Pereira Orenha Renato, Muñoz-Castro Alvaro, Piotrowski Maurício Jeomar, Caramori Giovanni F, Rocha Renato Gonçalves, Parreira Renato Luis Tame
Núcleo de Pesquisas em Ciências Exatas e Tecnológicas, Universidade de Franca, Av. Dr. Armando de Sáles Oliveira 201, Franca, São Paulo 14404-600, Brazil.
Facultad de Ingeniería, Arquitectura y Diseño, Universidad San Sebastián, Bellavista 7, Santiago 8420524, Chile.
ACS Phys Chem Au. 2025 Jan 6;5(2):183-194. doi: 10.1021/acsphyschemau.4c00090. eCollection 2025 Mar 26.
Cations have significant applications in fields such as medicinal inorganic chemistry and catalysis. Rotaxanes are composed of a macrocyclic structure that is mechanically interlocked with a linear molecule. These mechanically interlocked molecules (MIMs) provide a potential chemical environment that allows for the interaction with cations. In this study, the bonding situations between rotaxanes or their acyclic/cyclic molecular derivatives and: (i) transition metal (Zn and Cd); or (ii) alkali metal (Li, Na, and K), cations have been studied. It is notable that among the MIMs structures, the rotaxanes demonstrate enhanced interactions with cations in comparison to the cyclic and, notably, the acyclic derivative molecules. The modification of rotaxane structures through structural changes and chemical reduction represents an intriguing approach to enhance cationic recognition, which is supported by the formation of more favorable electrostatic and/or orbital interaction energies in comparison with Pauli repulsive energies. The findings of this investigation can be employed in the synthesis of compounds with enhanced cation recognition capabilities.
阳离子在药用无机化学和催化等领域有着重要应用。轮烷由与线性分子机械互锁的大环结构组成。这些机械互锁分子（MIMs）提供了一个潜在的化学环境，使得能够与阳离子发生相互作用。在本研究中，已对轮烷或其无环/环状分子衍生物与：（i）过渡金属（锌和镉）；或（ii）碱金属（锂、钠和钾）阳离子之间的键合情况进行了研究。值得注意的是，在MIMs结构中，与环状分子尤其是无环衍生物分子相比，轮烷表现出与阳离子更强的相互作用。通过结构变化和化学还原对轮烷结构进行修饰，是增强阳离子识别的一种有趣方法，与泡利排斥能相比，更有利的静电和/或轨道相互作用能的形成支持了这一点。本研究的结果可用于合成具有增强阳离子识别能力的化合物。
