New [4.4]Cyclophanes: Molecular Parallelograms, Triangles, Rhombuses, Pentagons, and Supramolecular Constructions

The fair or good yield synthesis of new [(4.4)n]cyclophanes (n = 1−5), starting from 1,4-bis(2-hydroxymethyl-5,5-dimethyl-1,3-dioxan-2-yl)benzene and several diacid−dichlorides, based on monomer and oligomer formation reactions (from 1 + 1 to 5 + 5), is reported. The structure and the complex architectures of the lattices for these cyclophanes are revealed by the X-ray molecular structure for five compounds, NMR investigations, and mass spectrometry measurements. Intramolecular and intermolecular CH−π, p−π, and π−π interactions are observed, both in solid state and solution.

本文报道了以1,4-双(2-羟甲基-5,5-二甲基-1,3-二氧杂环己烷-2-基)苯与多种二酰氯为起始原料，通过1+1至5+5配比的单聚体与低聚体形成反应，以中等至良好产率合成系列新型[(4.4)ₙ]环蕃（cyclophanes，n=1~5）的研究工作。通过对五种目标化合物的X射线分子结构解析、核磁共振（NMR）波谱表征及质谱检测，阐明了此类环蕃的分子结构及其晶格的复杂构筑特征。在固态与溶液状态下，均观测到分子内与分子间存在CH-π、p-π及π-π相互作用。