在混合电子系统的质子电子合中d-元素的作用
Mikihiro Hayashi1,2, Yuki Takahashi1, Yukihiro Yoshida1
1Division of Chemistry, Graduate School of Science , Kyoto University , Kitashirakawa-Oiwakecho , Sakyo-ku, Kyoto 606-8502 , Japan.
Journal of the American Chemical Society
|July 13, 2019
概括
这项研究表明d-元素如何影响d-π混合系统中的质子转移过程中的分子电子状态. 复合体表现出比复合体更强的质子电子合,表明d元素对这些电子性质的控制.
科学领域:
- * 无机化学
- * 材料科学
- * 超分子化学
背景情况:
- 合成了具有质子2,3-化硫酸盐 (L) 的金属复合物.
- * 这些复合物,M(HL) 2 (M=Ni,Pd,Pt),通过键自组.
- * 核心结构是M(S2C2)2单元,表现出d-π杂交,特别是在Pt复合体中.
研究的目的:
- * 研究d元素 (Ni,Pt) 与质子转移相结合的电子状态交替的影响.
- 在这些金属复合体中探索d-π杂交的作用.
- * 了解d元素替代如何控制质子电子合.
主要方法:
- * 紧和平面金属复合物的合成.
- * 结构和理论研究 (例如,X射线衍射,DFT).
- *依赖pH的光学和电化学测量 (例如UV-Vis光谱,循环电压测量).
主要成果:
- * 特别是在Pt复合体中观察到显著的d-π杂交.
- * Ni复合体表现出比Pt复合体更高的质子接受性和更强的氧化还原潜力的pH依赖性.
- 在H键多元仪中,潜在分裂 (ΔE1/2) 表示了不同程度的质子-电子合 (Ni:0.28 V,Pt:0.17 V).
结论:
- * D元素替代有效调节d-π混合系统中的质子电子合度.
- *电子特性和质子转移行为可以通过金属选择进行调整.
- 这项工作提供了对具有可控电子反应的功能材料设计的见解.
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