Zhigileva Ekaterina A, Enakieva Yulia Yu, Chernyshev Vladimir V, Senchikhin Ivan N, Demina Liudmila I, Martynov Alexander G, Stenina Irina A, Yaroslavtsev Andrey B, Gorbunova Yulia G, Tsivadze Aslan Yu
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. 2024 Oct 8;53(39):16345-16354. doi: 10.1039/d4dt02143f.
Post-synthetic modification of proton-conducting metal-organic frameworks (MOFs) by loading small molecules capable of generating protons into pores is an efficient approach for developing a new type of material with improved ionic conductivity. Herein, the synthesis, characterization and proton conductivity of a novel electroneutral MOF based on palladium(II) -tetrakis(4-(phosphonatophenyl))porphyrinate, IPCE-1Pd, are reported. The exposure of the obtained framework to imidazole by the diffusion vapor method has surprisingly led to its complete crystal-to-crystal MOF-to-HOF transformation, resulting in the formation of a novel hydrogen-bonded organic framework (HOF) IPCE-1Pd_Im, which is the first example of such kind of structural change among all known MOFs. This modification has led to an almost 25-fold increase in the proton conductivity in comparison with the pristine MOF, reaching up to 6.54 × 10 S cm at 85 °C and 95% relative humidity, which is one of the highest values among all known porphyrin-based HOFs.
通过将能够产生质子的小分子负载到孔中对质子传导金属有机框架（MOF）进行合成后修饰，是开发一种具有改善离子传导性的新型材料的有效方法。在此，报道了一种基于钯（II）-四（4-（膦酰基苯基））卟啉的新型电中性MOF即IPCE-1Pd的合成、表征和质子传导率。通过扩散气相法将所得框架暴露于咪唑中，令人惊讶地导致其发生从晶体到晶体的完全MOF到HOF转变，从而形成一种新型氢键有机框架（HOF）IPCE-1Pd_Im，这是所有已知MOF中此类结构变化的首个实例。与原始MOF相比，这种修饰使质子传导率提高了近25倍，在85°C和95%相对湿度下达到6.54×10 S cm，这是所有已知卟啉基HOF中的最高值之一。
