Department of Chemistry, Lomonosov Moscow State University, Leninskie Gory, 1-3, Moscow 119991, Russian Federation.
Frumkin Institute of Physical Chemistry and Electrochemistry, Russian Academy of Sciences, Leninskiy prosp. 31, Building 4, Moscow 119071, Russian Federation.
Dalton Trans. 2023 Jun 20;52(24):8237-8246. doi: 10.1039/d3dt01118f.
Hydrogen-bonded organic frameworks (HOFs) possessing high crystallinity, simple synthetic procedure and easy regeneration provide high efficiency as multifunctional systems, including applications as proton conductors. Porphyrinylphosphonates having acidic moieties, which can form multiple hydrogen bonds, together with tunable physical-chemical properties of a macrocycle may significantly improve the proton conductivity of such materials. Herein, the synthesis, characterization and proton-conducting properties of a novel anionic HOF based on a new complex of palladium(II) with -tetrakis(4-(phosphonatophenyl))porphyrin, HOF-IPCE-1Pd, are reported. Directed structural transformation of the framework by the exchange of dimethylammonium counterions for ammonium cations along with the absorption of ammonia and water molecules led to the formation of a more hydrolytically stable structure of HOF-IPCE-1Pd-NH3, demonstrating the proton conductivity of 1.27 × 10 S cm at 85 °C and 85% RH, which is one of the highest among all known HOFs based on porphyrins. It is noteworthy that the reversible absorbance of water/ammonia molecules preserves the crystal structure of HOF-IPCE-1Pd-NH3.
具有高结晶度、简单合成步骤和易于再生的氢键有机骨架 (HOFs) 作为多功能系统提供了高效率，包括作为质子导体的应用。具有酸性部分的卟啉膦酸酯可以形成多个氢键，并且大环的物理化学性质可调，这可能会显著提高此类材料的质子电导率。本文报道了一种基于钯 (II) 与 -四（（膦酸基苯基））卟啉的新型阴离子 HOF 的合成、表征和质子传导性质，HOF-IPCE-1Pd。通过用铵阳离子交换二甲基铵抗衡离子以及吸收氨和水分子，对骨架进行定向结构转化，导致形成更水解稳定的 HOF-IPCE-1Pd-NH3 结构，在 85°C 和 85%RH 下表现出 1.27×10 S cm 的质子电导率，这是所有已知基于卟啉的 HOF 中最高的之一。值得注意的是，水/氨分子的可逆吸收保留了 HOF-IPCE-1Pd-NH3 的晶体结构。
