Coordinated water modulation for proton conductivity via post-synthetic transmetalation in yttrium-based coordination polymers

IF 2.6 3区化学 Q2 CHEMISTRY, MULTIDISCIPLINARY

CrystEngComm Pub Date : 2025-08-20 DOI:10.1039/D5CE00639B

Byoung Gwan Lee, Dongwook Kim, Jin Young Bae, Ji Woo Jeong and Dae-Woon Lim

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Abstract

Understanding the correlation between structural variations and proton transport in coordination polymers (CPs) is essential for developing efficient solid-state proton conductors (SSPCs). In this study, we demonstrate that post-synthetic transmetalation via alkali metal exchange enhances proton conductivity in a pseudo-three-dimensional yttrium-based CP, {[Y(H₂O)₄(HDSNDC)]·H₂O}_n (H₄DSNDC = 4,8-disulfonaphthalene-2,6-dicarboxylic acid). Immersion in 1 M KCl solution induces transmetalation, yielding a potassium-substituted analogue, {K₃(H₂O)₂(HDSNDC)}_n. Structural analysis reveals that transmetalation induces structural reorganization, in which terminal H₂O ligands are converted into μ-bridging ones. These bridging H₂O ligands exhibit increased acidity due to cooperative polarization by adjacent K⁺ ions, facilitating proton dissociation and significantly enhancing conductivity from 7.23 × 10⁻⁵ S cm⁻¹ for Y-DSNDC to 2.50 × 10⁻³ S cm⁻¹ for K-DSNDC at 363 K under 95% RH. This work highlights transmetalation-induced coordination tuning as an effective strategy to enhance proton transport in CPs.

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三元基配位聚合物合成后金属转化对质子电导率的配位水调制

了解配位聚合物（CPs）结构变化与质子输运之间的关系对于开发高效的固态质子导体（sspc）至关重要。在这项研究中，我们证明了通过碱金属交换的合成后金属转化提高了伪三维三元基CP {[Y(H2O)4(HDSNDC)]·H2O}n （H4DSNDC = 4,8-二磺萘-2,6-二羧酸）中质子的导电性。浸泡在1 M KCl溶液中可诱导金属转化，生成钾取代类似物{K3(H2O)2(HDSNDC)}n。结构分析表明，金属转化引起结构重组，末端H2O配体转化为μ桥接配体。由于相邻K+离子的合作极化，这些桥接H2O配体的酸性增强，促进了质子解离，并显著提高了Y-DSNDC的电导率，从7.23 × 10−5 S cm−1提高到2.50 × 10−3 S cm−1，温度为363 K，相对湿度为95%。这项工作强调了跨金属诱导的配位调谐是增强CPs中质子传输的有效策略。

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