Templated synthesis of zirconium(IV)-based metal-organic layers (MOLs) with accessible chelating sites

First published 17 Dec 2021Metal-organic layers (MOLs) are of great interest in heterogeneous catalysis, particularly materials that can accommodate extraneous metal centres. Here, we demonstrate a two-step preorganisation/delamination synthetic strategy using CuI as a template to prepare Zr-based MOLs with accessible 'syn' bis-pyrazolyl chelating sites (named UAM-2·ns) that are poised for quantitative post-synthetic metalation with late transition metals.Pol Gimeno-Fonquernie, Weibin Liang, Jorge Albalad, Andrew Kuznicki, Jason R. Price, Eric D. Bloch, Christian J. Doonan and Christopher J. Sumb

Understanding the structural landscape of Mn-based MOFs formed with hinged pyrazole carboxylate linkers

OnlinePublMetal–organic frameworks (MOFs) capable of post-synthetic metalation (PSMet) have garnered significant interest as supports for catalytic metals. The Mn-based MOF, MnMOF-1 ([Mn3(L2Me)3] where L2Me = bis- (4-carboxyphenyl-3,5-dimethylpyrazolyl)methane), has been an exemplar for studying PSMet. Herein we investigate the synthesis of Mn-based MOFs from related flexible ditopic pyrazole carboxylate links, along with the formation of MOFs with similar tetratopic hinged linkers. We show for the first time that MnMOF-1 is likely a kinetic or metastable phase and a newly identified 2D layered material (MnMOF-2D) is the thermodynamically favoured product for this metal–linker combination. Formation of a MnMOF-1 structure with shorter linkers is thwarted by steric clashes that preclude the formation of the Mn3 cluster. This observation prompted the use of density functional theory (DFT) simulations that showed the target material to be very dense, highly strained and thereby energetically unfavourable, but potentially, a hypothetical MnMOF-1 structure with a longer phenylethynyl spacer would be energetically feasible. Finally, the predominance of 2D MOFs formed with shorter flexible links encouraged us to use tetratopic hinged linkers to form 3D frameworks, which was vindicated by the successful synthesis of two new porous 3D Mn-based MOFs, MnMOF-L4 and MnMOF-L5. These results highlight that reticular synthesis of MOFs formed with flexible, non-linear linkers is challenging.Josephine F. Smernik, Pol Gimeno-Fonquernie, Jorge Albalad, Tyla S. Jones, Rosemary J. Young, Neil R. Champness, Christian J. Doonan, Jack D. Evans and Christopher J. Sumb