A Redox-Switchable, Allosteric Coordination Complex
A Redox-Switchable, Allosteric Coordination Complex
复制标题
DOI：
10.1021/jacs.8b09321
复制
发表时间：
2018-11-07
影响因子：
15
通讯作者：
Mirkin, Chad A.
中科院分区：
文献类型：
--
作者：
Cheng, Ho Fung;d'Aquino, Andrea I.;Mirkin, Chad A.
采用弱连接法合成了一种氧化还原调控的分子钳配合物。Pt-II复合物的特点是用二茂铁基部分官能化的氧化还原可切换的半不稳定配体（RHL），其氧化态调节特定配位位点的开放。通过氧化还原剂的变构调节提供了两种不同的结构状态-完全封闭状态和半开放状态-其相互转化通过多核NMR光谱，循环伏安法和UV-vis-NIR光谱进行了研究的可逆访问。通过SCXRD进一步表征了该四态系统中的两种结构，而其他结构则通过DFT计算进行了建模。这种完全可逆的基于RHL的系统定义了对特定配位位点的占用的不寻常的电化学控制水平，从而在单个系统内提供了对四种不同配位状态的访问，每种状态由结构和氧化态定义和区分。
A redox-regulated molecular tweezer complex was synthesized via the weak-link approach. The Pt-II complex features a redox-switchable hemilabile ligand (RHL) functionalized with a ferrocenyl moiety, whose oxidation state modulates the opening of a specific coordination site. Allosteric regulation by redox agents gives reversible access to two distinct structural states-a fully closed state and a semi-open state-whose interconversion was studied via multinuclear NMR spectroscopy, cyclic voltammetry, and UV-vis-NIR spectroscopy. Two structures in this four-state system were further characterized via SCXRD, while the others were modeled through DFT calculations. This fully reversible, RHL-based system defines an unusual level of electrochemical control over the occupancy of a specific coordination site, thereby providing access to four distinct coordination states within a single system, each defined and differentiated by structure and oxidation state.