A flexible Ni(ii)-based metal-organic framework exhibiting reversible breathing and enhanced proton conductivity.

IF 2.4 3区化学 Q2 CHEMISTRY, MULTIDISCIPLINARY

CrystEngComm Pub Date : 2026-08-21 DOI:10.1039/d6ce00589f

Nippich Kaeosamut, Dukula De Alwis Jayasinghe, Tianze Zhou, Justyna M Rogacka, Sergei A Sapchenko, George Whitehead, Martin Schröder, Sihai Yang

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Abstract

Flexible metal-organic frameworks (MOFs) exhibit stimuli-responsive phase transitions that enable diverse applications. In this article we report the synthesis and characterisation of a flexible MOF, MFM-261a, [H₂N(CH₃)₂]₂[Ni₃(sbpdc)₄(η-H₂O)₂(μ-OH₂)₂]·solv (H₂sbpdc = sulfonyl-4,4'-biphenyldicarboxylic acid), which exhibits a reversible structural phase transition. Single-crystal X-ray diffraction reveals that MFM-261a crystallises in the orthorhombic space group Pnnm. Upon activation via desolvation, MFM-261a undergoes a single-crystal-to-single-crystal (SCSC) transformation to yield MFM-261b, [H₂N(CH₃)₂]₂[Ni₃(sbpdc)₄(η-H₂O)₂(μ-OH₂)₂]. Crystallographic analysis confirms that MFM-261b retains the metal-ligand coordination as the parent framework but shows a different pore geometry. Notably, MFM-261b can be reversibly converted to MFM-261a by exposure to dimethylformamide, demonstrating structural breathing. Impedance spectroscopic measurements reveal a proton conductivity of 3.00 × 10^-5 S cm^-1 for MFM-261a at 50 °C and 3.41 × 10^-6 S cm^-1 for MFM-261b at 70 °C under 99% relative humidity. The calculated activation energies of 0.63 and 0.68 eV support a vehicular transport mechanism with water molecules facilitating proton transfer. This work demonstrates the potential of flexible MOFs for applications requiring tuneable proton conduction properties.

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一种灵活的Ni（ii）基金属有机框架，具有可逆呼吸和增强的质子导电性。

柔性金属有机框架（mof）表现出刺激响应相变，使各种应用成为可能。本文报道了柔性MOF MFM-261a， [H2N(CH3)2]2[Ni3(sbpdc)4(η-H2O)2(μ-OH2)2]·solv （H2sbpdc =磺酰基4,4′-联苯二甲酸）的合成和表征，该MOF具有可逆的结构相变。单晶x射线衍射表明，MFM-261a在正交空间群Pnnm中结晶。经脱溶活化后，MFM-261a发生单晶到单晶（SCSC）转变，生成MFM-261b， [H2N(CH3)2]2[Ni3(sbpdc)4(η-H2O)2(μ-OH2)2]。晶体学分析证实MFM-261b保留了金属配体配位作为母体骨架，但显示出不同的孔隙几何形状。值得注意的是，MFM-261b可以通过暴露于二甲基甲酰胺可逆地转化为MFM-261a，显示出结构性呼吸。阻抗谱测量显示，MFM-261a在50°C时的质子电导率为3.00 × 10-5 S cm-1， MFM-261b在70°C和99%相对湿度下的质子电导率为3.41 × 10-6 S cm-1。计算得到的活化能分别为0.63和0.68 eV，支持了水分子促进质子转移的载体传输机制。这项工作证明了柔性mof在需要可调谐质子传导特性的应用中的潜力。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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