Multi-State Dynamic Coordination Complexes Interconverted through Counterion-Controlled Phase Transfer
Multi-State Dynamic Coordination Complexes Interconverted through Counterion-Controlled Phase Transfer
复制标题
通过反离子控制相转移相互转换的多态动态协调配合物
DOI：
10.1021/acs.inorgchem.0c03708
复制
发表时间：
2021
影响因子：
4.6
通讯作者：
Mirkin, Chad A.
中科院分区：
文献类型：
--
作者：
Cheng, Ho Fung;Paul, McKinley K.;d’Aquino, Andrea I.;Stern, Charlotte L.;Mirkin, Chad A.
我们研究了一系列的动态弱连接方法（WLA）的配合物，可以穿梭在两个不混溶的溶剂之间，并通过离子交换在两个结构状态之间切换。在这里，我们建立了疏水阴离子转移阳离子，两亲性复合物从水相到有机相，而氯源逆转的过程。由于WLA配合物的动态金属配位特性，这些配合物（单-至双-）的齿度可以在它们分配成不同相时进行调制。此外，我们发现，heteroligated配合物轴承不同的供体强度的配位体优先重排成两个homoligated配合物相分区，以最大限度地增加更强的配位键的数量。在具有一种溶剂的系统中没有观察到这种行为，这突出了半不稳定配体在多相溶剂环境中的动态和刺激响应性质。总之，这项工作表明，高度可重构的WLA模式可以实现由直接的盐复分解反应驱动的两相反应网络或化学分离的设计。
We studied a series of dynamic weak-link approach (WLA) complexes that can be shuttled between two immiscible solvents and switched between two structural states via ion exchange. Here, we established that hydrophobic anions transfer cationic, amphiphilic complexes from the aqueous phase to the organic phase, while a chloride source reverses the process. As a result of the dynamic metal coordination properties of WLA complexes, the denticity of these complexes (mono- to bi-) can be modulated as they partition into different phases. In addition, we discovered that heteroligated complexes bearing ligands of different donor strengths preferentially rearrange into two homoligated complexes that are phase-partitioned to maximize the number of stronger coordination bonds. This behavior is not observed in systems with one solvent, highlighting the dynamic and stimuli-responsive nature of hemilabile ligands in a multiphasic solvent environment. Taken together, this work shows that the highly reconfigurable WLA modality can enable the design of biphasic reaction networks or chemical separations driven by straightforward salt metathesis reactions.