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

基本信息

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

项目摘要

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.

尽管已经进行了iodo桥的铂（II），（iv）双甲胺络合物的合成和结晶，但未成功获得光激发晶体学研究的良好晶体样品。取而代之的是，用于发光卤素桥的铜（i）聚合物配合物的光启用状态X射线衍射研究已得到进展。发光的双子（I）复合物[CU_2X_2（PPH_3）_2L]∞（X = I，Br，Cl; L = Bipyridine或Pyradine）由{Cu_2x_2}菱形单元组成，这些单元由二胺配体构建无形链结构。发射带的起源主要分配给Cu（i）到配体电荷转移（MLCT）和卤素到配体（XLCT）激发态。碘 - 复合物[Cu_2i_2（pph_3）_2（bpy）]∞的单晶X射线衍射实验表明，两个碘原子在{Cu_2i_2}平面中彼此靠近。在[Cu_2i_2（pph_3）_2（Pyz）]∞中发现了金属和卤素原子运动的相同方式。在相关的离散复合物[Cu_2i_2（pph_3）（pyz）_2]的情况下，具有相同{Cu_2i_2}的{Cu_2i_2}，表明晶体中{Cu_2i_2}核心的一小部分旋转，且较小的键呈旋转。在另一个离散复合物[Cu_2i_2（pph_3）（ph-py）_2]中没有明显的几何变形，该复合物显示出强烈的发光，该发光被分配给了不同的性质作为配体π-π*过渡态。在{Cu2i2}框架中，极端状态结构的变化与基态几何形式之间已经揭示了一些显着的相关性，这也与它们的发光特性有关。

项目成果

期刊论文数量（19）

专著数量（0）

科研奖励数量（0）

会议论文数量（0）

专利数量（0）

A new molecular oxide with a Pt_2Mo_2O_8 core and its two conformers

以Pt_2Mo_2O_8为核的新型分子氧化物及其两种构象异构体

DOI：
发表时间：
2005
期刊：
Inorganic Chemistry Communications 8
影响因子：
0
作者：
K.Noro;Y.Ozawa;A.Yagasaki
通讯作者：
A.Yagasaki

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

DOI：
发表时间：
2006
期刊：
Angewandte Chemie, International Edition 45(39)
影响因子：
0
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.

Direct Observation of Photochromic Dynamics in the Crystalline State of an Organorhodium Dithionite Complex

有机铑连二亚硫酸盐配合物晶态光致变色动力学的直接观察

DOI：
发表时间：
2006
期刊：
Angew.Chem.Int.Ed. 45
影响因子：
0
作者：
Y.Sawai;H.Nabika;M.Kiguchi;Y.Sawai;B.Takimoto;M.Kiguchi;B.Takimoto;M.Kiguchi;B.Takimoto;H.Nabika;K.Murakoshi;J.Li;Y.Sawai;沢井良尚;沢井良尚;H.Takashima;H.Fujiwara;H.Takashima;藤原英樹;H.Konishi;A.Chiba;H.Fujiwara;藤原英樹;Y.Miyano;H.Nakai
通讯作者：
H.Nakai

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。

DOI：
发表时间：
2006
期刊：
ingewandte Chemie, International Edition 45(31)
影响因子：
0
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