Studies on Photo-excited State valence Tautomerism of Multinuclear Metal Complexes by X-ray Crystallographic Analyses

X射线晶体学分析多核金属配合物光激发态价态互变异构现象的研究

• 批准号: 17550065
• 负责人: OZAWA Yoshiki
• 金额: $ 2.05万
• 依托单位: University of Hyogo
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2005
• 资助国家: 日本
• 起止时间: 2005 至 2006
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-17550065/
• 关键词: X-ray structure analysis; photo-excited states; multinuclear metal complex; Copper compound; luminescent Properties; synchrotron radiation; metal-organic framework; 金属錯体; 結晶構造; 単結晶X線構造解析; 放射光; 多核銅錯体; 原子価互変異性; X線構造解析; 光物性; 物性実験

Although syntheses and crystallization of iodo-bridged platinum(II),(IV) bis-diamine complex have been performed, no good crystal sample for photo-excited crystallographic studies was successfully obtained. Instead, photo-excited state X-ray diffraction studied for luminescent halogen-bridged copper(I) polymer complexes have been progressed. Luminescent dicopper(I) complexes [Cu_2X_2(PPh_3)_2L]∞(X=I, Br, Cl; L=bipyridine or pyradine) consist of {Cu_2X_2} rhombic units, which are bridged by diimine ligands constructing an infinite chain structure. The origin of emission bands are assigned mainly to a Cu(I) to ligand charge transfer (MLCT) and a halogen to ligand (XLCT) excited states. Single crystal X-ray diffraction experiments under photo-illumination for the iodine-complex [Cu_2I_2(PPh_3)_2(bpy)]∞ have shown that two iodine atoms are moved toward close to each other within the {Cu_2I_2} plane. The same manner in the motion of the metal and halogen atoms have found in [Cu_2I_2(PPh_3)_2(pyz)]∞. While in the case of a related discrete complex [Cu_2I_2(PPh_3)(pyz)_2] which has the same {Cu_2I_2} indicate that a very small portion of {Cu_2I_2} core in the crystal is rotated with little bond enlarge or shrinkage. There are no significant geometrical distortion has found in another discrete complex [Cu_2I_2(PPh_3)(Ph-py)_2] which shows intense luminescence which is assigned to a different nature as a ligand π-π* transition state. Some significant correlations have been revealed between excited-state structure changes and ground state geometries in the {Cu2I2} framework, which are also related with their luminescent properties.

虽然碘桥铂（II），（IV）双二胺配合物的合成和结晶已经进行，没有良好的晶体样品的光激发晶体学研究成功地获得。相反，光激发态X-射线衍射研究的发光卤素桥接的铜（I）聚合物配合物已取得进展。[Cu_2X_2（PPh_3）_2L]∞（X=I，Br，Cl; L=联吡啶或吡啶）是由{Cu_2X_2}菱形单元通过二亚胺配体桥接而成的无限链状结构。发射带的起源主要归属于Cu（I）到配体电荷转移（MLCT）和卤素到配体（XLCT）激发态。碘配合物[Cu_2I_2（PPh_3）_2（bpy）]_∞的X射线单晶衍射实验表明，在{Cu_2I_2}面内，两个碘原子相互靠近。在[Cu_2I_2（PPh_3）_2（pyz）]∞中，金属原子和卤素原子的运动也是同样的方式。而在具有相同{Cu_2I_2}的相关离散配合物[Cu_2I_2（PPh_3）（pyz）_2]的情况下，表明晶体中{Cu_2I_2}核心的很小一部分发生旋转，键的放大或收缩很小。在另一个不连续的配合物[Cu_2I_2（PPh_3）（Ph-py）_2]中，没有发现明显的几何畸变，但却显示出强烈的发光，并归属于配体π-π* 过渡态的不同性质。在{Cu_2I_2}骨架中，激发态结构的变化与基态几何结构之间存在着一些显著的相关性，这也与它们的发光性质有关。

项目成果

A High-Conductivity Crystal Containing a Copper(l) Coordination Polymer Bridged by the Organic Acceptor TANC.

含有由有机受体 TANC 桥接的铜 (I) 配位聚合物的高电导率晶体。

• 发表时间: 2006
• 期刊: ingewandte Chemie, International Edition 45(31)
• 作者: Tadokoro;M.;S. Yasuzuka;M. Nakamura;a. Shinoda;T. Tatenuma;M. Mitsumi;Y. Ozawa;K. Toriumi;H. Yoshino;D. Shiomi;K. Sato;T. Takui;T. Mon;K. Murata
• 通讯作者: K. Murata

X-ray structures of the tris(2,4-xylyl)phosphane and its trisulfonated derivative:Molecular architecture of a water-soluble sulfonated phosphane with propeller chiralitv

三(2,4-二甲苯基)膦及其三磺化衍生物的X射线结构：具有螺旋桨手性的水溶性磺化膦的分子结构

• 发表时间: 2007
• 期刊: Journal of Organometallic Chemistry 692(9)
• 作者: Benyei;A.C.;H. Gulyas;Y. Ozawa;K. Kimura;K. Toriumi;T. Kegl;J. Bakos
• 通讯作者: J. Bakos

Isobe, Direct Observation of Photochromic Dynamics in the Crystalline State of al Organorhodium Dithionite Complex

Isobe，有机铑连二亚硫酸盐络合物晶态光致变色动力学的直接观察

• 发表时间: 2006
• 期刊: Angewandte Chemie, International Edition 45(39)
• 作者: Nakai;H.;M. Mizuno;T. Nishioka;N. Koga;K.Shiomi;Y. Miyano;M. Irie;B. K. Breedlove;I. Kinoshita;Y. Hayashi;Y. Ozawa;T. Yonezawa;K. Toriumi;K.
• 通讯作者: K.

X-ray structures of the tris (2, 4-xylyl) phosphane and its trisulfonated derivative : Molecular architecture of a water-soluble sulfonated phosphane with propeller chirality

三(2, 4-二甲苯基)膦及其三磺化衍生物的X射线结构：具有螺旋桨手性的水溶性磺化膦的分子结构

• 发表时间: 2007
• 期刊: Journal of Organometallic Chemistry 692(9)
• 作者: Benyei;A. C.; Gulyas;H.; Ozawa;Y.; Kimura;K.; Toriumi;K.; Kegl;T.; Bakos;J.
• 通讯作者: J.

Poly(p-phenylene)-Type Polymer Composed of an(R, R)-C_2-Symmetric Chiral Recurring Unit: Solution Behavior, Packing Structure,and Large Circular Dichroism Observed with a Film of the Polymer

(R,R)-C_2-对称手性重复单元组成的聚对亚苯基型聚合物：溶液行为、堆积结构和聚合物薄膜观察到的大圆二色性

• 发表时间: 2007
• 期刊: J. Polym. Sci.: Part A: Polym. Chem. 45
• 作者: T. Yamamoto;et. al.
• 通讯作者: et. al.