An Allosterically Regulated, Four-State Macrocycle,Inorganic Chemistry

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An Allosterically Regulated, Four-State Macrocycle
Inorganic Chemistry ( IF 4.3 ) Pub Date : 2018-01-05 00:00:00 , DOI: 10.1021/acs.inorgchem.7b02745
Andrea I. d’Aquino ₁ , Ho Fung Cheng ₁ , Joaquín Barroso-Flores ₂ , Zachary S. Kean ₁ , Jose Mendez-Arroyo ₁ , C. Michael McGuirk ₁ , Chad A. Mirkin ₁

Affiliation

Macrocycles capable of host–guest chemistry are an important class of structures that have attracted considerable attention because of their utility in chemical separations, analyte sensing, signal amplification, and drug delivery. The deliberate design and synthesis of such structures are rate-limiting steps in utilizing them for such applications, and coordination-driven supramolecular chemistry has emerged as a promising tool for rapidly making large classes of such systems with attractive molecular recognition capabilities and, in certain cases, catalytic properties. A particularly promising subset of such systems are stimuli-responsive constructs made from hemilabile ligands via the weak-link approach (WLA) to supramolecular coordination chemistry. Such structures can be reversibly toggled between different shapes, sizes, and charges based upon small-molecule and elemental-anion chemical effectors. In doing so, one can deliberately change their recognition properties and both stoichiometric and catalytic chemistries, thereby providing mimics of allosteric enzymes. The vast majority of structures made to date involve two-state systems, with a select few being able to access three different states. Herein, we describe the synthesis of a new allosterically regulated four-state macrocycle assembled via the WLA. The target structure was made via the stepwise assembly of ditopic bidentate hemilabile N-heterocyclic carbene thioether (NHC,S) and phosphino thioether (P,S) ligands at Pt^II metal nodes. The relatively simple macrocycle displays complex dynamic behavior when addressed with small-molecule effectors, and structural switching can be achieved with several distinct molecular cues. Importantly, each state was fully characterized by multinuclear NMR spectroscopy and, in some cases, single-crystal X-ray diffraction studies and density functional theory computational models. This new structure opens the door to complex multicue switching reminiscent of multistate chemoswitches that could be important in controlling stoichiometric and catalytic transformations as well as generating molecular logic systems.

中文翻译：

变构调控的四态宏周期

具有主客体化学功能的大环化合物是一类重要的结构，由于其在化学分离，分析物感测，信号放大和药物递送中的用途而备受关注。此类结构的精心设计和合成是将其用于此类应用的限速步骤，并且配位驱动超分子化学已成为一种有前途的工具，可用于快速制造出具有吸引力分子识别功能的此类系统，在某些情况下，催化性能。这种系统的一个特别有希望的子集是由半不稳定的配体通过弱链接方法（WLA）到超分子配位化学制备的刺激响应性构建体。这样的结构可以在不同的形状，大小，以及基于小分子和元素阴离子化学效应器的电荷。这样，可以故意改变其识别特性以及化学计量和催化化学性质，从而提供变构酶的模拟物。迄今为止，绝大多数结构都涉及两个状态的系统，只有少数几个能够访问三个不同的状态。在这里，我们描述了通过WLA组装的新的变构调节四态大环的合成。通过在Pt逐步组装对位二齿半不稳定的N-杂环卡宾硫醚（NHC，S）和膦硫醚（P，S）配体来制备目标结构从而提供了变构酶的模拟物。迄今为止，绝大多数结构都涉及两个状态的系统，只有少数几个能够访问三个不同的状态。在这里，我们描述了通过WLA组装的新的变构调节四态大环的合成。目标结构是通过在Pt上逐步组装对位二齿半不稳定的N-杂环卡宾硫醚（NHC，S）和膦硫醚（P，S）配体而制成的从而提供了变构酶的模拟物。迄今为止，绝大多数结构都涉及两个状态的系统，只有少数几个能够访问三个不同的状态。在这里，我们描述了通过WLA组装的新的变构调节四态大环的合成。通过在Pt逐步组装对位二齿半不稳定的N-杂环卡宾硫醚（NHC，S）和膦硫醚（P，S）配体来制备目标结构^二，金属节点。当使用小分子效应子处理时，相对简单的大环化合物显示出复杂的动力学行为，并且可以通过几种不同的分子线索来实现结构转换。重要的是，每种状态都可以通过多核NMR光谱进行全面表征，在某些情况下还可以通过单晶X射线衍射研究和密度泛函理论计算模型来表征。这种新结构为复杂的多提示开关打开了大门，使人想起多态化学开关，这对于控制化学计量和催化转化以及生成分子逻辑系统可能很重要。

更新日期：2018-01-05

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