Kondinski Aleksandar, Ghorbani-Asl Mahdi
Department of Chemical Engineering and Biotechnology, University of Cambridge Philippa Fawcett Dr Cambridge CB3 0AS UK
Institute of Ion Beam Physics and Materials Research Helmholtz-Zentrum Dresden-Rossendorf 01328 Dresden Germany
Nanoscale Adv. 2021 Aug 13;3(19):5663-5675. doi: 10.1039/d1na00387a. eCollection 2021 Sep 28.
In organic systems, dynamic covalent chemistry provides an adaptive approach (, "covalent dynamics") where thermodynamic equilibria are used to tailor structural and electronic changes in molecular assemblies. The covalent dynamics finds utility in the design of novel self-healing materials, sensors, and actuators. Herein, using density functional theory (DFT) we explore the structural, electronic and transport properties of the Pt-based polyoxometalate (POM) [Pt O(SO)] and its derivatives. The latter POM has six redox responsive {O-Pt-Pt-O} moieties and prospects for storage of up to twelve electrons, thus exemplifying how dynamic covalent chemistry may manifest itself in fully inorganic systems. Simulations of the Au/POM/Au junction show that the electron conduction strongly depends on the redox of the POM but more weakly on its rotations with respect to the Au surface. Moreover, the POM shows promising spin-polarized current behaviour, which can be modulated using bias and gate voltages.
在有机体系中，动态共价化学提供了一种适应性方法（即“共价动力学”），其中利用热力学平衡来调整分子组装体中的结构和电子变化。共价动力学在新型自愈材料、传感器和致动器的设计中具有实用价值。在此，我们使用密度泛函理论（DFT）研究了基于铂的多金属氧酸盐（POM）[Pt O(SO)]及其衍生物的结构、电子和传输性质。后一种POM具有六个氧化还原响应性的{O-Pt-Pt-O}基团，并且具有存储多达十二个电子的前景，从而例证了动态共价化学如何在完全无机体系中体现自身。对Au/POM/Au结的模拟表明，电子传导强烈依赖于POM的氧化还原，但相对于Au表面的旋转依赖性较弱。此外，POM表现出有前景的自旋极化电流行为，可使用偏置电压和栅极电压对其进行调制。
