Weak covalent interactions and anionic charge-sharing polymerisation in cluster environments
Weak covalent interactions and anionic charge-sharing polymerisation in cluster environments
复制标题
簇环境中的弱共价相互作用和阴离子电荷共享聚合
DOI：
10.1039/d1cp01213d
复制
发表时间：
2021
影响因子：
3.3
通讯作者：
Sanov, Andrei
中科院分区：
文献类型：
--
作者：
Dauletyarov, Yerbolat;Sanov, Andrei
我们讨论了形成弱共价键导致阴离子电荷共享二聚或聚合在微观集群环境。簇结构单元之间的共价键合描述的相干电荷共享，概念化使用耦合单体分子轨道模型。该模型假设一阶分离的内部和内部的单体键合结构。结合休克尔式的形式主义，适合弱共价和溶剂化相互作用，它提供了洞察两种类型的力量之间的竞争，并阐明了负责电荷共享二聚和聚合的单体间轨道的性质。在典型条件下，溶剂化的累积效应阻碍聚合，限制共价结合的核心阴离子的大小。
We discuss the formation of weak covalent bonds leading to anionic charge-sharing dimerisation or polymerisation in microscopic cluster environments. The covalent bonding between cluster building blocks is described in terms of coherent charge sharing, conceptualised using a coupled-monomers molecular-orbital model. The model assumes first-order separability of the inter- and intra-monomer bonding structures. Combined with a Hückel-style formalism adapted to weak covalent and solvation interactions, it offers insight into the competition between the two types of forces and illuminates the properties of the inter-monomer orbitals responsible for charge-sharing dimerisation and polymerisation. Under typical conditions, the cumulative effect of solvation obstructs the polymerisation, limiting the size of covalently bound core anions.