在一系列的生物复合体中控制激素连接的分子内和分子间电子合
Brice J O Kessler1, Iram F Mansoor1, Derek I Wozniak1
1Department of Chemistry and Chemical Biology, Rutgers, The State University of New Jersey, 123 Bevier Road, Piscataway, New Jersey 08854, United States.
Journal of the American Chemical Society
|July 17, 2023
概括
研究人员通过不同的复合体调节金属桥合混合 (MV) 系统的电子合. 这实现了前所未有的电子移位控制,从局部到移位状态,而不会改变氧化还原点或金属.
科学领域:
- 无机化学
- 材料科学
- 超分子化学
背景情况:
- 控制具有多个氧化还原点的分子中的电子合对于调整电子性质至关重要.
- 经典的混合度 (MV) 系统通过有机桥梁提供可调性,但由于金属的固定电子,金属桥系统具有挑战性.
- 现有的金属桥接MV系统缺乏独立控制金属的电子状态,独立于氧化还原活性联体.
研究的目的:
- 克服控制金属桥混合价值系统的局限性.
- 在生物中演示桥梁金属中心的独立电子调.
- 探索MV状态中的电子结构范围,从本地化到非本地化.
主要方法:
- 合成具有不同辅助配体供体强度的生物复合物 ([1-Co]和[2-Co]).
- 电化学分析以探测氧化还原特性和混合价值状态.
- 分析间隔电荷转移 (IVCT) 频段的UV-Vis-NIR光谱.
- 单晶X射线衍射 (XRD) 用于描述固态结构和相互作用.
主要成果:
- 一系列具有可调的基捐赠体的基生物 ([1-Co]) 允许逐渐电子调桥梁Co(II) 中心.
- 复杂的[2-Co]与NHC捐赠者保持了Co(III) 状态,即使在减少viologen.
- 电子结构从完全局部化 (罗宾-戴一级) 到完全移位化 (三级) 的MV状态.
- 单晶XRD揭示了基因配对相互作用和3D基因 π 堆叠在固态中,赋予了机械灵活性.
结论:
- 通过调节辅助连接剂捐赠强度,在金属桥接MV系统中实现了前所未有的电子合控制.
- 在没有改变氧化还原点或桥梁金属的情况下,在MV状态下展示了广泛的电子结构.
- 在金属生物体的固态中发现了新的通过空间的电子合.
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