Water-stable PCPs/MOFs based on the synergism of pyrazolate, carboxylate and phosphonate
Final Report Abstract
Examples of the suggested pyrazolylbenzoic acids and pyrazolylphosphonic acids as ligands for coodinatinon networks were synthesized. Because of low-yield pyrazolylphosphonic acid had to be substituted by mixedfunctional phosphonocarboxylic acid ligands. Both, pyrazolylbenzoic acids and the phosphonocarboxylic acid ligand lead to a series of water-stable coordination networks. A pleasant surprise were the solvent-dependent single-crystal transformations of the Cu-network with the mixed-functional linker HMe2pzC6H4CO2–. We have to admit that while networks from pyrazolylbenzoic acid or phosphonocarboxylic acid ligands are more water stable than common prototypical Zn-MOFs (e.g. MOF-5) or the Cu-MOF HKUST-1 they probably still do not reach the now manifested water-stability of MIL-101Cr or aluminum fumarate. Also, for envisioned large-scale MOF applications, e.g., in gas storage (CH4 in fuel tanks) or reversible water sorption for heat transformations, the ligands are probably "too expensive" to synthesize. Moreover, the charge-density analysis of ZIF-8 was the first one for a truly porous MOF (and not just a coordination network). ZIF-8 had been activated prior to the data set collections.
Publications
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A rare alb-4,8-Cmce metal-coordination network based on tetrazolate and phosphonate functionalized 1,3,5,7-tetraphenyladamantane; CrystEngComm 2013, 15, 1235-1243
I. Boldog, K.V. Domasevitch, I. A. Baburin, H. Ott, B. Gil-Hernández, J. Sanchiz, C. Janiak
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Bifunctional pyrazolate-carboxylate ligands for isoreticular cobalt and zinc MOF-5 analogs with magnetic analysis of the {Co4(µ4-O)} node; CrystEngComm 2013, 15, 9757-9768
C. Heering, I. Boldog, V. Vasylyeva, J. Sanchiz, C. Janiak
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A fluorite isoreticular series of porous framework complexes with tetrahedral ligands: new opportunities for azolate PCPs; CrystEngComm 2014, 16, 148-151
I. Boldog, K. Domasevitch, J. K. Maclaren, C. Heering, G. Makhloufi, C. Janiak
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Brønsted Instead of Lewis Acidity in Functionalized MIL-101Cr MOFs for Efficient Heterogeneous (nano-MOF) Catalysis in the Condensation Reaction of Aldehydes with Alcohols; Inorg. Chem. 2014, 53, 7319–7333
A. Herbst, A. Khutia, C. Janiak
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Programming MIL-101Cr for selective and enhanced CO2 adsorption at low pressure by postsynthetic amine functionalization; Dalton Trans. 2014, 43, 1338-1347
A. Khutia, C. Janiak
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Charge density distribution and electrostatic flexibility of ZIF-8 based on high resolution X-ray diffraction data and periodic calculations; Inorg. Chem. 2015, 54 (6), 2660-2670
S. B. Novaković, G. A. Bogdanović, C. Heering, G. Makhloufi, D. Francuski, C. Janiak
