北海道大学 · 材料科学
Atsushi Kobayashi教授の研究室は、主に銅(I)錯体ならびにパラジウム・イridium錯体を対象に、外部刺激(熱・蒸気・光・圧力)に応じて発光特性を変化させる「クロミック発光材料」の開発を進めています。特に、四核型銅クラスターとダイナリック銅錯体の構造・発光機構の解明に注力しており、機械的圧力や揮発性蒸気による発光色の可逆的変化を実現する新規センサー材料の創出を目指しています。また、高圧下での超伝導転移を示す金属錯体の研究を通じて、分子性超伝導体の理解を深めています。
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Extensive studies of luminescent copper(I) complexes were conducted, revealing that some of them exhibit interesting chromic luminescence in response to external stimuli such as temperature, vapor, light, and mechanical force. In this review, recent progress in the field of luminescent chromic copper(I) complexes is discussed. Tetranuclear copper(I) clusters with a cubane-type {Cu4I4} core are the most prominent group, which shows thermochromic, vapochromic, and mechanochromic luminescence, and
Abstract Vapochromic materials that show reversible color change driven by vapor adsorption/desorption have drawn significant attention because of their potential applications in chemical sensors and chemical‐switching modules. Among the vapochromic coordination complexes reported so far, a series of square‐planar Pt II complexes has been studied and represents one of the most promising systems for practical chemical sensors. For such systems, the color of the complexes strongly depends not only
Abstract High-pressure resistivity studies on [(CH3)4N][Pd(dmit)2]2 have revealed the system to be a new molecular superconductor. The superconducting transition has been observed above 6 kbar. The mid-point transition temperature T is 6.2 K at 6.5 kbar. The crystal has the structure almost isomorphous to the high-pressure superconductor, [(CH3)4N][Ni(dmit)2]2.
Luminescent dinuclear Cu(I) complexes, [Cu2X2(dpypp)2] [Cu-X; X = Cl, Br, I; dpypp = 2,2'-(phenylphosphinediyl)dipyridine], were successfully synthesized by a solvent-assisted mechanochemical method. A trace amount of the assisting solvent plays a key role in the mechanochemical synthesis; only two solvents possessing the nitrile group, CH3CN and PhCN, were effective for promoting the formation of dinuclear Cu-X. X-ray analysis revealed that the dinuclear structure with no Cu···Cu interactions,
Abstract α-Ba2SiW12O40·16H2O is monoclinic, space group C2/c, with a=25.09(5), b=12.10(2), c=18.79(3) Å, β=122.5(3)°; Dm=4.95 g cm−3 and Dx=4.78 g cm−3 for Z=4. The crystal consists of the well known Keggin ion SiW12O404−, having a SiO4 tetrahedron in the center, bound by Ba2+ and water molecules to form a three-dimensional framework. Four water molecules could not be located on electron-density maps, which seem to be disordered or “zeolitic”. The structural relationship of the Keggin ion to its
Halide-bridged rhombic dicopper(I) complexes, [Cu2(μ-X)2(DMSO)2(PPh3)2] (X = I–, Br–; DMSO = dimethyl sulfoxide; PPh3 = triphenylphosphine), were synthesized, the iodide complex of which exhibited interesting photochromic luminescence driven by photoirradiation and by exposure to DMSO vapor in the solid state. Single-crystal X-ray diffraction measurements revealed that the iodo and bromo complexes (abbreviated Cu2I2-[O,O] and Cu2Br2-[O,O]) were isomorphous, and that the two DMSO ligands were coo
Was die Kontraktion verursacht: Das metall-organische Gerüst [Cu3(btc)2] weist über einen breiten Temperaturbereich eine negative thermische Ausdehnung (NTE) auf. Ursache sind zwei parallel ablaufende Mechanismen, von denen jeder einzigartig für NTE-Systeme ist: die konzertierte transversale Schwingung dreieckiger organischer Linker und die lokale dynamische Verzerrung zweikerniger Metallzentren im Netzwerkgerüst. Detailed facts of importance to specialist readers are published as ”Supporting In
We synthesized a novel Pt(II)-diimine complex with a typical ambidentate thiocyanato ligand, [Pt(thiocyanato)(2)(H(2)dcbpy)] (1; H(2)dcbpy =4,4'-dicarboxy-2,2'-bipyridine), and found that the complex 1 exhibits unique linkage isomerizations with drastic color and luminescence changes driven by exposure to volatile organic chemical (VOC) vapors in the solid state. Reaction between [PtCl(2)(H(2)dcbpy)] and KSCN in aqueous solution at 0 °C enabled successful isolation of an isomer with the S-coordi
A novel two-legged MX-ladder complex {[(dien)PtIVBr2-bpy-PtII(dien)]Br4.2H2O}infinity was synthesized and analyzed by single-crystal X-ray diffraction method and Raman and diffuse reflectance spectra. The electronic structure on two-legged MX-ladder is a pair of out-of-phase charge-density-waves state within each ladder, and these pairs of CDWs are also ordered from ladder to ladder. The intervalence charge-transfer (PtII to PtIV) excitation energy is significantly larger than that in the MX-cha
We synthesized a new Pt/Zn-based coordination polymer, {Zn[Pt(CN)(2)(5,5'-dcbpy)].4H(2)O}(n), (5,5'-H(2)dcbpy = 5,5'-dicarboxy-2,2'-bipyridine), which exhibits reversible colour changes in response to temperature change or exposure to chemical vapours and liquids. Such chromic behaviour shows promise for sensing not only changes in temperature but also for detecting chemical solvents and vapours. The single crystal X-ray structure indicates that one-dimensional coordination polymeric chains form
We synthesized and investigated a new series of metal-hydrazone complexes, including deprotonated [MX(mtbhp)] and protonated forms [MX(Hmtbhp)](ClO(4)) (M = Pd(2+), Pt(2+); X = Cl(-), Br(-); Hmtbhp = 2-(2-(2-(methylthio)benzylidene)hydrazinyl)pyridine) and hydrogen-bonded proton-transfer (HBPT) assemblies containing [PdBr(mtbhp)] and bromanilic acid (H(2)BA). The mtbhp hydrazone ligand acts as a tridentate SNN ligand and provides a high proton affinity. UV-vis spectroscopy revealed that these me
Four new bimetallic coordination polymers (CPs), {M[Pt(CN)(2)(5,5'-dcbpy)]·4H(2)O}(n) (M = Mg(2+), Ca(2+), Sr(2+), Ba(2+); 5,5'-H(2)dcbpy = 5,5'-dicarboxy-2,2'-bipyridine) were synthesized using four alkaline-earth metal ions and a Pt(II)-diimine metalloligand [Pt(CN)(2)(5,5'-H(2)dcbpy)]. All four CPs are isomorphous with the Zn complex, {Zn[Pt(CN)(2)(5,5'-dcbpy)]·4H(2)O}(n), which exhibits effective metallophilic interactions between Pt(II) ions. These CPs exhibited colourful thermochromic beha
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