate-pyridine, [Zn-II(OOCC2H2COO)(C5H5N)(3)] (.) C5H5N (.) (H2O)(0.5) (3), zinc(II)terephthalate-pyridine,[Zn-II(OOCC6H4COO)(C5H5N)(2)(H2O)(2)] (.) (C5H5N)(2) (.) (H2O)(2) (4), nickel(II) fumarate-pyridine, [Ni-II(OOCC2H2COO)(C5H5N)(3)] (.) C5H5N (.) (H2O)(2) (5), and nickel(II) terephthalate-pyridine, [Ni-II(OOCC6H4COO)(C5H5N)(3)](6) (.) (C5H5N)(2) (.) (DMF)(6) (.) (H2O)(9) (6), have been prepared. A porous structure, which is formed by stacking and self-assembly of the linear metal(II) dicarboxylates, has been determined by X-ray crystallography. When released with guest solvents, these complexes, except for 5, occlude large amounts of gases such as N-2 and Ar. The maximum amount of N-2 gas is 0.7-10.7 mol per mole of metal(II) salt, indicating the presence of a large number of micro- and/or mesopores. The magnetic susceptibilities of 1 and 2 obey the Curie-Weiss law over the range of 70-300 K (theta = -1.4 K and theta = +5.5 K, respectively); the obtained Weiss constants (theta) indicate the existence of small antiferromagnetic interactions (1), and ferromagnetic interactions (2). The different magnetic behaviors between 1 and 2 demonstrate that hydrogen bonding between the carboxylate groups and coordinated water molecules plays an important role in determining the bridge geometries and superexchange interaction between the Cu(II) ions through the Cu-O C-O-H-O-Cu pathways. In contrast to those of the copper(II) complexes, the magnetic susceptibilities of 5 and 6 obey the Curie law.
Novel inclusion complexes between host microporous molybdenum(II) dicarboxylates (fumarate (7), terephthalate (8), trans-trans-muconate (9), and pyridine-2,5-dicarboxylate (10)) and guest organic polyethers (poly(ethylene glycol) (PEG) and poly(propylene glycol) (PPG)) of various molecular weights have been synthesized. The rate of complex formation depends on the shapes of the micropores and polyethers. The amount of included polyethers increases with their molecular weight, and reaches up to a saturated amount, with the exception that complex 10 does not form complex with bulky PPG. The amount of absorbed argon in the microporous molybdenum(II) dicarboxylates decreases with increase in the amount of include polyethers. The C-13 CP/MAS NMR measurement of complex 8 with PEG has demonstrated that PEG chains are included in the capillaries. This is an effective method for synthesizing supramolecular complexes.
Three dimensional microporous polymers of Rh fumarate (Rh(f)) (11), Rh terephthalate (Rh(t)) (12), and a novel porphyrin rhodium coordination polymer, [Rh-2(H2TCPP)] (H2TCPP = 4,4',4",4'''-(21H,23H-porohine-5,10,15,20-tetrayl)tetrakis benzoic acid) complexes (13) have exhibited high catalytic activities for hydrogen exchange and hydrogenation of olefins (ethylene, propene, and butene) at 200 K. The turnover frequencies of complexes 11, 12, and 13 for hydrogenation of ethylene at 194 K are much higher than those of other published Rh-containing materials. The microwave spectroscopic analyses of the deuterium isotopic distribution of formed propene-d(1) during C3H6-C3D6 reaction over complexes 11 and 12 reveal that the hydrogen exchange reactions take place only inside the nanopores of complexes 11 and 12 without complete scission of C-H bond of olefin molecule. Such a novel bimolecular pathway may play an important role for development of new heterogeneous hydrogenation catalysts. (C) 2004 Elsevier Inc. All rights reserved.

DOI： 10.1016/j.micromeso.2004.02.019

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その他リンク： http://orcid.org/0000-0002-6677-3781

担当区分：筆頭著者,　責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：WILEY-V C H VERLAG GMBH  

DOI： 10.1002/anie.200352982

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その他リンク： http://orcid.org/0000-0002-6677-3781

担当区分：筆頭著者,　責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：WILEY-V C H VERLAG GMBH  

DOI： 10.1002/anie.200351368

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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：ACADEMIC PRESS INC  

Copper(II) terephthalate absorbs a large amount of gases such as N-2, Ar, O-2, and Xe. The maximum amounts of absorption of gases were 1.8, 1.9, 2.2, and 0.9 mole per mole of the copper(II) salt for N-2, Ar, O-2, and Xe, respectively, indicating that the gases were not adsorbed on the surface but occluded within the solid. Other microporous copper(II) dicarboxylates are also reviewed. The porous structure of copper(II) terephthalate, in which the gas is occluded, is deduced from the temperature dependence of magnetic susceptibilities and the linear structure of terephthalate. Microporous molybdenum(II) and ruthenium(II, III) dicarboxylates are discussed. We describe that rhodium(II) monocarboxylate bridged by pyrazine farm stable micropores by self-assembly of infinite linear chain complexes. (C) 2000 Academic Press.

DOI： 10.1006/jssc.2000.8675

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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：GORDON BREACH SCI PUBL LTD  

Magnetic properties of oxygen physisorbed in Cu-trans-1,4-cyclohexanedicarboxylic acid having one-dimensional micropores are studied. O-2 is well known as a magnetic molecule with S=1. In the case of the low adsorption, temperature dependence of the susceptibility shows the Schottky-type broad peak and the high-field magnetization process has a step at around 34T with saturation moment of 2 mu(B)/O-2. These results are interpreted by the dimer model of S=1/2 with an antiferromagnetic exchange interaction. Broadening of the step of magnetization with increasing the adsorption may be due to the interdimer interaction or the distribution of the intra-dimer exchange interaction. Linear magnetization process which is characteristic of one-dimensional Heisenberg antiferromagnet has not been observed even in the full pore region.

DOI： 10.1080/10587259708044542

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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：CHEMICAL SOC JAPAN  

Copper(II) terephthalate absorbs a large amount of gases such as N-2, Ar, O-2, and Xe. The maximum amounts of absorption of gases were 1.8, 1.9, 2.2, and 0.9 mole per one mole of the copper(II) salt for N-2, Ar, O-2, and Xe, respectively, indicating that the gases were not adsorbed on the surface but occluded within the solid. The porous structure of copper(II) terephthalate, in which the gas is occluded, is deduced from the temperature dependence of magnetic susceptibilities and the linear structure of terephthalate.

DOI： 10.1246/cl.1997.1219

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掲載種別：研究論文（学術雑誌）   出版者・発行元：Royal Society of Chemistry (RSC)  

A series of polyhalogenated platinum(<sc>ii</sc>)–bipyridine complexes showed solvent-of-crystallisation-dependent elastic flexibility and luminescence.

DOI： 10.1039/d1ce00459j

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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：ROYAL SOC CHEMISTRY  

Mechanically adaptable molecular crystals have potential applications in flexible smart materials and devices. Here, we report the mechanism of plastic deformation in single crystals of a small organic molecule (N-(4-ethynylphenyl)-3-fluoro-4-(trifluoromethyl)benzamide) that can be repeatedly irreversibly bent and returned to its original shape without concomitant delamination or loss of integrity. Along with the quantification of the crystals' local and bulk mechanical properties (hardness, indentation modulus and Young's modulus), micro-focus synchrotron X-ray diffraction mapping show that upon deformation, molecular layers lined with trifluoromethyl groups cooperatively slip past one another resulting in their impressive plastic malleability.

DOI： 10.1039/d0cc05904h

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担当区分：責任著者   掲載種別：研究論文（学術雑誌）   出版者・発行元：American Chemical Society (ACS)  

DOI： 10.1021/acs.cgd.0c00964

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掲載種別：研究論文（学術雑誌）   出版者・発行元：Wiley  

DOI： 10.1002/ange.201914610

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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：WILEY-V C H VERLAG GMBH  

Ferroelasticity has been reported for several types of molecular crystals, which show mechanical-stress-induced shape change under twinning and/or spontaneous formation of strain. Aiming to create materials that exhibit both ferroelasticity and light-emission characteristics, we discovered the first examples of ferroelastic luminescent organometallic crystals. Crystals of arylgold(I)(N-heterocyclic carbene)(NHC) complexes bend upon exposure to anisotropic mechanical stress. X-ray diffraction analyses and stress-strain measurements on these ferroelastic crystals confirmed typical ferroelastic behavior, mechanical twinning, and the spontaneous build-up of strain. A comparison with single-crystal structures of related gold-NHC complexes that do not show ferroelasticity shed light on the structural origins of the ferroelastic behavior.

DOI： 10.1002/anie.201914610

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記述言語：英語   掲載種別：研究論文（学術雑誌）  

Here, we report practical method for asymmetric synthesis of cyclopropane-fused GABA analogs. Starting from 2–furaldehyde, the cis–isomer (CAMP) was synthesized over 10 steps; (–)– and (+)–CAMP•HCl were synthesized by employing d– and l–menthol as the chiral auxiliary for total 2.5% and 1.3% yields, respectively. On the other hand, the trans–isomer (TAMP) was elaborated via double asymmetric induction, i.e. organocatalytic asymmetric cyclopropanation on chiral substrate. Thus, starting from l– and d–menthyl acrylate, in combination with quinidine-derived and quinine-derived organocatalysts, (–)– and (+)–TAMP•HCl were synthesized in total 6.6% and 3.7% yields, respectively, over 8 steps each. Configurational analysis of the synthetic intermediates based on 13C NMR is also reported. Preliminary oncological assays showed the weak but specific activities of CAMP and TAMP as the molecular basis of GABA analogs, which are still left unexplored.

DOI： 10.1246/bcsj.20190168

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記述言語：英語   掲載種別：研究論文（学術雑誌）  

A synthetic strategy for accessing protoaculeine B (1), the N-terminal amino acid of the highly modified peptide toxin aculeine, was developed via the synthesis of the fully protected natural homologue of 1 with a 12-mer poly(propanediamine). The synthesis of mono(propanediamine) analog 2, as well as core amino acid 3, was demonstrated by this strategy. New amino acid 3 induced convulsions in mice; however, compound 2 showed no such activity.

DOI： 10.1021/acs.orglett.8b01331

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担当区分：責任著者   掲載種別：研究論文（学術雑誌）  

DOI： 10.1039/C8CE00295A

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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：PHYSICAL SOC JAPAN  

Inelastic neutron scattering experiments are performed on the nanoporous metal complex Cu-trans-1,4-cyclo-hexanedicarboxylic acid (Cu-CHD) adsorbing O-2 molecules to identify the spin model of the O-2-based magnet realized in the host complex. It is found that the magnetic excitations of Cu-CHDs adsorbing low- and high-concentration O-2 molecules are explained by different spin models, the former by spin dimers and the latter by spin trimers. By using the obtained parameters and by assuming that the levels of the group of the highest energy states are reduced because of the nonnegligible spin dependence of the molecular potential of oxygen, the magnetization curves are explained quantitatively.

DOI： 10.7566/JPSJ.85.034717

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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：PHYSICAL SOC JAPAN  

Inelastic neutron scattering experiments are performed on the nanoporous metal complex Cu-trans-1,4-cyclo-hexanedicarboxylic acid (Cu-CHD) adsorbing O-2 molecules to identify the spin model of the O-2-based magnet realized in the host complex. It is found that the magnetic excitations of Cu-CHDs adsorbing low- and high-concentration O-2 molecules are explained by different spin models, the former by spin dimers and the latter by spin trimers. By using the obtained parameters and by assuming that the levels of the group of the highest energy states are reduced because of the nonnegligible spin dependence of the molecular potential of oxygen, the magnetization curves are explained quantitatively.

DOI： 10.7566/JPSJ.85.034717

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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：Physical Society of Japan  

Inelastic neutron scattering experiments are performed on the nanoporous metal complex Cu-Trans-1,4-cyclohexanedicarboxylic acid (Cu-CHD) adsorbing O2 molecules to identify the spin model of the O2-based magnet realized in the host complex. It is found that the magnetic excitations of Cu-CHDs adsorbing low-And high-concentration O2 molecules are explained by different spin models, the former by spin dimers and the latter by spin trimers. By using the obtained parameters and by assuming that the levels of the group of the highest energy states are reduced because of the nonnegligible spin dependence of the molecular potential of oxygen, the magnetization curves are explained quantitatively.

DOI： 10.7566/JPSJ.85.034717

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担当区分：責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）  

Deformation twinning, which is a type of plastic deformation, has been particularly investigated in metal materials. However, only a few examples are found in organic solids. We observed mechanical twinning deformation on a simple ferrocene crystal, which is considered the most representative organometallic compound, and evaluated the crystal structures under the twinning state and the shear deformation characteristics by single-crystal X-ray diffraction analysis and uniaxial compression tests. The structural analyses showed the molecular rearrangement during twinning deformation. The shear deformation properties depend on the rotational mobility of the cyclopentadienyl rings in comparison with crystals of nickelocene, ruthenocene, and mixed crystals of ferrocene/ruthenocene.

DOI： 10.1039/c4dt03922j

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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：CHEMICAL SOC JAPAN  

The synthetic efforts to dysibetaine CPb, isolated from Micronesian marine sponge, amenable to analog synthesis are reported. Cyclopropane was constructed by a sulfonium ylide-mediated reaction and enantioselective desymmetrization was performed by methanolysis mediated by a quinine derivative. (+)-N-(Desmethyl)dysibetaine CPb was finally synthesized in 0.37% yield in total 14 steps. This is the first synthesis of the dysibetaine CPb analog.

DOI： 10.1246/cl.141049

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担当区分：筆頭著者,　責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：WILEY-V C H VERLAG GMBH  

Generally, superelastic behavior cannot be expected in mechanically twinned crystals because there is essentially no strain on the interface that is a driving force for spontaneous shape recovery. However, we found that single crystals of 3,5-difluorobenzoic acid are superelastic organic crystals under mechanical twinning. The unexpected shape recovery can be explained by molecular distortion on the twinning interface, which suggests a new mechanism for superelasticity in molecular materials.

DOI： 10.1002/anie.201411447

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担当区分：責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：ROYAL SOC CHEMISTRY  

A novel microporous single crystal of [Cu(II)2(1-NA)4(pyz)]n (1-NA: 1-naphthoate, pyz: pyrazine) exhibited bending and straightening action on a macroscopic scale during the first-order crystal phase transition induced by methanol vapor sorption.

DOI： 10.1039/c4cc09948f

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記述言語：英語  

DOI： 10.1039/c3dt53388c

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その他リンク： http://orcid.org/0000-0002-6677-3781

記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：PERGAMON-ELSEVIER SCIENCE LTD  

The first total syntheses of (-)-dysibetaine CPa and the antipode have been achieved using enantioselective solvolysis of meso-cyclic anhydride mediated by quinine derivative as an organocatalyst. The synthesis features a demonstration of an enantiodivergent organic synthesis of both enantiomers of dysibetaine CPa whereby the absolute configurations of natural product were elucidated as (3R,4R). Application of the present methodology to an enantiomerically pure novel GABA analog is also reported. (C) 2014 Elsevier Ltd. All rights reserved.

DOI： 10.1016/j.tet.2014.05.053

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担当区分：責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：ROYAL SOC CHEMISTRY  

A novel molecular crystal membrane [Cu(II)2(9-AC)4(pyz)]n (9-AC: 9-anthracenecarboxylate, pyz: pyrazine) shows high permselectivity for H2/CO (79.0), H2/CH4 (137), and H2/CO2 (12.1) due to the high rate of H2 permeation (3820 Barrer) while inhibiting the permeation of such a large gaseous particle even in its wider channel than the Lennard-Jones diameter of each gas.

DOI： 10.1039/c4cc01494d

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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：PERGAMON-ELSEVIER SCIENCE LTD  

Here we report total synthesis of enantiomerically pure dysibetaine CPa, isolated from Micronesian marine sponge and expected to serve as a neuroactive agent. Starting from meso-cyclopropane triester, the synthesis was achieved in 12.8% overall yield over 10 steps including organocatalytic enantioselective solvolysis of meso-succinic anhydride as a key step. This work established the absolute configurations of the natural product as (3R,4R). (C) 2013 Elsevier Ltd. All rights reserved.

DOI： 10.1016/j.tetlet.2013.08.113

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記述言語：英語  

DOI： 10.1021/jm301590z

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その他リンク： http://orcid.org/0000-0002-6677-3781

記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：ELSEVIER SCIENCE SA  

The crystal structure of the thermoelectric clathrate Sn24P19.3I8 was determined down to 10 K showing no variations with the temperature. Even at 10 K Sn24P19.3I8 crystallizes in the type-I clathrate structure, space group Pm3-n, with the cubic unit cell parameter ranging from 10.9173 angstrom at 10 K to 10.9554 angstrom at room temperature. In its crystal structure, tin and phosphorus atoms form the framework that traps the guest iodine atoms in the polyhedral cavities of two different shapes. The temperature-dependent crystal structure data and the results of the heat capacity measurements revealed the localized vibrations of the guest atoms inside the oversized cavities with the characteristic Einstein temperatures of theta(E1) = 60 K and theta(E2) = 78 K, whereas the characteristic Debye temperature for Sn24P19.I-3(8) is 265 K. The room temperature lattice thermal conductivity was calculated using the Debye model to be kappa(L) = 0.85 W m(-1) K-1, which is in excellent agreement with the experimentally measured data and demonstrates that the thermal conductivity is almost entirely phononic. (C) 2012 Elsevier B.V. All rights reserved.

DOI： 10.1016/j.jallcom.2011.12.171

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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：ELSEVIER SCIENCE SA  

A homoleptic hexanuclear Cu cluster, [(Cu(DSB)(CBT))(2)(Cu2Br)(2)][PPh4](2) (1-PPh4) [DSB = 2,3-disulfidobenzoate; CBT = 3-carboxybenzene-1,2-bis(thiolate)] was synthesized as dark green crystals by the reaction of CuCl2 with 2,3-dimercaptobenzoic acid in acetate buffer solution. The X-ray crystal study of 1-PPh4 revealed its unique structural features: (1) one of two types of crystallographically distinct Cu centers adopted a square planer geometry and the other center had a tetrahedral geometry, and (2) intermolecular H-bonding interactions connected between carboxylic acid group of CBT and the carboxylate group of DSB led to the construction of an unprecedented topologic architecture of a zigzag patterned infinite sheet. In addition, taking into account the total charge of the molecule, which contained 2,3-disulfidobenzoate and 3-carboxybenzene-1,2-bis(thiolate), and the diamagnetic nature of 1-PPh4, 1-PPh4 led to it is assignment as a mixed-valence Cu(I)/Cu(III) cluster. Such mixed valence states of Cu atoms were also examined by density functional theory calculation. (C) 2011 Elsevier B.V. All rights reserved.

DOI： 10.1016/j.ica.2011.03.055

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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：ROYAL SOC CHEMISTRY  

Two porous supramolecular isomeric frameworks show unique sorption properties, one with temperature dependent stepwise and hysteretic selective sorption of CO2 while the other one shows gas uptake capacity for CO2, N-2, H-2 and CH4 at low temperature and selective sorption of CO2 over N-2 around room temperature.

DOI： 10.1039/c1cc10899a

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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：ROYAL SOC CHEMISTRY  

A highly stable copper(II) microporous framework with cylindrical channels constructed from 1,4-di(1H-imidazol-4-yl)benzene (H2L) and CuCl2 center dot 2H(2)O is composed of Cu(II)-imidazolate tubes interconnected by the 1,4-phenylene group of L2-, and shows temperature dependent selective gas sorption properties.

DOI： 10.1039/c0cc04085a

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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：ROYAL SOC CHEMISTRY  

A unique 4-fold interpenetrated (10,3)-b copper(II) framework exhibits reversible dehydration and rehydration in a single-crystal-to-single-crystal (SC-SC) process, and the dehydrated material can encapsulate CH(3)OH molecules, again in a SC-SC fashion, and shows selective adsorption of H(2) and CO(2) over N(2).

DOI： 10.1039/c0cc04689b

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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：CHEMICAL SOC JAPAN  

An anomalous isotope effect was observed in the (35)C1NQR frequency of pyrrolidinium p-chlorobenzoate (C4H8NH2+center dot C1C(6)H(4)COO(-)) by deuterium substitution of hydrogen atoms which form two kinds of N-H center dot center dot center dot O type hydrogen bonds. Large negative frequency shifts of the 35CI resonance lines, reaching 309 kHz at 77K and 267 kHz at 293K, were obtained upon deuteration, although the Cl atom in the molecule formed no hydrogen bonds in the crystal. H-1 MAS NMR lines showed significant changes by the deuterium substitution, while in contrast, small shifts of (CCP)-C-13/ MASNMR signals were obtained. Our measurements of H-1 NMR spin-lattice relaxation times (T-1) suggested that the H/D isotope shifts detected from the (35)C1NQR frequencies and 1H NMR spectra are due to structural changes rather than molecular dynamics. Single-crystal X-ray diffraction measurements showed two remarkable H/D isotope differences in the molecular arrangements, (i) the N-H length along the crystallographic a axis became I pm shorter, and (ii) the dihedral angle between benzene and the pyrrolidine ring changed by 1.1(2)degrees upon deuteration. Using density functional theory estimations, the anomalous (35)C1NQR frequency shifts and H-1 MASNMR line-shape changes could be explained by the dihedral angle change rather than the N-H length difference.

DOI： 10.1246/bcsj.20090300

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記述言語：英語   掲載種別：研究論文（国際会議プロシーディングス）   出版者・発行元：SPRINGER  

H/D isotope effects onto Br-79 NQR frequencies of piperidinium p-bromobenzoate were studied by deuterium substitution of hydrogen atoms which form two kinds of N-H center dot center dot center dot O type hydrogen bonds, and the isotope shift of ca. 100 kHz were detected for a whole observed temperature range. In addition, H-1 MAS NMR spectra measurements of piperidinium and pyrrolidinium p-bromobenzoate were carried out and little isotope changes of NMR line shape were detected. In order to reveal effects of molecular arrangements into the obtained isotope shift of NQR frequencies, single-crystal X-ray measurement of piperidinium p-bromobenzoate-d2 and density-functional-theory calculation were carried out. Our estimation showed the dihedral-angle change between piperidine and benzene ring contributes to isotope shift rather than those of N-H lengths by deuterium substitution.

DOI： 10.1007/s10751-010-0198-z

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その他リンク： http://orcid.org/0000-0002-6677-3781

記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：AMER PHYSICAL SOC  

Spin dynamics of the square lattice Heisenberg antiferromagnet, Ba(2)MnGe(2)O(7), is studied by a combination of bulk measurements, neutron diffraction, and inelastic neutron-scattering techniques. Easy plane type antiferromagnetic order is identified at T &lt; 4.0 K. The exchange interactions are estimated as J(1)=27.8(3) mu eV and J(2)=1.0(1) mu eV, and the saturation field H(C) is 9.75 T. Magnetic excitation measurements with high experimental resolution setup by triple axis neutron spectrometer reveals the instability of one magnon excitation in the field range of 0.7H(C)less than or similar to H less than or similar to 0.85H(C).

DOI： 10.1103/PhysRevB.81.100402

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担当区分：筆頭著者,　責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：ROYAL SOC CHEMISTRY  

The adsorption behavior of a flexible single-crystal host [Cu(2)(bza)(4)(pyz)](n) was studied for a planar triangular molecule and investigated for large host structural changes including a switch of channel geometry responding to included guest molecules.

DOI： 10.1039/b917263g

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担当区分：筆頭著者,　責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1039/c002569k

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担当区分：筆頭著者,　責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：ROYAL SOC CHEMISTRY  

In order to investigate the methane-included condition in porous materials and its response to external stimuli, the methane adsorption state of a single-crystal adsorbent, [Cu(II)(2)(bza)(4)(pyz)](n), was studied by single-crystal X-ray analysis and adsorption measurement as functions of temperature (90-298 K) and pressure (3.2-42 MPa). The included methane molecule was encapsulated into the channel of the adsorbent and stabilized through the interactions between the surrounding aromatic rings. The single-crystal host readily adsorbed methane gas and easily achieved the saturated condition with the included amount of 2 methane molecules per Cu(2) unit. The results from the gas adsorption measurements were consistent with the results from the crystallographic structures. Single-crystal X-ray analysis showed that the methane-saturated crystal has a critical temperature of the crystal phase transition from the C2/c to the P (1) over bar space group between 150 and 200 K. In temperature swinging, the thermal factors of the atoms of the guest methane and host skeleton monotonically decreased as the temperature decreased. In contrast, in pressure swinging at 298 K, the thermal factors gradually decreased as the pressure increased, after passing 11 MPa only the thermal factor of the guest methane decreased in response to an increase in gas pressure while those of the host skeleton remained almost constant. It is suggested that the channel acts as "force guide," propagating the outside gas pressure into the crystal inside through a guest-guest interaction in the included gas array. In addition, the difference in the pressure dependencies of the thermal factors on the host and guest suggested that the structural susceptibility to external gas pressure and temperature is different between open porous solids and non-porous solids.

DOI： 10.1039/b813178c

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担当区分：筆頭著者,　責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：ROYAL SOC CHEMISTRY  

The CO(2) adsorption behavior and inclusion structure of a flexible single-crystal host [Cu(2)(bza)(4)(pyz)](n) were studied under various conditions (203-373 K, &lt;15.4 MPa) and the correlation between changes in gas adsorption behavior and the structures of guest arrangement and host component packing were investigated.

DOI： 10.1039/b914922h

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担当区分：筆頭著者,　責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：ROYAL SOC CHEMISTRY  

The adsorption behavior of a single-crystal host [Cu(2)(bza)(4)(pyz)](n) under vapor was studied by adsorption measurements and single-crystal X-ray analyses, demonstrating the sharp replacement of the included guest by mixing the surrounding vapor.

DOI： 10.1039/b904160e

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記述言語：英語   出版者・発行元：PHYSICAL SOC JAPAN  

We performed an inelastic neutron scattering, experiment to Study the magnetic excitation of O-2 molecules adsorbed in a microporous compound. A dispersion less excitation with characteristic intensity modulation is observed at h omega = 7.8 meV at low temperature. The neutron cross section is explained by using a spin dimer model with an intradimer distance of 3.1 angstrom. Anomalous behaviour in the temperature dependence is discussed in the context of enhanced magnetoelasticity in the soft framework of the O-2 molecule.

DOI： 10.1143/JPSJ.77.083703

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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：AMER CHEMICAL SOC  

Reactions of nickel(II) nitrate with 4,5-imidazoledicarboxylic acid (H3L) in neutral or basic environment result in a series of novel nickel coordination polymers with a uniform Ni-8 cubic building block, [(Ni-8(H2L)(8)(HL)(4))center dot 8(C2H5OH)center dot 18(H2O) 1, K-20[Ni8L12]center dot 74(H2O) 2a, K-20[Ni8L12]center dot 50(H2O) 2b, and K-20[Ni8L12]center dot 29(H2O) 2c. The result shows that complex 1 assembles into a discrete neutral metal-organic polyhedron with 20 protons located in the carboxyl oxygen atoms, which are linked into a three-dimensional supramolecular architecture by intermolecular hydrogen bonds between guest ethanol and host carboxyl oxygen atoms. Complex 2a exhibits a-water ocean, in which there are 20 potassium ions and 74 water molecules around each Ni-8 cubic building block. During the course of gradual loss of the guest water molecules, the adjacent cubic building blocks in 2a rearrange to form its dehydrated products 2b and 2c, the crystallinity remaining. The magnetic properties have been investigated.

DOI： 10.1021/cg8000762

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その他リンク： http://orcid.org/0000-0002-6677-3781

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

Anomalous isotope effects were detected in the (35)Cl nuclear quadrupole resonance (NQR) frequency of piperidinium p-chlrobenzoate (C(5)H(10)NH center dot ClC(6)H(4)COOH) by deuteration of hydrogen atoms. The atoms were determined to form two kinds of N-H center dot center dot center dot O type H-bonds in the crystal structure. Large frequency shifts of the (35)Cl resonance lines reaching 288 kHz at 77 K and 278 kHz at room temperature were caused upon deuteration, in spite of the fact that the Cl atoms in the molecule do not form hydrogen bonds in the crystal. Results of single crystal X-ray diffraction measurements and density-functional-theorem calculations suggest that a dihedral-angle change of 1.8 degrees between benzene and the piperidine ring contributes to (35)Cl NQR anomalous frequency shifts.

DOI： 10.1007/s10751-008-9701-1

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担当区分：筆頭著者,　責任著者   記述言語：英語   出版者・発行元：INT UNION CRYSTALLOGRAPHY  

DOI： 10.1107/S0108767308086492

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担当区分：責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：PERGAMON-ELSEVIER SCIENCE LTD  

The crystalline one-dimensional compounds, [M-2(bza)(4)(pyz)](n) (bza = benzoate; pyz = pyrazine; M = Cu-II (1)) and [M-2(bza)(4)(2-mpyz)](n) (2-mpyz = 2-methylpyrazine; M = Rh-II (2), Cu-II (3)), demonstrate gas absorbency of NO. The amounts of adsorbed NO gas are 0.61 for 1, 0.30 for 2, and 0.23 for 3 per M-2 unit at 195 K (800 Torr). The crystals of I adsorbed more NO molecules than did those of 2 and 3. The magnetic susceptibilities of the NO-inclusion crystals indicate that included NO molecules interact antiferromagnetically with neighboring guests without dimerization to N2O2. Magnetic behaviors indicated NO aggregation in the narrow ID channels of 1-3 under unsaturated adsorption conditions.

DOI： 10.1016/j.poly.2006.09.024

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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：PERGAMON-ELSEVIER SCIENCE LTD  

Adsorption properties of magnetic species in nano-porous crystals were studied theoretically. The crystal [Rh(2)bza(4)pyz](n), which had been reported by Mori, Takamizawa and their co-workers in detailed, was employed in this study. As adsorbed magnetic radicals, a oxygen molecule (O-2; S = 1) was treated. From the results by our MO calculations, weak magnetic interactions between O-2 molecules in cavities existed. Two types of magnetic interactions (ferro- and antiferro-magnetic) made alignment of trimer spin structure. Our theoretical calculations analyzed not only position but also orientation of the adsorbed O-2 molecules. For the position, cloud of mass densities of O-2 molecules by MD simulation showed stacking styles in nano-pores statistically. Number of adsorbed gas was estimated to be 3.00 molecules/unit. For the orientation, a certain adsorbed O-2 molecule was stabilized by contribution of the two next O-2 molecules as well as four phenyl groups. (c) 2007 Elsevier Ltd. All rights reserved.

DOI： 10.1016/j.poly.2007.01.056

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記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1021/jp065321x

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記述言語：英語   出版者・発行元：AMER CHEMICAL SOC  

The coordination properties of multidentate nonplanar aromatic ligands containing two and three benzene rings, namely [2.2]- and [2.2.2]paracyclophanes, have been explored. A gas-phase deposition approach has been used to examine metal-pi interactions in a solvent-free environment as well as to prepare organometallic pi-complexes of paracyclophane ligands in crystalline form. To force bridging modes of paracyclophanes and to achieve the formation of extended organometallic assemblies, a dinuclear metal complex having two centers of Lewis acidity, namely [Rh-2(O2CCF3)(4)], has been used. As a result, a product with Rh-2:L-2 = 1: 1 composition (1) has been obtained from the reaction of dirhodium(II,II) tetrakis-(trifluoroacetate) with [2.2]paracyclophane (L-2 = C16H16). Complex 1 consists of alternating dimetal units and [2.2]paracyclophane bridges that form I-D organometallic chains: [Rh-2(O2CCF3)(4)center dot(mu(2)-eta(2):eta(2)-C16H16)](infinity)(1). In the case of [2.2.2]paracyclophane (L-3 = C24H24), two new rhodium-based products of the stoichiometries Rh-2:L-3 = 1:2 (2) and 3:2 (3) have been prepared in crystalline form. Complex 2 is a discrete bis adduct with terminally bound aromatic ligands, [Rh-2(O2CCF3)(4)center dot(eta(1)-C24H24)(2)], while 3 exhibits a unique 2-D layered structure built on an unprecedented tridentate mu(3)-eta(2):eta(2):eta(2) coordination of [2.2.2]-paracyclophane. Since the layers in 3 overlay to form [2.2.2]paracyclophane-based open channels running along the c direction, the gas sorption properties of the crystalline material, {[Rh-2(O2CCF3)(4)](3)center dot(C24H24)(2)}, have been tested. In addition to mono- and tridentate coordination Of C24H24 revealed in 2 and 3, a rare bidentate bridging mode of [2.2.2]paracyclophane is found in its ruthenium(I) complex obtained by gas-phase reaction of hydrocarbon with the diruthenium(I,I) carbonyl trifluoroacetate unit, [RU2(O2CCF3)(2)-(CO)(4)]. The resulting product of the Ru-2:L-3 = 1: 1 composition exhibits a 1-D chain structure, namely [Ru-2(O2CCF3)(2)(CO)(4)center dot(mu(2)-eta(2):eta(2)-C24H24)](infinity)(1) (4). Overall, three new coordination modes of [2.2.2]paracyclophane have been revealed to afford a discrete complex, as well as I-D and 2-D extended organometallic networks. This versatility of [2.2.2]paracyclophane has been fully realized under gas-phase deposition conditions that allow one to utilize effectively the geometrical and electronic structures of aromatic ligands in the formation of new organometallic products.

DOI： 10.1021/om051100m

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担当区分：筆頭著者,　責任著者  

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その他リンク： http://orcid.org/0000-0002-6677-3781

担当区分：責任著者  

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その他リンク： http://orcid.org/0000-0002-6677-3781

担当区分：責任著者  

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その他リンク： http://orcid.org/0000-0002-6677-3781

担当区分：責任著者  

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その他リンク： http://orcid.org/0000-0002-6677-3781

担当区分：筆頭著者,　責任著者   記述言語：英語   出版者・発行元：INT UNION CRYSTALLOGRAPHY  

DOI： 10.1107/S0108767305086575

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担当区分：筆頭著者,　責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：ROYAL SOC CHEMISTRY  

The generation of oxygen inclusion crystals through oxygen gas adsorption was characterized at 90 K to show that a one-dimensional oxygen molecular chain crystallizes in the channels of the host lattice to be captured with its exact structure stabilized under the included state.

DOI： 10.1039/b406137c

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その他リンク： http://orcid.org/0000-0002-6677-3781

担当区分：筆頭著者,　責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：CHEMICAL SOC JAPAN  

The formation of CS2 inclusion crystals through vapor adsorption was characterized to show that large CS2 guests are tightly confined in the channel supported on the pi orbital of the conjugate planes of the channel surface: the manner of guest alignment is strongly influenced by the structures of the guest and channel.

DOI： 10.1246/cl.2004.538

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担当区分：筆頭著者,　責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：ROYAL SOC CHEMISTRY  

Single-crystal X-ray analysis at 10 K revealed adsorbed oxygen within the ultramicropores of a single crystal gas adsorbent, rhodium(II) benzoate-pyrazine. This indicates that the oxygen molecules were captured on the necks of infinite channels by the intermolecular interaction between the guest O-2 and the benzoate moieties on the inner host surface and the guest probably diffuses through the narrow necks driven by surface local motion.

DOI： 10.1039/b316963d

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その他リンク： http://orcid.org/0000-0002-6677-3781

担当区分：筆頭著者,　責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：ELSEVIER SCIENCE BV  

A crystalline solid, [Rh(II)(2)(bza)(4)(1,5-nptd)](n) (bza and 1,5-nptd = benzoate and 1,5-naphthyridine), was synthesized and characterized by single-crystal X-ray diffraction analysis; the microporous compound demonstrates gas adsorbency with a N-2 BET surface area of 291.6 m(2) g(-1). (C) 2003 Elsevier B.V. All rights reserved.

DOI： 10.1016/j.inoche.2003.10.028

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その他リンク： http://orcid.org/0000-0002-6677-3781

担当区分：筆頭著者,　責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：ELSEVIER SCIENCE BV  

A novel gas inclusion solid was generated by cooling an empty host crystal of copper(II) benzoate-pyrazine in a carbon dioxide environment and characterized by single-crystal X-ray diffraction analysis. (C) 2003 Elsevier B.V. All rights reserved.

DOI： 10.1016/j.inoche.2003.09.011

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その他リンク： http://orcid.org/0000-0002-6677-3781

担当区分：筆頭著者,　責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：ELSEVIER SCIENCE BV  

A novel inclusion crystal, {[Rh(II)(2)(bza)(4)(pyz)](n) (.) 3n(N2O)} (1), was prepared and characterized by single-crystal X-ray diffraction analysis; linear alignment (N2O)(n) coherently generates in the channels of host rhodium benzoate pyrazine and there is a high possibility of the existence of an intermediate phase induced by a slight amount of adsorbed N2O inside the crystal even at room temperature. (C) 2003 Elsevier B.V. All rights reserved.

DOI： 10.1016/j.inoche.2003.08.026

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その他リンク： http://orcid.org/0000-0002-6677-3781

担当区分：筆頭著者,　責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：ELSEVIER SCIENCE BV  

A novel crystalline solid, [CU(II)(2)(O2CPh)(4)(2,5-dmpyz)](n) (2,5-dmpyz = 2,5-dimethyl-pyrazine), was synthesized and characterized by single-crystal X-ray diffraction analysis. The compound demonstrates multistep phase transition induced by CO2 adsorption, which readily obeys the Clausius-Clapeyron equation in terms of the set of partial pressures of CO2 and transition temperatures. (C) 2003 Elsevier B.V. All rights reserved.

DOI： 10.1016/j.inoche.2003.08.010

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その他リンク： http://orcid.org/0000-0002-6677-3781

担当区分：筆頭著者,　責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：ROYAL SOC CHEMISTRY  

The crystal structures of two gas inclusion compounds containing carbon dioxide and argon have been determined by conventional single-crystal X-ray diffraction analysis at room temperature. The analysis revealed different manners of gas inclusion, where hydrogen bond interaction and the pi orbital of the conjugate plane cooperatively capture the adsorbed gaseous guests.

DOI： 10.1039/b312553j

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その他リンク： http://orcid.org/0000-0002-6677-3781

担当区分：筆頭著者,　責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：ELSEVIER SCIENCE BV  

A novel porous solid of ruthenium(II, III) dimer complex, [Ru-2(p-(O2CC6H4NHCOBu)-Bu-1)(4)Cl], constructed by intermolecularly linking the hydrogen bonds of NH...O and NH...Cl was synthesized and the porous structure was crystallographically determined. The dried crystalline solid shows a high BET surface area determined by measuring the adsorption of nitrogen gas and water vapor. (C) 2003 Elsevier B.V. All rights reserved.

DOI： 10.1016/S1387-7003(03)00240-5

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記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1246/cl.2003.854

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その他リンク： http://orcid.org/0000-0002-6677-3781

担当区分：筆頭著者,　責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：ELSEVIER SCIENCE BV  

A novel crystalline solid, [Cu(II)(2)(O2CPh)(4)(pyz)](n), was synthesized and characterized by single-crystal X-ray diffraction analysis; the compound demonstrates thermal phase transition that is correlated with CO2 adsorption. (C) 2003 Elsevier Science B.V. All rights reserved.

DOI： 10.1016/S1387-7003(03)00078-9

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その他リンク： http://orcid.org/0000-0002-6677-3781

担当区分：筆頭著者,　責任著者   記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：CHEMICAL SOC JAPAN  

The structure of a linear chain complex [Rh(II)(2)(O2CPh)(4)(pyz)](infinity) was characterized by X-ray diffraction analysis. The solid indicates nitrogen adsorption on a microporous medium although the crystal does not seem to have a microporous structure. There is a high possibility that the structure changes to open the crystal packing for gas molecules.

DOI： 10.1246/cl.2002.1208

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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：ELSEVIER SCIENCE SA  

Previous theoretical models of organometallic magnetic conductors and superconductors are examined on the basis of ab initio Hamiltonians and Hubbard models for clusters of p-d and pi-d systems in relation to the recently developed pi-d systems such as (BEDT-TTF)(2)Y and (BETS)(2)Y (Y = Cu(NCS)(2), Cu[N(CN)(2)]X, Fe(III)X-4 (X = halogens, etc.)). The Fe(III) complexes have been used as spin sources in these systems. The phase diagrams observed for the species are similar to those of cuprate and heavy fermion superconductors because of the existence of a magnetic phase near superconducting phase. In order to elucidate the characteristic electronic structures of these species, effective exchange integrals (J(ab)) for magnetic clusters are calculated by ab initio density functional (DFT) methods. From the computational results, several model Hamiltonians such as t-J, Kondo and RKKY models are examined for a theoretical understanding of the experimental phase diagrams. Theoretical possibilities of magnetic conductors and spin-mediated superconductors are discussed on the basis of these models in the intermediate region for metal-insulator transitions. The importance of electron correlation and lattice dimensionality is emphasized in relation to high-T-e superconductivity. (C) 2002 Elsevier Science B.V. All rights reserved.

DOI： 10.1016/S0010-8545(01)00440-4

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担当区分：筆頭著者   記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：GEORG THIEME VERLAG KG  

Hydrogenation of aromatic nitrites takes place under the mild conditions using supported nickel catalysts to afford amino-methyl-substituted aromatics in good yields.

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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：CHEMICAL SOC JAPAN  

The reaction of Nil, with a tripodal hexadentate ligand (H3L = 1,1,1-tris(N-salicylideneaminomethyl)ethane) afforded the O-H . . .O bridged dinuclear [Ni-2(HL)(2)] complex. When Ni2+ was allowed to react with H3L in the presence of triethylamine (3 : 2 : 6), the linear trinuclear [Ni-3(L)(2)] complex formed, where the central nickel(II) ion is bridged by six phenolate oxygen atoms to the terminal nickel(II) ions.

DOI： 10.1246/cl.2001.842

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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：PERGAMON-ELSEVIER SCIENCE LTD  

The adsorption properties in nanoporous crystals of a metal-organic framework were studied theoretically. The Zn-3(BDC)(3). 6CH(3)OH (BDC = 1,4-benzenedicarboxylate) crystal was mainly treated as a stable metal-organic assembled species, which was reported by O.M. Yaghi and co-workers. Its crystalline structure very much resembles several crystals that have been reported by W. Mori et al. For adsorbed molecules, N-2, CO2, Ar and H-2 for nonmagnetic species and O-2 for magnetic radical species were treated. The following systematic procedures were carried out: (1) decision of parameters for MC simulations; (2) execute MC simulation; (3) search of configuration of O-2 molecules by MM method; and (4) study of magnetic interactions by means of ab initio HF, post-HF and DFT methods. Finally, magnetic interactions between O-2 pairs exist and this cooperation might run in the nanoporous cavity. (C) 2001 Elsevier Science Ltd. All rights reserved.

DOI： 10.1016/S0277-5387(01)00594-0

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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：CHEMICAL SOC JAPAN  

A three-dimensional coordination polymer was synthesized from porous copper(II) terephathlate and triethylenediamine (TED) as a pillar ligand, which has a higher porosity and higher capacity for methane adsorption than zeolites and porous coordination polymers reported previously.

DOI： 10.1246/cl.2001.332

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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：CHEMICAL SOC JAPAN  

Some microporous coordination polymers have been synthesized from copper salts and dicarboxylic acids. These stuctures were characterized by gas adsorption methods. The methane adsorption capacities of these coordination polymers were measured under high pressure. The measurement disclosed that these coordination polymers had uniform micropores and methane adsorption capacities almost the same as that of zeolite 5A.

DOI： 10.1246/cl.2001.122

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担当区分：筆頭著者   記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：AMER CHEMICAL SOC  

Novel inclusion complexes between host microporous molybdenum(II) dicarboxylates (fumarate, terephthalate, trans-trans-muconate, and pyridine-2,5-dicarboxylate) and guest organic polyethers (poly(ethylene glycol) (PEG) and poly(propylene glycol) (PPG)) of various molecular weights were synthesized. The rate of complex formation depends on the shapes of the micropores and polyethers. The amount of included polyethers increased with their molecular weight, and reached a saturated amount, with the exception that molybdenum(II) pyridine-2,5-dicarboxylate did not form complexes with bulky PPG. The amount of adsorbed argon in the microporous molybdenum(II) dicarboxylates decreased with increased amounts of included polyethers. The C-13 CP/MAS NMR measurement of molybdenum(II) terephthalate with PEG demonstrated that PEG chains are included in the capillaries. This is an effective method for synthesizing supramolecular complexes.

DOI： 10.1021/ma000336t

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担当区分：筆頭著者   記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：JOHN WILEY & SONS LTD  

A novel inclusion complex between molybdenum(II) fumarate and poly(ethylene glycol) was synthesized. The formation of the saturated inclusion complex, a supramolecule obtained by the one-pot method, was confirmed by elemental analysis and gas-occlusion measurement. This is a new method for synthesizing the hybrid inclusion complex between the transition-metal complex and the organic polymer bound by non-covalent interaction. Copyright (C) 2000 John Wiley & Sons, Ltd.

DOI： 10.1002/1099-1581(200008/12)11:8/12<840::AID-PAT62>3.0.CO;2-C

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記述言語：英語   掲載種別：研究論文（国際会議プロシーディングス）   出版者・発行元：Taylor & Francis  

DOI： 10.1080/10587250008023515

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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：GORDON BREACH SCI PUBL LTD  

Adsorption properties in nanoporous crystals, especially Zn(BDC) (BDC=1,4-benzenedicarboxylate) crystal, were studied theoretically, For sorbed molecules N-2 and CO2 were employed and gas adsorption isotherms were obtained. In addition, O-2 as S=1 magnetic radical species was also treated in order to study the magnetic properties. Magnetic interaction between O-2 pairs exists and these cooperation might run in the nanoporous cavity. These results lead new approach to arrangement of organic spin radical sources and it is found that nanoporous organic-metal crystals are useful for controlling their position and orientation.

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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：GORDON BREACH SCI PUBL LTD  

Magnetic properties for the K2MX4 type solids (M=Cu2+, Ni2+ X=F-, O2-, Cl-) were investigated by the ab initio calculations using UHF and the hybrid Density Functional methods (B2VWN, S2VWN and UB3LYP). It was found that these type solids had the antiferromagnetic interactions.

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担当区分：筆頭著者   記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：GORDON BREACH SCI PUBL LTD  

The bis-mu-dicarboxylate ruthenium (II,III) complexes, Ru (II,III)(2)L2Br (L=trans-O2C-CH=CH-CO2 (1), trans-trans-O2C-CH=CH-CH=CH-CO2 (2), and p-O2C-C6H4-CO2 (3)), were prepared and their gas-occlusion properties were measured. The effective magnetic moments at room temperature are in the range 3.76 and 4.02 BM per dinuclear, consistent with the Values of Ru(II)-Ru(III) compounds. All these complexes are capable of occluding a large amount of gas. The maximum amounts of occluded nitrogen for 1-3 are 0.6, 0.9, and 1.4 moles per one mole of ruthenium atoms, respectively. These amounts are almost the same as those of the correspondent chloride complexes. This suggests that bromide complexes 1-3 would form a highly similar capillary structure to that of ruthenium (II,III) dicarboxylate bridged by chloride atoms.

DOI： 10.1080/10587250008038265

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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：GORDON BREACH SCI PUBL LTD  

DOI： 10.1080/10587250008038281

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担当区分：筆頭著者   記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：GORDON BREACH SCI PUBL LTD  

The gas-adsorption behavior in microporous transition-metal complexes was investigated by the use of Monte Carlo simulations. We prepared the models of Cu(3)TMA(2) and Zn(BDC), which were crystallographically determined. The pressure dependence of the amount of adsorbed gases (argon, nitrogen, and hydrogen) was simulated at the boiling temperature of the gases. In the gas adsorption in Cu(3)TMA(2), the effect of the charge distribution on the framework is negligible. However, the coordinating water narrows the cavity and stabilizes the adsorbed argon molecules. The amounts of adsorbed gases and the isosteric heats were calculated for Cu(3)TMA(2) and Zn(BDC) and the pictures of probability distribution of gases in the cavity were obtained. The probability distributions indicated that the adsorbed gases tend to be distributed as a zig-zag column in the capillary of Zn(BDC) and as a shape like a four-leaf clover avoiding the four benzene rings in the narrow cavity of Cu(3)TMA(2).

DOI： 10.1080/10587250008038279

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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：GORDON BREACH SCI PUBL LTD  

Rhodium(II) benzoate bridged by pyrazine derivatives occlude a large amount of N-2 gas, reversibly. The maximum amounts of the occluded N-2 were 1.8, 1.7, 0.5, 0.1, 1.3, and 1.3 mol per one mole of rhodium(II) salt with 2-methylpyrazine, 2,3-dimethylpyrazine, quinoxaline, 1,5-naphthyrizine, and triethylenediamine, respectively, indicating the presence of a large number of micropores in these rhodium(II) carboxylates. The porous structure which is formed by the self-assembly of linear rhodium(II) benzoate-pyrazine derivatives was deduced by analogy to the structure of rhodium(II) benzoate-pyradine reported previously.

DOI： 10.1080/10587250008038264

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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：CHEMICAL SOC JAPAN  

Reaction of copper(II) benzoate with pyrazine (pyz) gave a compound, [Cu-2(bz)(4)(pyz)](n) (1) which has a gas-occlusion properly. The X-ray structure analysis of 1.2nCH(3)CN shows a microporous structure formed by chains where the carboxylate dimer units are linked by pyrazine molecules.

DOI： 10.1246/cl.1999.367

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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：CHEMICAL SOC JAPAN  

Rhodium(II) carboxylates bridged by pyrazine occlude a large amount of N-2 gas, reversibly. The maximum amounts of the occluded N-2 gas were 1.8, 1.1, 0.8, 0.6, 0.2, 0.2, 0.5, and 0.6 mol per one mole of rhodium(II) salt with benzoate, o-hydroxybenzoate, m-hydroxybenzoate, p-hydroxybenzoate, o-toluate, m-toluate and p-toluate, respectively indicating the presence of a large number of micropores in these rhodium(II) carboxylates.
The porous structure which is formed by self-assembly of linear rhodium(II) carboxylates-pyrazine was deduced from the magnetic susceptibilities and by analogy to the structure of copper(II) dicarboxylates which show similar gas-occlusion behavior.

DOI： 10.1246/cl.1999.331

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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：ELSEVIER SCIENCE SA  

The dinuclear nickel(II) complexes [Ni-2(L-1)(OAc) (H2O)(2)] (ClO4)(2). 3H(2)O (1), [Ni-2(L-2)(OAc) (H2O)(2)] (ClO4)(2) (2) and [Ni-2(L-2)(OPr) (H2O)(2)] (ClO4)(2). H2O (3) (HL1 = N,N,N',N'-tetrakis [ (1-methyl-2-benzimidazolyl) methyl] -2-hydroxy-1,3-diaminopropane, HL2=N,N,N',N'-tetrakis[(1-ethyl-2-benzimidazoyl)methyl]-2-hydroxy-1,3-diaminpropane, OPr=propionate anion) were synthesized and characterized. The crystal structures of [Ni-2(L-2)(OAc) (CH3OH)(2)] (ClO4)(2). CH3OH . H2O (2') and [Ni-2(L-2)(OPr)-(CH3OH)(2)] (ClO4)(2). CH3OH . 2H(2)O (3'), which become 2 and 3 upon exposure of 2' and 3' to air, respectively, were determined by X-ray diffraction. 2' and 3' are isostructural. They consist of dinuclear cations and uncoordinated perchlorate ions. In the complex cations, the two nickel(II) centers are in a distorted octahedral coordination with an alkoxo and an acetato or a propionato bridge. The distances between the two nickel(II) ions are 3.521(2) and 3.507(2) A for 2' and 3', respectively. Variable temperature magnetic susceptibility measurements of 2 and 3 show an antiferromagnetic exchange coupling (2J= -43.2 cm(-1) for 2, and 2J= -34.4 cm(-1) for 3, H= -2JS(1). S-2) between two nickel(II) ions. (C) 1998 Elsevier Science S.A. All rights reserved.

DOI： 10.1016/S0020-1693(98)00225-4

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担当区分：筆頭著者   記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：ELSEVIER SCIENCE SA  

lThe bis-mu-dicarboxylate molybdenum(II) complexes Mo(II)(2)L-2 (L = trans-O2C-CH=CH-CO2 (1), p-O2C-C6H4-CO2 (2), trans-trans-O2C-CH=CH-CH=CH-CO2 (3), 2,5-O2C-C5H3N-CO2 (4), and trans-O2C-C6H10-CO2 (5)) were prepared and their gas-occlusion properties were characterized. The dinuclear complexes have quadruple Mo-Mo bonds, with the ground electronic configuration (sigma)(2)(pi)(4)(delta)(2). All of these complexes are capable of occluding a large amount of gas (1 or 2 mol of N-2 gas per 1 mol of molybdenum atoms). Investigation of the structures of these complexes indicates that gases are most probably occluded in homogeneous and linear micropores which are composed of micropore units surrounded by four dicarboxylate bridges. C-13-CP/MAS NMR measurements indicate that gas molecules are held in the micropores created by the dicarboxylate ligands. (C) 1998 Elsevier Science S.A. All rights reserved.

DOI： 10.1016/S0020-1693(98)00312-0

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記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1246/bcsj.71.1831

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その他リンク： http://orcid.org/0000-0002-6677-3781

記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：CHEMICAL SOC JAPAN  

Protonated and deprotonated forms of nickel(II) complex with N-salicylidene-N'-(2-phenylimidazol-4-ylmethylidene)-1,3-propanediamine, 1 and 1', were synthesized and characterized. The X-ray crystal structures of 1 . H2O and 1' were determined: 1 . H2O, P2(1)/n (No. 14), a = 11.642(2), b = 12.908(3), c = 15.264(2) Angstrom, beta = 96.642(1)degrees; 1', I4(1)/a (No. 88), a = 22.651(3), c = 13.950(7) Angstrom. The crystal of 1 . H2O assumes a dinuclear structure bridged by the di-mu-phenoxo moiety in an out-of-plane fashion with Ni-Ni = 3.173(1) Angstrom and Ni-O = 2.126(3) Angstrom of the Ni2O2 core and two perchlorate ions as counter anions, in which the nickel(II) ion assumes an octahedral coordination geometry with N3O3 donor atoms consisting of four donor atoms of a quadridentate ligand, a bridging phenoxo-oxygen atom, and an oxygen atom of methanol. A ferromagnetic interaction with J = +7.1 cm(-1) operates between the two high-spin nickel(II) ions. 1 undergoes a deprotonation of the imidazole proton under basic conditions to give the deprotonated complex 1'. The crystal of 1' consists of an electrically-neutral imidazolate-bridged cyclic-tetranuclear molecule with Ni-Ni = 6.339(2) Angstrom and Ni-N = 2.051(7) Angstrom, in which the nickel(II) ion assumes a square-pyramidal geometry with N4O donor atoms consisting of the quadridentate ligand and an imidazolate nitrogen of the adjacent nickel(II) complex. An antiferromagnetic interaction with J = -6.3 cm(-1) is observed between the adjacent nickel(II) ions through the imidazolate group. Since the corresponding deprotonated copper(II) complex with the same ligand assumed an imidazolate-bridged zigzag-chain structure, the result with the nickel(II) complex demonstrates a very marked influence of the metal ion on the formation of the assembly structure.

DOI： 10.1246/bcsj.71.1831

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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：ROYAL SOC CHEMISTRY  

The dinuclear diruthenium complexes ligated by the (mu-aryloxo)bis(mu-carboxylato) system M[Ru2L(mu-O2CR)(2)] (M = Na, R = Me 1; M = Na, R = Ph 2; M = K, R = Me 3; M = K, R = Ph 4; H5L = 2-hydroxy-5-methyl-m-phenylenedimethylenedinitrilotetraacetic acid) were prepared by the reaction of [RuCl2(Me2SO)(4)] with L5- and carboxylic acid. The structure of the benzoate-bridged complex 4 0.5MeOH . 0.5EtOH . 4H(2)O was elucidated by X-ray crystallography. The Ru ... Ru distance was 3.416 Angstrom (average for two crystallographically independent molecules), comparable to those of (mu-alkoxo)bis(mu-carboxylato)diruthenium complexes The magnetic properties were analysed by a general isotropic exchange Hamiltonian H= -2JS(1). S-2 (S-1 = S-2 = 1/2) yielding meaningfully large antiferromagnetic spin coupling constants (-J= 728 and 649 cm(-1) for 1 and 2, respectively). The cyclic voltammogram of 4 in dmf demonstrated two reduction and one oxidation wave corresponding to the four redox states Ru-2(II), (RuRuIII)-Ru-II Ru-2(III), (RuRuIV)-Ru-III. The intervalence coupling constant K-c estimated from the potential gap between Ru-2II/(RuRuIII)-Ru-II and Ru(II)Run(III)/Ru-2(III), indicated that the introduction of the mu-aryloxo bridge stabilizes the (RuRuIII)-Ru-II mixed-valence species.

DOI： 10.1039/a800857d

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記述言語：英語   掲載種別：研究論文（学術雑誌）  

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その他リンク： http://orcid.org/0000-0002-6677-3781

担当区分：筆頭著者   記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：ELSEVIER SCIENCE BV  

The gas-occlusion properties of some ruthenium(II,III) dicarboxylate derivatives are reported. (C) 1998 Published by Elsevier Science S.A. All rights reserved.

DOI： 10.1016/S1387-7003(98)00048-3

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その他リンク： http://orcid.org/0000-0002-6677-3781

記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1021/ic970640b

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PubMed

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その他リンク： http://orcid.org/0000-0002-6677-3781

記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：CHEMICAL SOC JAPAN  

In this paper we report our recent research on the dinuclear copper(II) and nickel(II) complexes 1-10 (Chart 1) containing Schiff bases, derived from acetylacetone, benzoylacetone, or trifluoroacetylacetone, and 1,3-diaminopropane-2-ol. These complexes are bridged by an alkoxide and a pyridazine (pyd) or phthalazine (phta). The magnetic susceptibilities, visible absorption spectra, conductivities, and redox properties of the complexes were investigated and the molecular structures of 2, 4, and 5 are described. The Cu-O-Cu angles found in these complexes indicate a role of the alkoxo-bridge as one of the principal antiferromagnetic exchange pathways. At the same time, the coplanarity of two coordination planes of copper(II) ions is also shown to relate to the exchange process.

DOI： 10.1246/bcsj.70.2429

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その他リンク： http://orcid.org/0000-0002-6677-3781

記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：CHEMICAL SOC JAPAN  

The linear trinuclear copper(II) complexes Cu-3(L(1))(2)(N-3)(2) (NO3)(2) . 2H(2)O . 2CH(3)OH 1 and Cu-3(L(1))(2)(OH)(2)(ClO4)(2) 2 containing 3-[{2-(2-pyridinyl)ethyl}imino]-2-butanone oximato ligand (L(1)) were prepared; the crystal structure of I was determined by X-ray crystallography. Magnetic susceptibility measurements from liquid helium temperature to room temperature showed a very strong antiferromagnetic exchange coupling between copper(II) ions(J = -266 cm(-1) and -245 cm(-1) for 1 and 2, respectively, H = -2JS(1) . S-2).

DOI： 10.1246/cl.1997.181

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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：CHEMICAL SOC JAPAN  

Monomethyl carbonate-bridged dinuclear nickel(II) complexes [Ni-2(L)(OOC-O-CH3)(CH3OH)(2)](ClO4)(2) . H2O . CH3OH, 1 and [Ni-2(L)(OOC-O-CH3)(H2O)(2)](ClO4)(2) . H2O, 2 were obtained in the presence of [Ni-2(L)(OH)(H2O)(2)](ClO4)(2) and N-methylurea at room temperature in air, where HL is N,N,N',N'-tetrakis[(1-ethyl-2-benzimidazolyl)methyl]- 2-hydroxy-1,3-diaminopropane. The crystal structure of 1 was determined by X-ray crystallography and 2 was characterized by the magnetic susceptibility and visible absorption spectrum.

DOI： 10.1246/cl.1997.891

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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：CHEMICAL SOC JAPAN  

Monomethyl carbonate-bridged dinuclear nickel(II) complexes [Ni-2(L)(OOC-O-CH3)(CH3OH)(2)](ClO4)(2) . H2O . CH3OH, 1 and [Ni-2(L)(OOC-O-CH3)(H2O)(2)](ClO4)(2) . H2O, 2 were obtained in the presence of [Ni-2(L)(OH)(H2O)(2)](ClO4)(2) and N-methylurea at room temperature in air, where HL is N,N,N',N'-tetrakis[(1-ethyl-2-benzimidazolyl)methyl]- 2-hydroxy-1,3-diaminopropane. The crystal structure of 1 was determined by X-ray crystallography and 2 was characterized by the magnetic susceptibility and visible absorption spectrum.

DOI： 10.1246/cl.1997.891

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その他リンク： http://orcid.org/0000-0002-6677-3781

記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：GORDON BREACH SCI PUBL LTD  

The dependency of the magnetic susceptibility on temperature has elucidated that the mineral atacamite Cu2Cl(OH)(3) has the antiferromagnetic property. In order to explain this behavior and the spin arrangement derived from experimental studies, the ab initio UHF MO and UNO CASCI calculations were carried out for the tetranuclear cluster of copper(II), Cu4Cl(OH)(3), which is the constitution in the atacamite crystal structure. The results of the CASCI calculations appreciate the relative stabilities among various spin arrangements for the tetranuclear cluster, being consistent with the experiments.

DOI： 10.1080/10587259708044546

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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：CHEMICAL SOC JAPAN  

New bis(beta-diketonato)Cr(III) and Ni(II) complexes with a chelating nitronyl nitroxide radical were synthesized and characterized, The intensification and/or large Stokes shift of the spin-forbidden components and the charge transfer transitions revealed by the resonance Raman spectra in the visible region were found, which result from the moderate exchange coupling.

DOI： 10.1246/cl.1997.603

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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：GORDON BREACH SCI PUBL LTD  

Polymers containing paramagnetic metalloporphyrins in their main chains were prepared by condensation copolymerization of 5,10-bis(ethoxyphenyl)-15,20-bis(hydroxyphenyl)porphyrin (HETPP) with dibromomethane. Paramagnetic metal ions were introduced to porphyrin moieties. This type of polymer is expected to show novel magnetic behavior through both intra- and intermolecular interactions. PolyHETPP-M (M = Ag-II, Cu-II, Co-II, or (VO)-O-IV) contains 5-10 HETPP units and is soluble in many organic solvents. Magnetic properties of polymer and monomer were investigated by measurements of magnetic susceptibilities. In the course of this research, solvent effects on magnetic properties of obtained polymers in reprecipitation of polymer containing vanadyl ion was observed. Magnetic interactions of vanadyl complex of polymer were varied from antiferromagnetic to ferromagnetic by precipitation in methanol. ESR measurements indicated that the origin of the difference was caused from ligation of methanol, which was used as precipitation solvent, to vanadyl ion to prevent stacking of porphyrin moieties. From this result, it is possible that magnetic property of polyHETPP-(VO)-O-IV can be controlled by the selection of solvents for purification of polymers.

DOI： 10.1080/10587259708044545

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記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1246/cl.1997.603

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その他リンク： http://orcid.org/0000-0002-6677-3781

記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：GORDON BREACH SCI PUBL LTD  

Ab initio UMP calculations were carried out for binuclear transition-metal fluorides in order to elucidate variations of the superexchange integrals with intermetallic distances. It was shown that the antiferromagnetic superexchange integrals calculated for tricentric systems MFM(+3) (M=divalent ions) by the approximately spin-projected UMPn (n= 1 - 4) method with the triple zeta basis set are about -134, -22 and -1 cm(-1) in the cases of Cu(II), Ni(II) and Mn(II), respectively. These are consistent with the experimental results available. The hole-or electron doping into antiferromagnetic systems is also discussed in relation to previous proposals to obtain the switching type molecular magnets controlled by thermal, photochemical, electrochemical and other techniques.

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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：GORDON BREACH SCI PUBL LTD  

Cu(HCOO)(OH) exhibits a strong ferromagnetic interaction (theta =+43K). The susceptibility shows a sharp maximum at T-m=21K and a plateau below 12K. This magnetic behavior is characteristic of antiferromagnetic materials. The spin-flop behavior is observed below T-m. To examine the spin-flop behavior of Cu(HCOO)(OH), magnetic phase diagram was drawn up. Magnetic phase diagram of Cu(DCOO)(OD) was also constructed to examine whether magnetic interaction between layers is due to hydrogen bond or not. Between them there is little difference in the phase diagram, but there is a remarkable difference in the hysteresis curves at 2K. Besides, temperature dependence of susceptibility and hysteresis curve at 1.8K of Cu-3(HCOO)(2)(OH)(4) was measured. In consequence it was found that this material also showed spin-flop behavior.

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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：GORDON BREACH SCI PUBL LTD  

The orbital-symmetry rules for superexchange couplings of unpaired electrons via ligands were applied to one-dimensional (1D) polymers composed of heteropoly transition-metal tetrathiolates (poly(M1TM2), T: tetrathiolate). The polymers composed of the Cu(II)-Fe(III)(LS) and Ni(II)(HS)-Fe(III)(LS) units are predicted to be ferromagnetic within 1D chains, whereas several polymers such as the Co(II)(HS)-Cu(II) alternating one are considered to be ferrimagnetic. Ferromagnetic metals, dense Kondo and spin-mediated superconductors composed of trinuclear M2TM1TM2 complexes (M1=Ni) are also designed on the basis of the theoretical results. According to these guiding principles, we have performed the synthesis of ferro- and ferrimagnetic polymers composed of heteropoly transition-metal tetrathiolates (poly(M1TM2), T: tetrathiolate). The magnetic measurements of the solids were also carried out and the observed intrachain effective exchange integrals are summarized.

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記述言語：日本語   出版者・発行元：東京化学同人  

CiNii Books

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記述言語：日本語  

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記述言語：日本語   出版者・発行元：錯体化学会  

In this article, gas inclusion phenomena for a flexible single-crystal host have been described. The synthesized single crystal hosts exhibit high flexibility and adjustability for the properties of adsorbed guests to realize the highly ordered gas inclusion state. Because the crystal remains intact under gas adsorption state, it is possible to analyze the resulting host-guest aggregate in great and accurate details by conventional single-crystal X-ray diffraction. Here, the relationship between incorporated gaseous guest and walls of pores cannot be compared to the contact between a ball and a flat surface, but to the atomic contact of a point (atom) to a point (atom), raising the necessity of regarding a gas adsorption state as a co-crystal state. The study of flexible single-crystal host system will contribute to clarify the mechanism of dynamic adsorption to develop the new functions from the view point of the host-guest chemistry. Furthermore, the homogeneity, anisotropy, integrity, transparency, etc. of crystal hosts would contribute to the advancing of new techniques for future society.

DOI： 10.4019/bjscc.53.33

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記述言語：日本語   出版者・発行元：日本結晶学会  

DOI： 10.5940/jcrsj.51.127

CiNii Books

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記述言語：日本語   出版者・発行元：アグネ技術センタ-  

CiNii Books

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記述言語：日本語   出版者・発行元：日本化学会  

CiNii Books

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記述言語：日本語   出版者・発行元：触媒学会  

CiNii Books

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記述言語：日本語   出版者・発行元：日本化学会  

CiNii Books

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出願人：公立大学法人横浜市立大学

出願番号：特願2005-169087  出願日：2005年6月

公開番号：特開2006-341188  公開日：2006年12月

特許番号/登録番号：特許第5099615号  発行日：2012年10月

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出願人：公立大学法人横浜市立大学

出願番号：特願2005-169081  出願日：2005年6月

公開番号：特開2006-342249  公開日：2006年12月

特許番号/登録番号：特許第5099614号  発行日：2012年10月

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出願人：公立大学法人横浜市立大学

出願番号：特願2005-169083  出願日：2005年6月

公開番号：特開2006-342100  公開日：2006年12月

特許番号/登録番号：特許第4951728号  発行日：2012年3月

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出願人：大阪瓦斯株式会社

出願番号：特願2004-330879  出願日：2004年11月

公開番号：特開2005-104834  公開日：2005年4月

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出願人：大阪瓦斯株式会社

出願番号：特願2004-330879  出願日：2004年11月

公開番号：特開2005-104834  公開日：2005年4月

特許番号/登録番号：特許第4204535号  発行日：2008年10月

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出願人：よこはまティーエルオー株式会社

出願番号：特願2003-141474  出願日：2003年5月

公開番号：特開2004-043454  公開日：2004年2月

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出願人：財団法人相模中央化学研究所

出願番号：JP2000000586  出願日：2000年2月

公開番号：WO2000-046179  公開日：2000年8月

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出願人：大阪瓦斯株式会社, 森 和亮

出願番号：特願平10-283047  出願日：1998年10月

公開番号：特開2000-109493  公開日：2000年4月

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出願人：大阪瓦斯株式会社, 森 和亮

出願番号：特願平10-283051  出願日：1998年10月

公開番号：特開2000-109485  公開日：2000年4月

特許番号/登録番号：特許第3985114号  発行日：2007年7月

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出願人：大阪瓦斯株式会社, 森 和亮

出願番号：特願平10-229133  出願日：1998年8月

公開番号：特開2000-063393  公開日：2000年2月

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出願人：大阪瓦斯株式会社

出願番号：特願平9-147704  出願日：1997年6月

公開番号：特開平10-099680  公開日：1998年4月

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出願人：大阪瓦斯株式会社

出願番号：特願平9-147705  出願日：1997年6月

公開番号：特開平10-057754  公開日：1998年3月

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出願人：大阪瓦斯株式会社

出願番号：特願平9-122160  出願日：1997年5月

公開番号：特開平10-316684  公開日：1998年12月

特許番号/登録番号：特許第3760255号  発行日：2006年1月

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出願人：大阪瓦斯株式会社

出願番号：特願平8-226216  出願日：1996年8月

公開番号：特開平10-066864  公開日：1998年3月

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出願人：大阪瓦斯株式会社

出願番号：特願平8-226218  出願日：1996年8月

公開番号：特開平10-066865  公開日：1998年3月

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出願人：大阪瓦斯株式会社

出願番号：特願平8-226217  出願日：1996年8月

公開番号：特開平10-066949  公開日：1998年3月

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出願人：大阪瓦斯株式会社

出願番号：特願平7-294018  出願日：1995年11月

公開番号：特開平9-132580  公開日：1997年5月

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