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0 25080293 - 25080293

DOI: https://doi.org/10.6023/A25080293

Article

Hierarchical pore engineering and single-site synergy: in situ construction of functionalized MOF for highly active C-N coupling

  • 吕灿 ,
  • 丁钰敏 ,
  • 余卓斌 ,
  • 周延涛 ,
  • 郭佳瑞 ,
  • 李杰 ,
  • 刘开建 ,
  • 欧金花 ,
  • 刘进轩
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  • a School of Materials Science and Engineering, Hunan Institute of Technology, Hengyang 421002;
    b State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian 116024
1These authors contributed equally

Received date: 2025-08-28

  Online published: 2025-10-28

Supported by

National Natural Science Foundation of China (No.22202067, No.22272018), the Hunan Provincial Natural Science Foundation of China (No. 2024JJ5121), the Research Foundation of Education Bureau of Hunan Province, China (No. 23A0631), the Characteristic Application Discipline of Material Science and Engineering in Hunan Province (No. [2022]351).

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Abstract

Nitrogen heterocycles serve as key structural components in modern pharmaceutical, materials, and agrochemical applications. Addressing the intrinsic limitations of conventional C-N coupling catalysts—particularly their poor catalytic efficiency and narrow substrate range—this investigation engineered an advanced catalytic architecture based on an Al(BPY) metal-organic framework (MOF). The synthetic route involved: (1) hydrothermal assembly of microporous Al(BPY) MOF employing 2,2'-bipyridine (BPY, rigid bidentate N-ligand) and AlCl₃, followed by (2) controlled liquid-phase loading of Cu(BF₄)₂ as a bifunctional reagent (dual etchant and metal source). This innovative approach successfully accomplished two critical objectives concurrently: (i) in situ formation of hierarchically porous networks (pore size distribution: 1-50 nm) and (ii) atomic-level precision immobilization of mono-disperse copper active centers. Structural analysis showed BF₄⁻ etches Al-O-C bonds forming mesopores, while Cu²⁺ coordinates with pyridinic N ensuring atomic dispersion. Rigorous evaluation of Al(BPY)-Cu(BF₄)₂'s catalytic behavior in Ullmann C-N coupling reactions established distinct structure-activity correlations, with the Cu(BF₄)₂-modified catalyst exhibiting substantially superior activity relative to Cu(NO₃)₂-, CuCl₂-, and Cu(acac)₂-modified analogs. The Al(BPY)-Cu(BF₄)₂-0.5 demonstrated optimal catalytic performance, achieving 93% product yield under optimized reaction parameters (Cs₂CO₃ base, DMSO solvent, 120°C, 16 h). Notably, the catalyst displayed exceptional functional group compatibility (55%-95% yields across 42 diverse substrates including fused-ring systems, non-aromatic N-heterocycles, and P-H compounds) while maintaining remarkable tolerance toward both electronic and steric perturbations. The system successfully transcended conventional catalytic constraints by accomplishing: (i) efficient coupling of sterically demanding non-aromatic amines and (ii) pioneering MOF-mediated C-P bond formation—the first documented instance of such transformation in MOF-based catalytic systems. Furthermore, the material exhibited outstanding cycling stability, retaining >94% initial activity through 8 successive reaction cycles with negligible copper leaching (<0.2 ppm). The exceptional catalytic efficiency originates from synergistic interplay between hierarchically porous channels (facilitating enhanced mass transport and active site accessibility) and atomic Cu centers (activating aryl iodides and X-H bonds).

Key words： Hierarchically porous MOF; Single-atom copper sites; Nitrogen heterocycles; C-N coupling

Cite this article

吕灿 , 丁钰敏 , 余卓斌 , 周延涛 , 郭佳瑞 , 李杰 , 刘开建 , 欧金花 , 刘进轩 . Hierarchical pore engineering and single-site synergy: in situ construction of functionalized MOF for highly active C-N coupling[J]. Acta Chimica Sinica, 0 : 25080293 -25080293 . DOI: 10.6023/A25080293

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