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直接形成D₂-对称交替圆形体的连接体与连接体相互作用

Tan Yan Bing¹, Tsuyoshi Kawai¹, Junpei Yuasa^2,3

¹Graduate School of Materials Science , Nara Institute of Science and Technology , 8916-5 Takayama , Ikoma , Nara 630-0192 , Japan.

Journal of the American Chemical Society

|February 14, 2018

概括

研究人员使用 bis-β-diketonate 和 chiral bis- 4-phenyl-2-oxazolinyl) pyridine 连接物制造了性兰他化物. 这些纳米尺度结构表现出独特的圆形螺旋性和圆极化发光.

科学领域:

超分子化学
协调化学
兰化物化学

背景情况:

对相互作用对于构建复杂的超分子结构至关重要.
在金属复合体中诱导不对称性和特定性质的过程中,基质连接物是必不可少的.
兰化物复合物具有独特的光物理特性,包括发光.

研究的目的:

使用特定的配体和化物离子制造D2对称的交替圆形合体.
研究合成的螺旋体的结构,立体化学和光物理性质.
探索连接体性对螺旋体形成和特性的影响.

主要方法:

乙二甲基酸盐 (BTP) 和乙二甲基酸盐 (bis(4-phenyl-2-oxazolinyl) 酸盐 (R) 或 (S) -Ph-Pybox) 配合兰酸盐 (III) 离子的自组合.
进行X射线结构分析以确定螺旋体的精确三维布局.
循环二极化 (CD) 和循环极化发光 (CPL) 光谱,以研究溶液中的光学特性.

主要成果:

成功制造了一个D2-对称的交替圆形螺旋体,配方是[(R) -或 (S) -Ph-Pybox]4(LnIII) 4(BTP) 6.
纳米大小的正方形网格结构表现出不同的 (M) 和 (P) 螺旋性.
在EuIII中心周围的Ph-Pybox和BTP连体之间存在π-π叠加相互作用的证据.
螺旋体存在于溶液中的单个和同体基质二聚体,显示CD和CPL.
观察到在圆形螺旋体中偏爱异体结构.

结论:

有关联体的相互作用使得复杂的,性兰坦化螺旋体的构建成为可能.
合成的螺旋体具有独特的结构和手术特性,包括CPL.
这些发现为设计用于光学应用的基于合兰他尼德的新材料开辟了道路.

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