对多核Ru-TPPZ复合物的综合计算和实验研究:了解协调聚合物的电子和光学特性
Simona Fantacci1, Filippo De Angelis, Jingjing Wang
1Istituto CNR di Scienze e Tecnologie Molecolari, Dipartimento di Chimica, Università di Perugia, via Elce di Sotto 8, I-06123, Perugia, Italy. simona@thch.unipg.it
Journal of the American Chemical Society
|August 5, 2004
概括
我们合成并研究了多核 (Ru) 聚二基复合物. 较长的寡合物种在可见的吸收光谱中呈现红移,这表明了先进光活性聚合物应用的潜力.
科学领域:
- 无机化学 无机化学 有机化学
- 材料科学 材料科学 材料科学
- 摄影化学的使用.
背景情况:
- 多核复合体与多基联体对于开发先进的光活性材料至关重要.
- 了解结构和光物理性质之间的关系是设计高效光活性聚合物的关键.
研究的目的:
- 为了合成和表征多核 (Ru) 聚基复合物 ([Ru(n) ((TPPZ) ((n+1))) ((2n+)).
- 研究寡合物链长度对这些复合物的电子结构和光学特性的影响.
- 通过计算阐明合成复合物的几何,电子结构和激发状态.
主要方法:
- 寡合物的合成和光谱表征 (UV-Vis吸收).
- 密度函数理论 (DFT) 和时间依赖的DFT (TD-DFT) 计算.
- 分析电子结构,兴奋状态和电荷转移过渡.
主要成果:
- 成功合成和表征寡合物 (n=1-4, >5).
- 观察到可见吸收最大值的红移随着寡合体长度的增加 (单体到n>5).
- 实验和计算光谱之间的良好一致性,证实金属对金属加联体电荷转移 (MMLCT) 是主要的过渡.
结论:
- 主要可见的吸收带被分配给MMLCT过渡,在整个综合体上分散.
- 在n>1.1.的实验光谱中,旋转禁止的单点-三点过渡有助于低能肩.
- 这些发现为设计新型光活性聚合物提供了对结构属性关系的见解.
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