Modulator-Controlled Synthesis of Microporous STA-26, an Interpenetrated 8,3-Connected Zirconium MOF with the the-i Topology, and its Reversible Lattice Shift

作者：Bumstead Alice M; Cordes David B; Dawson Daniel M; Chakarova Kristina K; Mihaylov Mihail Y; Hobday Claire L; Duren Tina; Hadjiivanov Konstantin I; Slawin Alexandra M Z; Ashbrook Sharon E; Prasad Ram R R; Wright Paul A

来源：Chemistry - A European Journal, 2018, 24(23): 6115-6126.

DOI：10.1002/chem.201705136

• hafnium
• metal-organic frameworks
• modulators
• reversible lattice shift
• zirconium

A fully interpenetrated 8,3-connected zirconium MOF with the the-i topology type, STA-26 (St Andrews porous material-26), has been prepared using the 4,4', 4 ''-( 2,4,6-trimethylbenzene-1,3,5-triyl) tribenzoate (TMTB) tritopic linker with formic acid as a modulating agent. In the as-prepared form STA-26 possesses Im (3) over barm symmetry compared with the Pm (3) over barm symmetry of the non-interpenetrated analogue, NU-1200, prepared using benzoic acid as a modulator. Upon removal of residual solvent there is a shift between the interpenetrating lattices and a resultant symmetry change to Cmcm which is fully reversible. This is observed by X-ray diffraction and C-13 MAS NMR is also found to be remarkably sensitive to the structural transition. Furthermore, heating STA-26(Zr) in vacuum dehydroxylates the Zr-6 nodes leaving coordinatively unsaturated Zr4+ sites, as shown by IR spectroscopy using CO and CD3CN as probe molecules. Nitrogen adsorption at 77 K together with grand canonical Monte Carlo simulations confirms a microporous, fully interpenetrated, structure with pore volume 0.53 cm(3) g(-1) while CO2 adsorption at 196 K reaches 300 cm(3) STP g(-1) at 1 bar. While the pore volume is smaller than that of its non-interpenetrated mesoporous analogue, interpenetration makes the structure more stable to moisture adsorption and introduces shape selectivity in adsorption.

• 出版日期2018-4-20