稳定的混合复合体由胺连接金属集群的电子移位形成
Tyler M Porter1, Gavin P Heim1, Clifford P Kubiak1
1Department of Chemistry and Biochemistry , University of California, San Diego , 9500 Gilman Drive , La Jolla , California 92093-0358 , United States.
Journal of the American Chemical Society
|September 29, 2018
概括
在团的二聚体中,电子转移迅速发生,形成稳定的混合价值状态. 这表明通过键进行强大的电子通信,使得高度移位的电子结构成为可能.
科学领域:
- 无机化学
- 超分子化学
- 电子转移研究
背景情况:
- 氧中心的三团以其氧化还原活性而闻名.
- 键在分子自组和电子通信中起着至关重要的作用.
- 了解混合系统中的电子转移是开发分子电子学的关键.
研究的目的:
- 通过氧中心的三聚变体的结自相聚变体进行电子转移.
- 描述混合价值二元体的电子结构和稳定性.
- 探索结系统在强大的电子通信中的潜力.
主要方法:
- 在甲基中进行光电化学研究.
- 一个电子减少的三聚变二极体.
- 福里埃变换红外光谱 (FTIR) 和线形分析 (光学布洛赫) 来确定电子传输速率 (k_ET).
- 测定混合价值二次体的形成常数 (K_MV).
主要成果:
- 在一个电子的减少后快速自二元化,形成强合的混合价值二元体 ((1_2) ^-).
- 估计的电子转移速率 (k_ET) 约为10^11s^1,表明高度移位的电子结构.
- 高形成常数 (K_MV) ~10^6 M^-1,表示由于通过键进行电子交换而导致显著的稳定性 (~5.7 kcal/mol).
- 胺NH频段的强度增强,支持振动和电子波函数的强烈混合.
结论:
- 结合系统可以支持强大的捐赠器-桥梁-接受器合.
- 在键超分子组合中可以实现高度移位的电子结构.
- 这些发现挑战了键对于有意义的电子通信来说太弱的概念.
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