Wang Shaoshan, Li Zhuo, Ding Pengcheng, Mattioli Cristina, Huang Wujun, Wang Yang, Gourdon André, Sun Ye, Chen Mingshu, Kantorovich Lev, Yang Xueming, Rosei Federico, Yu Miao
School of Chemistry and Chemical Engineering, Harbin Institute of Technology, Harbin, 150001, China.
Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, 116023, China.
Angew Chem Int Ed Engl. 2021 Aug 2;60(32):17435-17439. doi: 10.1002/anie.202106477. Epub 2021 Jun 30.
On-surface synthesis (OSS) involving relatively high energy barriers remains challenging due to a typical dilemma: firm molecular anchor is required to prevent molecular desorption upon the reaction, whereas sufficient lateral mobility is crucial for subsequent coupling and assembly. By locking the molecular precursors on the substrate then unlocking them during the reaction, we present a strategy to address this challenge. High-yield synthesis based on well-defined decarboxylation, intermediate transition, and hexamerization is demonstrated, resulting in an extended and ordered network exclusively composed of the newly synthesized macrocyclic compound. Thanks to the steric hindrance of its maleimide group, we attain a preferential selection of the coupling. This work unlocks a promising path to enrich the reaction types and improve the coupling selectivity hence the structual homogeneity of the final product for OSS.
由于一个典型的两难困境，涉及相对较高能垒的表面合成（OSS）仍然具有挑战性：反应时需要牢固的分子锚来防止分子解吸，而足够的横向移动性对于后续的偶联和组装至关重要。通过将分子前体锁定在底物上，然后在反应过程中解锁它们，我们提出了一种应对这一挑战的策略。展示了基于明确的脱羧、中间体转变和六聚化的高产率合成，形成了一个仅由新合成的大环化合物组成的扩展且有序的网络。由于其马来酰亚胺基团的空间位阻，我们实现了偶联的优先选择。这项工作为丰富反应类型、提高偶联选择性从而改善OSS最终产物的结构均匀性开辟了一条有前景的道路。
