[N…X…N]<sup>+</sup> Halogen-bonded Organic Frameworks Stabilizing Pd(0) Active Centers and Their Catalytic Coupling Performance

Xiang-yi Ding; Yong-liang Chen; Xu-guan Bai; Lu Wang; Mei-mei Zhang; Hui Liu; Shi-gui Chen

doi:10.11777/j.issn1000-3304.2026.26212

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[N…X…N]⁺ Halogen-bonded Organic Frameworks Stabilizing Pd(0) Active Centers and Their Catalytic Coupling Performance

更新时间：2026-10-15

- [N…X…N]⁺ Halogen-bonded Organic Frameworks Stabilizing Pd(0) Active Centers and Their Catalytic Coupling Performance
- Acta Polymerica Sinica Pages: 1-10(2026)
- 作者机构：
  
  1.武汉工程大学化工与制药学院绿色化工过程教育部重点实验室武汉 430073
  2.武汉大学高等研究院武汉 430072
- 作者简介：
  
  Xu-guan Bai, E-mail: xuguanbai@whu.edu.cn
  Mei-mei Zhang, E-mail: zhangmeimei@whu.edu.cn
  Hui Liu, E-mail: huiliu@wit.edu.cn
  Shi-gui Chen, E-mail: sgchen@whu.edu.cn
- 基金信息：
- DOI：10.11777/j.issn1000-3304.2026.26212
  CLC：
- CSTR：32057.14.GFZXB.2026.7696
- Received：12 June 2026，
  
  Accepted：17 July 2026，
  
  Online First：15 October 2026，
- 稿件说明：
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丁香怡, 陈永亮, 白旭冠, 王璐, 张鹛媚, 刘慧, 陈世贵. [N···X···N]⁺型卤键有机框架稳定Pd(0)活性中心及其催化偶联性能的研究. 高分子学报, doi: 10.11777/j.issn1000-3304.2026.26212. CSTR: 32057.14.GFZXB.2026.7696.

Ding, X. Y.; Chen, Y. L.; Bai, X. G.; Wang, L.; Zhang, M. M.; Liu, H.; Chen, S. G. [N…X…N]⁺ Halogen-bonded organic frameworks stabilizing Pd(0) active centers and their catalytic coupling performance. Acta Polymerica Sinica (in Chinese), doi: 10.11777/j.issn1000-3304.2026.26212. CSTR: 32057.14.GFZXB.2026.7696.
丁香怡, 陈永亮, 白旭冠, 王璐, 张鹛媚, 刘慧, 陈世贵. [N···X···N]⁺型卤键有机框架稳定Pd(0)活性中心及其催化偶联性能的研究. 高分子学报, doi: 10.11777/j.issn1000-3304.2026.26212. CSTR: 32057.14.GFZXB.2026.7696. DOI：

Ding, X. Y.; Chen, Y. L.; Bai, X. G.; Wang, L.; Zhang, M. M.; Liu, H.; Chen, S. G. [N…X…N]⁺ Halogen-bonded organic frameworks stabilizing Pd(0) active centers and their catalytic coupling performance. Acta Polymerica Sinica (in Chinese), doi: 10.11777/j.issn1000-3304.2026.26212. CSTR: 32057.14.GFZXB.2026.7696. DOI：

摘要

卤键有机框架(XOFs)是一类新兴的有机框架材料，其骨架中带正电的卤键单元与抗衡阴离子之间的弱静电相互作用为功能化修饰提供了平台. 然而，利用这一特性实现金属活性中心的稳定负载并揭示卤键类型对催化性能的调控规律仍面临挑战. 本研究以1

5-三(吡啶-4-基)苯(TPy)为有机配体，通过阳离子置换策略成功构筑了基于[N…Br…N

]

和[N…I…N

]

相互作用的二维卤键有机框架XOF(Br)-TPy-BF

和XOF(I)-TPy-BF

. 在此基础上，采用阴离子交换和原位还原策略成功制备了Pd(0)稳定负载的非均相催化剂XOF(Br/I)-TPy-Pd

. 该催化剂在空气条件下典型C―C交叉偶联反应中表现出良好的催化活性和底物兼容性. 对比研究表明，卤键中心类型因键长、极化性及局域微环境上的差异，对催化性能具有显著影响，其中XOF(Br)-TPy-Pd

的产物收率普遍高于XOF(I)-TPy-Pd

. 本研究不仅展示了卤键有机框架作为可设计载体在非均相催化中的应用潜力，也为通过调控卤键中心优化金属负载催化剂性能提供了新思路.

Abstract

Halogen-bonded organic frameworks (XOFs) are an emerging class of organic framework materials

in which the weak electrostatic interactions between the positively charged halogen-bonding units and the counteranions provide a versatile platform for functionalization. However

achieving stable loading of metal active centers and elucidating the influence of the halogen-bond type on catalytic performance remain challenging. In this study

using TPy as the organic ligand

two-dimensional halogen-bonded organic frameworks

namely XOF(Br)-TPy-BF

and XOF(I)-TPy-BF

were successfully constructed

via

a cation exchange strategy

based on [N…Br…N

]

and [N…I…N

]

interactions. On this basis

stable Pd(0)-loaded heterogeneous catalysts

denoted as XOF(Br/I)-TPy-Pd

were successfully prepared through anion exchange and

in situ

reduction. These catalysts exhibited good catalytic activity and substrate compatibility in typical C―C cross-coupling reactions under ambient air. Comparative studies revealed that the type of halogen-bonding center significantly influencd the catalytic performance due to differences in bond length

polarizability

and local microenvironment; the product yields obtained with XOF(Br)-TPy-Pd

were generally higher than those with XOF(I)-TPy-Pd

. This work not only demonstrates the potential of halogen-bonded organic frameworks as designer supports for heterogeneous catalysis

but also provides a new strategy for optimizing metal-loaded catalysts by tuning the halogen-bonding center.

关键词

Keywords

references

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[N…X…N]+ Halogen-bonded Organic Frameworks Stabilizing Pd(0) Active Centers and Their Catalytic Coupling Performance

DOI：10.11777/j.issn1000-3304.2026.26212

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[N…X…N]⁺ Halogen-bonded Organic Frameworks Stabilizing Pd(0) Active Centers and Their Catalytic Coupling Performance