Metal-organic frameworks (MOFs) are a promising class of functional solid-state materials due to their structural modularity (e.g. use of different metals and various organic building blocks, post-synthetic modifications, etc.) and incomparable controlled porosity. These unique attributes make MOFs promising candidate materials for various key applications such as gas storage/separation, catalysis and selective sensing.1 The development of new MOF platforms necessitates: i) the isolation of reaction conditions that permit the in-situ synthesis of a given inorganic molecular building block (MBB) and ii) subsequently its reticulation into a target net topology by the judicious selection of the connecting polytopic organic ligand.2,3 Herein, we present a series of highly stable and porous rare earth (RE) porphyrinic MOFs (free and metalated (Mn3+, Fe3+ and Zn2+)) assembled by adopting the molecular building block (MBB) approach. The use of highly compatible 4-connected square porphyrinic ligand led to the formation of MOFs containing 12-connected RE nonanuclear clusters and exhibiting a novel (4, 12)-connected net with shp underlying topology. This fascinating net is assembled from square and hardly reported RE hexagonal prism/double six-membered ring (d6R) building units. The multi-functional properties of this unique RE shp platform has been demonstrated in the case of shp-MOF-1-Zn which exhibits one of the highest volumetric working capacities for methane storage. shp-MOF-1-Mn and shp-MOF-1-Fe can be used as excellent recoverable heterogeneous catalysts for the epoxidation of styrene, while the parent non-metalated compound shp-MOF-1 shows potential application as an electron donor in photovoltaics. References (1) Furukawa, H.; Cordova, K. E.; O’Keeffe, M.; Yaghi, O. M., Science 2013, 341. (2) (a) Xue, D.-X.; Cairns, A. J.; Belmabkhout, Y.; Wojtas, L.; Liu, Y.; Alkordi, M. H.; Eddaoudi, M., J. Am. Chem. Soc. 2013, 135, 7660-7667; (b) Alezi, D.; Belmabkhout, Y.; Suyetin, M.; Bhatt, P. M.; Weselinski, L. J.; Solovyeva, V.; Adil, K.; Spanopoulos, I.; Trikalitis, P. N.; Emwas, A.-H.; Eddaoudi, M., J. Am. Chem. Soc. 2015. DOI:10.1021/jacs.5b07053 (3) (a) Guillerm, V.; Kim, D.; Eubank, J. F.; Luebke, R.; Liu, X.; Adil, K.; Lah, M. S.; Eddaoudi, M., Chem. Soc. Rev. 2014, 43, 6141-6172; (b) Chen, Z.; Adil, K.; Weselinski, L. J.; Belmabkhout, Y.; Eddaoudi, M., J. Mater. Chem. A 2015, 3, 6276-6281.

Multi-functional rare-earth porphyrinic shp-MOF platform meets the needs for gas storage, catalysis, and electron sensitizer

251st National Meeting (2016)

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