Direct Construction of Isomeric Benzobisoxazole-Vinylene-Linked Covalent Organic Frameworks with Distinct Photocatalytic Properties

Shengxu Li; Rui Ma; Shunqi Xu; Tianyue Zheng; Guangen Fu; Yanling Wu; Zhongquan Liao; Yongbo Kuang; Yang Hou; Dashuai Wang; Petko Stoev Petkov; Kristina Simeonova; Xinliang Feng; Li-Zhu Wu; Xu-Bing Li; Tao Zhang

doi:10.1021/jacs.2c06042

Direct Construction of Isomeric Benzobisoxazole-Vinylene-Linked Covalent Organic Frameworks with Distinct Photocatalytic Properties

J Am Chem Soc. 2022 Aug 3;144(30):13953-13960. doi: 10.1021/jacs.2c06042. Epub 2022 Jul 25.

Authors

Shengxu Li¹, Rui Ma², Shunqi Xu³, Tianyue Zheng¹, Guangen Fu¹, Yanling Wu⁴, Zhongquan Liao⁵, Yongbo Kuang⁴, Yang Hou⁶, Dashuai Wang⁷, Petko Stoev Petkov⁸, Kristina Simeonova⁸, Xinliang Feng³, Li-Zhu Wu², Xu-Bing Li², Tao Zhang¹

Affiliations

¹ Key Laboratory of Marine Materials and Related Technologies, Ningbo Institute of Materials Technology and Engineering, Chinese Academy of Sciences, Ningbo 315201, China.
² Key Laboratory of Photochemical Conversion and Optoelectronic Materials, Technical Institute of Physics and Chemistry, The Chinese Academy of Sciences, Beijing 100190, China.
³ Center for Advancing Electronics Dresden (CFAED) and Faculty of Chemistry and Food Chemistry, Technische Universität Dresden, 01062 Dresden, Germany.
⁴ Key Laboratory of Advanced Fuel Cells and Electrolyzers Technology of Zhejiang Province, Ningbo Institute of Materials Technology and Engineering, Chinese Academy of Sciences, 1219 Zhongguan West Road, Ningbo 315201, Zhejiang, China.
⁵ Fraunhofer Institute for Ceramic Technologies and Systems (IKTS), Maria-Reiche-Strasse 2, 01109 Dresden, Germany.
⁶ Key Laboratory of Biomass Chemical Engineering of Ministry of Education, College of Chemical and Biological Engineering, Zhejiang University, Hangzhou 310027, China.
⁷ Institute of Zhejiang University - Quzhou, Quzhou 324000, China.
⁸ Faculty of Chemistry and Pharmacy, University of Sofia, 1164 Sofia, Bulgaria.

PMID: 35877552
DOI: 10.1021/jacs.2c06042

Abstract

Vinylene/olefin-linked two-dimensional covalent organic frameworks (v-2D-COFs) have emerged as advanced semiconducting materials with excellent in-plane conjugation, high chemical stabilities, and precisely tunable electronic structures. Exploring new linkage chemistry for the reticular construction of v-2D-COFs remains in infancy and challenging. Herein, we present a solid-state benzobisoxazole-mediated aldol polycondensation reaction for the construction of two novel isomeric benzobisoxazole-bridged v-2D-COFs (v-2D-COF-NO1 and v-2D-COF-NO2) with trans and cis configurations of benzobisoxazole. Interestingly, the isomeric benzobisoxazole linkers endow the two v-2D-COFs with distinct optoelectronic and electrochemical properties, ranging from light absorption and emission to charge-transfer properties. When employed as the photocathode, v-2D-COF-NO1 exhibits a photocurrent of up to ∼18 μA/cm² under AM 1.5G irradiation at -0.3 V vs reversible hydrogen electrode (RHE), which is twice the value of v-2D-COF-NO2 (∼9.1 μA/cm²). With Pt as a cocatalyst, v-2D-COF-NO1 demonstrates a photocatalytic hydrogen evolution rate of ∼1.97 mmol h^-1 g^-1, also in clear contrast to that of v-2D-COF-NO2 (∼0.86 mmol h^-1 g^-1) under identical conditions. This work demonstrates the synthesis of v-2D-COFs via benzobisoxazole-mediated aldol polycondensation with isomeric structures and distinct photocatalytic properties.