Solid-State Self-Assembly of Triazolylpyridine-Based Helicates and Mesocate: Control of the Metal–Metal Distances

Many materials properties are conditioned by the relative arrangement of metal ions in the solid state. Supramolecular architectures such as helicates may be designed with controlled metal to metal spacing in their midst. However, shorter distances and more extensive electronic communication may be achieved between individual architectures through their self-assembly in the solid state. In this manuscript, we report a rational analysis of the solid-state self-organization of dinuclear metallocylinders constructed by octahedral ion coordination with the 1,2,3-triazol-4-ylpyridyl chelate (FeII, NiII). Overall, aromatic and aliphatic spacers control the range and ranking of metal to metal distances in a predictive manner.诸多材料的性能均受固态下金属离子的相对排布所调控。诸如螺旋配合物（helicates）在内的超分子架构（supramolecular architectures），可被设计为在其内部实现可控金属间距的结构。然而，通过固态下的自组装，各超分子结构之间可实现更短的金属间距与更强的电子通讯耦合。本研究针对由八面体配位金属离子与1,2,3-三唑-4-基吡啶螯合配体（FeII、NiII）构筑的双核金属柱形配合物（dinuclear metallocylinders）的固态自组装行为开展了系统性理性解析。总体而言，芳香族与脂肪族间隔基可通过可预测的方式精准调控金属间距的分布范围与排布层级。