Construction of Photosensitive Device by Using of Hydrogen Bond-supported Metal Complex Assembly

利用氢键支撑的金属配合物组装体构建感光器件

• 批准号: 15550050
• 负责人: KAWATA Satoshi
• 金额: $ 2.43万
• 依托单位: Osaka University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2003
• 资助国家: 日本
• 起止时间: 2003 至 2004
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-15550050/
• 关键词: Metal Complex Assembly; Hydrogen Bond; Vapochromism; Spin-crossover; 層状化合物

Novel metal-complex assemblies constructed from the flexible hinge-like ligand H_2bhnq (H_2bhnq= 2,2' -bi(3-hydroxy-1,4-naphthoquinone))have been synthesized. The X-ray crystal structures of these compounds reveal that four types of architectures are accessible by variation of the metal ions. In copper(II) compounds 1-3, the chelating bhnq^<2-> ions bridge copper(II) centers to form one-dimensional zigzag chains. The chains of 1-3 are arranged by hydrogen-bonding interactions and stacking interactions to produce porous structures. Cobalt(II) and zinc(II) compounds 4 and 5 form one-dimensional helical chains. In 4 and 5, the crystal packing induces spontaneous resolution of the helical chains with chiral cavities formed perpendicular to the helices. Nickel(II) compounds 6 and 7 formcyclic tetramers. The fourth architecture, a dimer (compound 8), is obtained by the reaction of zinc(II) and bhnq^<2-> in McOH. In these compounds, changes of the dihedral angles and the metal-coordination mode of the bhnq^<2-> ion induce the structural versatility. The assemblies of the zigzag chains of the copper(II) compounds exhibit reversible vapochromic behavior. UV/V is, powder X-ray diffraction, EPR, and adsorption isotherm measurements indicate that this vapochromic behavior is based on the hinge-like flexibility of the bhnq^<2-> ion.

合成了由柔性铰链状配体H_2bhnq(H_2bhnq=2，2‘-双(3-羟基-1，4-萘醌))构筑的新型金属配合物。这些化合物的X射线晶体结构表明，不同的金属离子可以形成四种不同的结构。在铜(II)化合物1-3中，络合的bhnq^&lt；2-gt；离子桥接铜(II)中心，形成一维之字链。1-3的链通过氢键作用和堆积作用排列，形成多孔结构。钴(II)和锌(II)化合物4和5形成一维螺旋链。在4和5中，晶体堆积诱导螺旋链的自发分解，并形成垂直于螺旋的手性腔。镍(II)化合物6和7形成环状四聚体。第四种结构是二聚体(化合物8)，它是由锌(II)与bhnq^&lt；2-&gt；在McOH中反应得到的。在这些化合物中，bhnq^&lt；2-&gt；离子的二面角和金属配位方式的变化导致了结构的多样性。铜(II)化合物的锯齿形链组装体表现出可逆的汽致变色行为。UV/VIS，粉末X射线衍射，EPR和吸附等温线测量表明，这种汽致变色行为是基于bhnq^&lt；2-&gt；离子的铰链状柔性。

项目成果

Metal-complex assemblies constructed from the flexible hinge-like ligand H2bhnq: structural versatility and dynamic behavior in the solid state.

• DOI: 10.1002/chem.200305640
• 发表时间: 2004-06
• 期刊: Chemistry
• 作者: Koichi Yamada;Sadahiro Yagishita;Hirokazu Tanaka;Kazuhiro Tohyama;K. Adachi;S. Kaizaki;H. Kumagai

川田 知: "金属錯体をビルディングブロックとする水素結合により集積されたケモセンサーの構築"機能材料. (印刷中). (2004)

Satoshi Kawada：“使用金属配合物作为构建块通过氢键构建化学传感器”（正在出版）。

Reactions between Vanadium(III) and a Pyridylketone oxime Ligand and Structures of Reaction Products

钒(III)与吡啶酮肟配体的反应及反应产物的结构

• 发表时间: 2003
• 期刊: Coord.Chem.Rev. 237
• 作者: H.Kumagai;M.Endo;M.Kondo;S.Kawata;S.Kitagawa
• 通讯作者: S.Kitagawa

Module-Based Assembly of Copper(II)-chloranilate Compounds : Syntheses, Crystal Structures and Magnetic Properties of {[Cu2(CA)(terpy)2][Cu(CA)2]} and {[Cu2(CA)(terpy)2(dmso)2]-[Cu(CA)2(dmso)2]/EtOHI}(H2CA=chloraniliacid.terpy=2.2':6'.2"-terpyridine dmso=

基于模块的氯苯甲酸铜(II)化合物组装：{[Cu2(CA)(terpy)2][Cu(CA)2]}和{[Cu2(CA)(terpy)的合成、晶体结构和磁性

• 发表时间: 2004
• 期刊: Inorg.Chem. 43
• 作者: K.Hori;Y.Matsunaga;A.Yoshizawa;T.Kusumoto;T.Ozeki;A.Iida;H.Chiba;M.Kawahara et al.
• 通讯作者: M.Kawahara et al.

Direct Two-Step spin-Crossover through [HS-HS]…[LS-LS] at the Plateau in Binuclear Diiron(II) Complex [{Fe(NCBH3)(4phpy)}2(μ-bpypz)2]

在双核二铁 (II) 配合物 [{Fe(NCBH3)(4phpy)}2(μ-bpypz)2] 平台上通过 [HS-HS]…[LS-LS] 直接两步旋转交叉

• 发表时间: 2004
• 期刊: Chem.Commun. 2004-24
• 作者: 編者 広橋亮;坂本恵一;奥村映子;K.Nakano et al.
• 通讯作者: K.Nakano et al.