Studies on Photo-excited State valence Tautomerism of Multinuclear Metal Complexes by X-ray Crystallographic Analyses
Studies on Photo-excited State valence Tautomerism of Multinuclear Metal Complexes by X-ray Crystallographic Analyses
批准号:
17550065
负责人:
OZAWA Yoshiki
金额:
$2.05万
依托单位:
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
项目状态:
已结题
起止时间:
2005 至 2006
中文摘要
虽然已经合成和结晶了碘桥联的铂(II)、(IV)双二胺配合物,但还没有成功地获得用于光激发结晶学研究的良好的晶体样品。相反,发光卤素桥联铜(I)聚合物配合物的光激发态X射线衍射研究取得了进展。发光双铜(I)配合物[Cu2X2(PPh3)2L]∞(X=I,BrCl2;L=联吡啶或吡啶)由{Cu2X2}菱形单元组成,这些菱形单元由形成无限链状结构的二亚胺配体桥联。发射带的来源主要是铜(I)到配体的电荷转移(MLCT)和卤素到配体(XLCT)的激发态。对碘配合物[Cu2I_2(PPh_3)_2(Bpy)]∞的光致单晶X射线衍射实验表明,在{Cu2I_2}面内,两个碘原子相互靠近。在[Cu2I2(PPh3)2(PYZ)]∞中,金属原子和卤素原子的运动方式是相同的。而对于具有相同{Cu2I2}的相关离散络合物[Cu2I2(PPh3)(PYZ)2],则表明晶体中有很小一部分{Cu2I2}核心发生旋转,键几乎没有扩大或收缩。另一种离散型配合物[Cu2I2(PPh_3)(Ph-py)_2]没有发现明显的几何失真,它显示出不同性质的强烈发光,作为配体π-π*过渡态。在{Cu2I2}骨架中,激发态结构的变化与基态几何构型之间存在着显著的关联,这也与它们的发光性质有关。
英文摘要
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.
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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
DOI:
--
发表时间:
2007
期刊:
Journal of Organometallic Chemistry 692(9)
影响因子:
--
作者:
[Benyei, A.C., H. Gulyas, Y. Ozawa, K. Kimura, K. Toriumi, T. Kegl, J. Bakos]
通讯作者:
J. Bakos
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:
--
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
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:
--
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
DOI:
--
发表时间:
2007
期刊:
Journal of Organometallic Chemistry 692(9)
影响因子:
--
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
DOI:
--
发表时间:
2007
期刊:
J. Polym. Sci.: Part A: Polym. Chem. 45
影响因子:
--
作者:
[T. Yamamoto, et. al.]
通讯作者:
et. al.
共 14 条
Studies on Crystal Structures and Photophysical propertiea of Luminescent Multi-nuclear d10-metal Complexes
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批准号:21550065
-
项目类别:Grant-in-Aid for Scientific Research (C)
-
资助金额:$3.24万
-
财政年份:2009
-
负责人:OZAWA Yoshiki
-
依托单位:
Studies on photophysical properties and photoexcited structures of luminescent metal complexes by single crystal X-ray structure analyses.
-
批准号:19550069
-
项目类别:Grant-in-Aid for Scientific Research (C)
-
资助金额:$3.08万
-
财政年份:2007
-
负责人:OZAWA Yoshiki
-
依托单位:
Studies on Photo-excited State Crystal Structure of Multinuclear Metal Complexes by X-ray Structure Analyses.
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批准号:15350036
-
项目类别:Grant-in-Aid for Scientific Research (B)
-
资助金额:$8.32万
-
财政年份:2003
-
负责人:OZAWA Yoshiki
-
依托单位:
Light-induced excited state X-ray crystallography of multinuclear copper complexes
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批准号:11640570
-
项目类别:Grant-in-Aid for Scientific Research (C)
-
资助金额:$2.69万
-
财政年份:1999
-
负责人:OZAWA Yoshiki
-
依托单位:
海外基金