Synthesis approaches, characterisation and potential application of porphyrin-lanthanide based metal-organic frameworks Narhari Sapkota, Anssi Peuronen,Ari Lehtonen Intelligent Materials Chemistry research group, Department of Chemistry, University of Turku, FI-20014 Turku, Finland, Global climate change ensued by the rise in atmospheric CO 2 levels is one of the greatest challenges our planet is facing today. This worldwide distress demands technologies that can contribute to our society toward “negative carbon emissions”. 1 MOFs are polymeric structures where the metal ions or clusters (nodes) are coordinated with multitopic organic linkers to form 1D, 2D, 3D coordination networks. The key structural features and properties of MOFs are their porosity, which can be incredibly high (up to 90% in volume), high surface area (potentially as large as 1000m 2 /g). 2. Having large surface area, accessible internal volume and abundant active reaction sites, MOFs have evolved as prominent candidate materials for CO 2 capture and reduction, photosensitizer to enhance the photo-electric conversion efficiency of solar cells as well as photocatalyst for catalytic water splitting to generate molecular hydrogen. In this research, we have developed porphyrin-based MOFs using carboxylic acid functionalised iron porphyrin as the redox active linker and different lanthanide ions as nodes. Porphyrin core is coordinated with redox active metal centre, iron(III), which can act as the catalytic centre for the various reactions.
Figure 1 . Left: 5,10,15,20-Tetrakis(4-carboxyphenyl) porphyrin-FeCl. Right: Structure of Porphyrin-MOFs. Nd nodes are shown as light green and Fe ions as red polyhedra, respectively For example, MOFs with Nd nodes were synthesized by the reaction of iron porphyrin linker with Nd(NO 3 ) 3 ·8H 2 O in DMF/water mixture. The crystalline materials were obtained when some carboxylic acids, e.g. L -proline were used as modulators. Theses modulators also coordinate to the lanthanide nodes to lead MOFs with structural features. References 1. Mahajan, S.; Lahtinen, M. Journal of Environmental Chemical Engineering , 2022 ,10, 108930. 2. Reddy, N.L.; Rao, V.N.; Reddy, K.R.; Ravi, P.; Sathish, M.; Karthik, M.; Shankar, M.V. Environ Chem Lett, 2018 , 16, 765-796.
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