Deng Junmiao, Lu Hanwei, Ye Hebo, Hai Yu, Liu Zimu, You Lei
State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002, China.
College of Chemistry and Material Science, Fujian Normal University, Fuzhou 350007, China.
Org Biomol Chem. 2025 Mar 5;23(10):2498-2509. doi: 10.1039/d5ob00094g.
Dynamic covalent macrocycles offer the advantage of tunable ring-opening/ring-closure and structural transformation, but their control with precision remains a daunting task due to the labile nature of reversible bonds. Herein we demonstrate the precise formation/scission of covalent macrocycles with varied sizes by contrasting the reactivity, stability, and degradability of light-active and light-inactive dynamic covalent bonds. The incorporation of photoswitchable and non-photoresponsive aldehyde sites into one single dialdehyde component afforded the creation of [1 + 1] type macrocycles with primary diamines of suitable lengths. The manipulation of light and acid/base stimuli allowed on-demand breaking/remaking of macrocycles, achieving the interconversion between macrocyclic and linear skeletons. Moreover, a combination of the dialdehyde, primary diamines, and secondary diamines enabled the construction of hetero-type [2 + 1 + 1'] macrocycles enhanced discrimination and hierarchical assembly. Light-induced kinetic locking/unlocking of dynamic bonds further afforded macrocycle-to-macrocycle conversion when needed. Through leveraging controllable covalent connection/disconnection, switchable formation/disintegration of mechanically interlocked catenanes was further accomplished. The results described showcase the potential of photoinduced dynamic covalent chemistry for preparing complex architectures and should set the stage for molecular recognition, dynamic assemblies, synthetic motors, and responsive materials.
动态共价大环化合物具有可调节的开环/闭环和结构转变的优势，但由于可逆键的不稳定性质，精确控制它们仍然是一项艰巨的任务。在此，我们通过对比光活性和光非活性动态共价键的反应性、稳定性和可降解性，展示了不同尺寸共价大环化合物的精确形成/断裂。将光开关和非光响应醛基位点引入单个二醛组分中，可与合适长度的伯二胺形成[1 + 1]型大环化合物。通过光和酸/碱刺激的操控，可以按需破坏/重新形成大环化合物，实现大环和线性骨架之间的相互转化。此外，二醛、伯二胺和仲二胺的组合能够构建杂化型[2 + 1 + 1']大环化合物，增强识别能力和分级组装。光诱导的动态键的动力学锁定/解锁在需要时进一步实现了大环到大环的转化。通过利用可控的共价连接/断开，进一步实现了机械互锁连环烷的可切换形成/分解。所述结果展示了光诱导动态共价化学在制备复杂结构方面的潜力，应为分子识别、动态组装、合成马达和响应材料奠定基础。
