Metal-Free Wet Chemistry for the Fast Gram-Scale Synthesis of γ-Graphyne and its Derivatives.

Autor: Song T; School of Chemistry and Chemical Engineering, Harbin Institute of Technology, 150001, Harbin, China.; Department of Chemistry, Southern University of Science and Technology, 518055, Shenzhen, China.; Center of Artificial Photosynthesis for Solar Fuels and Department of Chemistry, School of Science, Westlake University, 310030, Hangzhou, China., Liu H; Department of Chemistry, Southern University of Science and Technology, 518055, Shenzhen, China., Zou H; Department of Chemistry, Southern University of Science and Technology, 518055, Shenzhen, China., Wang C; Department of Chemistry, Southern University of Science and Technology, 518055, Shenzhen, China.; Center of Artificial Photosynthesis for Solar Fuels and Department of Chemistry, School of Science, Westlake University, 310030, Hangzhou, China., Shu S; Department of Chemistry, Southern University of Science and Technology, 518055, Shenzhen, China.; Center of Artificial Photosynthesis for Solar Fuels and Department of Chemistry, School of Science, Westlake University, 310030, Hangzhou, China., Dai H; Department of Chemistry, Southern University of Science and Technology, 518055, Shenzhen, China.; Center of Artificial Photosynthesis for Solar Fuels and Department of Chemistry, School of Science, Westlake University, 310030, Hangzhou, China., Duan L; Center of Artificial Photosynthesis for Solar Fuels and Department of Chemistry, School of Science, Westlake University, 310030, Hangzhou, China.; Division of Solar Energy Conversion and Catalysis at Westlake University, Zhejiang Baima Lake Laboratory Co., Ltd, 310000, Hangzhou, Zhejiang, China.; Institute of Natural Sciences, Westlake Institute for Advanced Study, 310024, Hangzhou, China.
Jazyk: angličtina
Zdroj: Angewandte Chemie (International ed. in English) [Angew Chem Int Ed Engl] 2024 Dec 09; Vol. 63 (50), pp. e202411228. Date of Electronic Publication: 2024 Oct 31.
DOI: 10.1002/anie.202411228
Abstrakt: γ-Graphyne (GY), an emerging carbon allotrope, is envisioned to offer various alluring properties and broad applicability. While significant progress has been made in the synthesis of GY over recent decades, its widespread application hinges on developing efficient, scalable, and accessible synthetic methods for the production of GY and its derivatives. Here we report a facile metal-free nucleophilic crosslinking method using wet chemistry for fast gram-scale production of GY and its derivatives. This synthesis method involves the aromatic nucleophilic substitution reactions between fluoro-(hetero)arenes and alkynyl silanes in the presence of a catalytic amount of tetrabutylammonium fluoride, where the fluoride plays a crucial role in removing protective groups from alkynyl silanes and generating reactive alkynylides. Our comprehensive analysis of the as-prepared GY reveals a layered structure, characterized by the presence of the C(sp)-C(sp 2 ) bond. The synthetic strategy shows remarkable tolerance to various functional groups and enables the preparation of diverse F-/N-rich GY derivatives, using electron-deficient fluoro-substituted (hetero)arenes as precursors. The feasibility of producing GY and derivatives from fluorinated (hetero)arenes through the metal-free, scalable, and cost-effective approach paves the way for broad applications of GY and may inspire the development of new carbon materials.
(© 2024 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)
Databáze: MEDLINE
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