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Room‐Temperature Synthesis of Covalent Organic Frameworks with a Boronic Ester Linkage at the Liquid/Solid Interface
Authors:Chunhua Liu  Yanxia Yu  Prof. Dr. Wei Zhang  Prof. Dr. Qingdao Zeng  Prof. Dr. Shengbin Lei
Affiliation:1. State Key Laboratory of Robotics and System (HIT), Harbin Institute of Technology, Harbin, P. R. China;2. College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou, P. R. China;3. CAS Key Laboratory of Standardization and Measurement for Nanotechnology, CAS Center for Excellence in Nanoscience, National Center for Nanoscience and Technology (NCNST), Beijing, P. R. China;4. Department of Chemistry, School of Science and Collaborative Innovation Center of Chemical Science and Engineering, Tianjin University, Tianjin, P. R. China
Abstract:With various prospected applications in the field of nanoelectronics and catalysis, on‐surface synthesis of single‐layer covalent organic frameworks (surface COFs) with designable structures and properties have attracted enormous interest. Herein, we report on a scanning tunneling microscopic investigation of the surface‐confined synthesis of a covalently bonded boronic ester network directly at the octanoic acid/ highly oriented pyrolytic graphite(HOPG) interface under room temperature. The dynamic reaction process was investigated in detail. STM results indicate that the surface networks undergo structural evolution from a hybrid covalent/noncovalent multiwall porous network to single‐wall hexagonal COF with the decrease of monomer concentration. Further experimental observation disclosed that the boronic ester‐linked system is sensitive to instantaneous voltage pulses and the stimulation of the STM tip. In addition, the 1H NMR spectra has further confirmed that the surface and octanoic acid may play important roles in promoting the reaction between 4,4′‐phenylazobenzoyl diboronic acid (ABBA) and 2,3,6,7,10,11‐hexahydroxytriphenylene (HHTP) building units.
Keywords:boronic acid  covalent organic frameworks  polymers  scanning tunneling microscopy  solid/liquid interface
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