Double role of metalloporphyrins in catalytic bioinspired supramolecular metal–organic frameworks (SMOFs)

IUCrJ

Gotzone Barandika¹  Marta Iglesias²  Arkaitz Fidalgo-Marijuan³  Begoña Bazán³  María Isabel Arriortua³  Miren Karmele Urtiaga³  Eder Amayuelas³  Edurne S. Larrea³ 

[1] BCMaterials, Basque Center for Materials, Applications and Nanostructures, Bld. Martina Casiano, 3rd Floor, UPV/EHU Science Park, Barrio Sarriena s/n, Leioa, Bizkaia 48940, Spain;Materials Science Factory, Instituto de Ciencia de Materiales de Madrid-CSIC, Sor Juana Inés de la Cruz 3, Cantoblanco, Madrid 28049, Spain;Mineralogía y Petrología, Universidad del País Vasco (UPV/EHU), Barrio Sarriena s/n, Leioa, Bizkaia 48940, Spain;

关键词: metalloporphyrins;    supramolecular MOFs;    heterogeneous catalysts;    Knoevenagel condensations;    aldol condensations;    one-pot cascade reactions;   

DOI  :  10.1107/S2052252518007856

来源: DOAJ

【 摘 要 】

Heterogeneous catalysts are of great interest in many industrial processes for environmental reasons and, during recent years, a great effort has been devoted to obtain metal–organic frameworks (MOFs) with improved catalytic behaviour. Few supramolecular metal–organic frameworks (SMOFs) are stable under ambient conditions and those with anchored catalysts exhibit favourable properties. However, this paper presents an innovative approach that consists of using metal nodes as both structural synthons and catalysts. Regarding the latter, metalloporphyrins are suitable candidates to play both roles simultaneously. In fact, there are a number of papers that report coordination compounds based on metalloporphyrins exhibiting these features. Thus, the aim of this bioinspired work was to obtain stable SMOFs (at room temperature) based on metalloporphyrins and explore their catalytic activity. This work reports the environmentally friendly microwave-assisted synthesis and characterization of the compound [H(bipy)]2[(MnTPPS)(H2O)2]·2bipy·14H2O (TPPS = meso-tetraphenylporphine-4,4′,4′′,4′′′-tetrasulfonic acid and bipy = 4,4′-bipyridine). This compound is the first example of an MnTPPS-based SMOF, as far as we are aware, and has been structurally and thermally characterized through single-crystal X-ray diffraction, IR spectroscopy, thermogravimetry and transmission electron microscopy. Additionally, this work explores not only the catalytic activity of this compound but also of the compounds μ-O-[FeTCPP]2·16DMF and [CoTPPS0.5(bipy)(H2O)2]·6H2O. The structural features of these supramolecular materials, with accessible networks and high thermal stability, are responsible for their excellent behaviour as heterogeneous catalysts for different oxidation, condensation (aldol and Knoevenagel) and one-pot cascade reactions.

【 授权许可】

Unknown