Xia Qingchun, Yang Jingli, Zhang Suzhen, Zhang Jie, Li Zhiyong, Wang Jianji, Chen Xuenian
Henan Key Laboratory of Boron Chemistry and Advanced Energy Materials, Collaborative Innovation Center of Henan Province for Green Manufacturing of Fine Chemicals, Key Laboratory of Green Chemical Media and Reactions, Ministry of Education, School of Chemistry and Chemical Engineering, Henan Normal University, Xinxiang, Henan 453007, China.
Green Catalysis Center and College of Chemistry, Zhengzhou University, Zhengzhou, Henan 450001, China.
J Am Chem Soc. 2023 Mar 22;145(11):6123-6134. doi: 10.1021/jacs.2c11647. Epub 2023 Mar 13.
Boron dipyrromethene (also known as bodipy), as a class of versatile and robust fluorophores and a structural analogue of porphyrins, has received a great deal of interests in the field of light-harvesting and energy-transfer processes. However, the fabrication of bodipy monomers into metal-organic frameworks (MOFs) and the exploitation of their potential still lags behind the porphyrin MOFs. In this work, two bodipy-based MOFs, BMOF with 1D chain structure and BMOF with 2D layer structure, were assembled by using dicarboxyl-functionalized bodipy ligands. BMOF can also be converted to BMOF by inserting additional ligands into BMOF to cross-link the adjacent chains into the rhombic grid layer. During this process, spontaneous exfoliation occurred simultaneously and resulted in the formation of several hundred nanometer thickness BMOF (nBMOF ), which can be further exfoliated into one-layer MOF nanosheets (BMON ) by using the ultrasonic liquid exfoliation method in a high yield. Featuring the distinct bodipy scaffolds in the porous frameworks, both BMOF and BMON displayed high reactivity and recyclability in the photocatalytic inverse hydroboration and cross-dehydrogenative coupling reactions to afford α-amino organoborons and α-amino amides in moderate to high yields. This work not only highlights the cascade utilization of ligand installation and ultrasonic liquid exfoliation methods to provide the single-layer MOF sheets in high yields but also advances the bodipy-based MOFs as a new type of heterogeneous photocatalysts in the forging of C-B and C-C bonds driven by visible light.
硼二吡咯亚甲基（也称为BODIPY）作为一类多功能且稳定的荧光团以及卟啉的结构类似物，在光捕获和能量转移过程领域受到了广泛关注。然而，将BODIPY单体制备成金属有机框架（MOF）及其潜力的开发仍落后于卟啉基MOF。在这项工作中，通过使用二羧基功能化的BODIPY配体组装了两种基于BODIPY的MOF，具有一维链状结构的BMOF和具有二维层状结构的BMOF。通过向BMOF中插入额外的配体以将相邻链交联成菱形网格层，BMOF还可以转化为BMOF。在此过程中，同时发生自发剥离，形成了几百纳米厚的BMOF（nBMOF），通过超声液体剥离法可以将其高产率地进一步剥离成单层MOF纳米片（BMON）。由于多孔框架中独特的BODIPY支架，BMOF和BMON在光催化逆硼氢化和交叉脱氢偶联反应中均表现出高反应活性和可回收性，以中等到高产率得到α-氨基有机硼和α-氨基酰胺。这项工作不仅突出了配体安装和超声液体剥离方法的级联利用以高产率提供单层MOF片材，而且还推动了基于BODIPY的MOF作为一种新型的多相光催化剂在可见光驱动的C-B和C-C键形成中的应用。
