Citation: Yongzhen Chen, Jianxin Ma, Yuyang Wang, Qianqian Liu, Yunzuo Cui, Weibo Ren, Chen Wang, Zhong-Min Su, Hong-Ying Zang. Modulator-driven structural expansion: From 2D copper coordination polymer to 3D MOF with enhanced proton conductivity[J]. Chinese Chemical Letters, ;2026, 37(8): 111266. doi: 10.1016/j.cclet.2025.111266 shu

Modulator-driven structural expansion: From 2D copper coordination polymer to 3D MOF with enhanced proton conductivity

Yongzhen Chen ^{a, 1} ,
Jianxin Ma ^{c, 1} ,
Yuyang Wang ^b ,
Qianqian Liu ^b ,
Yunzuo Cui ^b ,
Weibo Ren ^b ,
Chen Wang ^a ,
Zhong-Min Su ^{a, c, **,} ,
Hong-Ying Zang ^{b, *,}

a.
State Key Laboratory of Supramolecular Structure and Materials, Institute of Theoretical Chemistry, College of Chemistry, Jilin University, Changchun 130021, China
b.
Key Laboratory of Polyoxometalate and Reticular Material Chemistry of Ministry of Education, Faculty of Chemistry, Northeast Normal University, Changchun 130024, China
c.
School of Chemistry and Environmental Engineering, Changchun University of Science and Technology, Changchun 130022, China

^**

suzhongmin@jlu.edu.cn

zanghy100@nenu.edu.cn

Received Date: 30 March 2025
Revised Date: 22 April 2025
Accepted Date: 27 April 2025
Available Online: 27 April 2025

Figures(4)

In this study, we employed sodium hydroxide and 2,6-pyridinedimethanol as modulators to tailor the structure of metal-organic crystals via “coordination modulation strategy”. Based on this strategy, two copper-based crystalline materials were synthesized via hydrothermal synthesis and structurally characterized. Single-crystal X-ray diffraction analysis elucidates that [Cu₂(μ₂–OH)(μ₃–OH)(H₂dcppa)(H₂O)]·H₂O (dcppa = 3-(3′,5′-dicarboxyphenoxy)phthalic acid, CP-1) exist a kind of [Cu₄(μ₂–OH)₂(μ₃–OH)₂(H₂O)₂]⁴⁺ cluster. Each [Cu₄(μ₂–OH)₂(μ₃–OH)₂(H₂O)₂]⁴⁺ is interconnected in-plane with H₂dcppa ligands, forming a four-directional extended coordination network that ultimately generates a periodically arranged layered architecture. In [Cu₄(Hdcppa)₂(H₂dcppa)(H₂O)₃] (MOF-1), there are two types of binuclear copper building blocks, [Cu₂(H₂O)]⁴⁺ and [Cu₂(H₂O)₂]⁴⁺, respectively. The adjacent [Cu₂(H₂O)]⁴⁺ units are interconnected via Hdcppa ligands, forming a 1D metal-organic chain. These 1D chains are connected by [Cu₂(H₂O)₂]⁴⁺ to establish a 2D layer, which is further extended by H₂dcppa ligands to a 3D framework. The successful implementation of this synthetic route further validates the feasibility and effectiveness of combining hydrothermal methods with coordination modulation strategies for the targeted construction of functionalized metal-organic crystals. The proton conductivities (σ) of CP-1 and MOF-1 were measured under conditions of 85 ℃ and 98% relative humidity (RH), resulting in values of 2.14 × 10⁻³ and 2.55 × 10^–2 S/cm, respectively. This study presents a novel approach to fabricating MOFs as proton conductors through coordination modulation strategy.
- Modulator,
- Metal-organic framework,
- Coordination polymer,
- Coordination modulation,
- Proton conduction
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