Light-induced excited state X-ray crystallography of multinuclear copper complexes

多核铜配合物的光诱导激发态X射线晶体学

• 批准号: 11640570
• 负责人: OZAWA Yoshiki
• 金额: $ 2.69万
• 依托单位: Himeji Institute of Technology
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 1999
• 资助国家: 日本
• 起止时间: 1999 至 2001
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-11640570/
• 关键词: X-ray crystallography; photoexcited states; synchrotron radiation; single crystal; copper complex; multinuclear metal cluster; image plate; 光励起構造; 単結晶X線構造解析; 白銀複核錯体; 多核銅錯体; 金属-金属結合; 低温構造解析; 結晶構造解析; 白金錯体; ロジウム錯体

Multinuclear Cu(I) complexes such as [Cul(py)]4 have shown luminescent by UV light irradiation. In the photoexcited states, distortion of metal cluster core has been expected. To observe this molecular distortion in the photoexcited states directly by single crystal X-ray diffraction analyses, we have performed development of a diffractometer, establishment of excited states structure refinement calculations, and survey of target compounds. Light illuminating devices has been installed in the "low-temperature vacuum X-ray camera" which are designed for obtaining low noise diffraction images at low temperature. The multiple-exposure image plate (IP) method is a new detection technique developed in this project and installed in this camera, by which both diffraction patterns measured for light irradiated and non-irradiated conditions are recorded on the same IP. The X-ray camera has settled in a Spring-8 beamline utilizing highbrilliant X-ray radiation sources. Molecular distortion in the light irradiated crystal can be detected by a differential Fourier syntheses using X-ray diffraction intensity changes between light-on and off conditions, followed by qualitative calculation of excited state population and geometrical changes in a crystal, using least square refinements. Structure analysis of a luminescent a diplatinum(II) complex (Bu_4N)_2H_2[Pt_2(pop)_4] single crystal under blue laser irradiation has been successfully performed. Photoexcited molecule of 1.4% population shows Pt-Pt bond shrinkage of 0.23 A under blue laser irradiation which is consistent with spectroscopic investigations.

多核 Cu(I) 配合物（例如 [Cul(py)]4）在紫外光照射下会发光。在光激发态下，金属簇核的变形是预料之中的。为了通过单晶X射线衍射分析直接观察光激发态的分子畸变，我们开发了衍射仪，建立了激发态结构细化计算，并对目标化合物进行了调查。 “低温真空X射线相机”中安装了光源照明装置，旨在在低温下获得低噪声衍射图像。多重曝光图像板（IP）方法是本项目开发并安装在该相机中的一种新检测技术，通过该技术，在光照射和非照射条件下测量的衍射图案都记录在同一IP上。 X 射线相机已安装在使用高亮度 X 射线辐射源的 Spring-8 光束线中。光照射晶体中的分子畸变可以通过微分傅立叶合成来检测，该合成使用光开和关条件之间的 X 射线衍射强度变化，然后使用最小二乘精修对晶体中的激发态布居和几何变化进行定性计算。成功地对蓝色激光照射下发光的二铂(II)配合物(Bu_4N)_2H_​​2[Pt_2(pop)_4]单晶进行了结构分析。 1.4% 群体的光激发分子在蓝色激光照射下显示出 0.23 A 的 Pt-Pt 键收缩，这与光谱研究一致。

项目成果

K. Toriumi and Y. Ozawa: "Photoexcited molecular structure of diplatinum(II) complex by single crystal X-ray structure analysis"Spring-8 Research Frontiers 2001/2002. in press.

K. Toriumi 和 Y. Ozawa：“通过单晶 X 射线结构分析二铂 (II) 络合物的光激发分子结构”Spring-8 研究前沿 2001/2002。

Y. Ozawa et al.: "Photo excited Crystallography of Diplatinum Complex by Multiple-exposure IP Method"Chemistry Letters. 32. 62-63 (2003)

Y. Ozawa 等人：“通过多重曝光 IP 方法进行二铂络合物的光激发晶体学”化学快报。

K.Toriumi et al.: "Improvement and Advancement of the Vacuum Type Low-Temperature IP Camer(2)"SPring-8 User Experiment Report. 6. 21-21 (2001)

K.Toriumi 等人：“真空型低温网络摄像机的改进和进步(2)”SPring-8 用户实验报告。

K.Toriumi et al.: "A Set-Up and a Performance Test of the Vacuum Type Low-Background X-ray Camera"SPring-8 User Experiment Report. 4. 22-22 (2002)

K.Toriumi 等人：“真空型低背景 X 射线相机的设置和性能测试”SPring-8 用户实验报告。

Y.Ozawa et al.: "Light-Induced Excited-States Crystallography of Metal Complexes"SPring-8 User Experiment Report. 8. 19-19 (2002)

Y.Ozawa 等人：“金属配合物的光诱导激发态晶体学”SPring-8 用户实验报告。