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

Alice Burnstead, David Cordes, Daniel Dawson, Krisina Chakarova, Mihail Mihaylov, Claire Hobday, Tina Duren, Konstantin Hadjiivanov, Alexandra M.z. Slawin, Sharon E. Ashbrook, Ram Prasad, Paul A. Wright

Research output: Contribution to journalArticle

Abstract

A fully interpenetrated 8,3-connected zirconium MOF with the the-i topology type, STA-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 it possesses Im-3m symmetry compared with the Pm-3m 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 13C MAS NMR is also found to be remarkably sensitive to the structural transition. Furthermore, heating STA-26(Zr) in vacuum dehydroxylates the Zr6 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 cm3 g−1 while CO2 adsorption at 196 K reaches 300 cm3 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.
LanguageEnglish
Pages6115-6126
JournalChemistry - A European Journal
Volume24
Issue number23
Early online date31 Jan 2018
DOIs
StatusPublished - 20 Apr 2018

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Modulators
Topology
Adsorption
formic acid
Benzoic Acid
Carbon Monoxide
Infrared spectroscopy
Nitrogen
Moisture
Nuclear magnetic resonance
Vacuum
Heating
X ray diffraction
Molecules

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Modulator-Controlled Synthesis of Microporous STA-26, an Interpenetrated 8,3-Connected Zirconium MOF with the the-i Topology, and its Reversible Lattice Shift. / Burnstead, Alice; Cordes, David; Dawson, Daniel; Chakarova, Krisina; Mihaylov, Mihail; Hobday, Claire; Duren, Tina; Hadjiivanov, Konstantin; Slawin, Alexandra M.z.; Ashbrook, Sharon E.; Prasad, Ram; Wright, Paul A.

In: Chemistry - A European Journal, Vol. 24, No. 23, 20.04.2018, p. 6115-6126.

Research output: Contribution to journalArticle

Burnstead, A, Cordes, D, Dawson, D, Chakarova, K, Mihaylov, M, Hobday, C, Duren, T, Hadjiivanov, K, Slawin, AM, Ashbrook, SE, Prasad, R & Wright, PA 2018, 'Modulator-Controlled Synthesis of Microporous STA-26, an Interpenetrated 8,3-Connected Zirconium MOF with the the-i Topology, and its Reversible Lattice Shift' Chemistry - A European Journal, vol 24, no. 23, pp. 6115-6126. DOI: 10.1002/chem.201705136
Burnstead, Alice ; Cordes, David ; Dawson, Daniel ; Chakarova, Krisina ; Mihaylov, Mihail ; Hobday, Claire ; Duren, Tina ; Hadjiivanov, Konstantin ; Slawin, Alexandra M.z. ; Ashbrook, Sharon E. ; Prasad, Ram ; Wright, Paul A./ Modulator-Controlled Synthesis of Microporous STA-26, an Interpenetrated 8,3-Connected Zirconium MOF with the the-i Topology, and its Reversible Lattice Shift. In: Chemistry - A European Journal. 2018 ; Vol. 24, No. 23. pp. 6115-6126
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abstract = "A fully interpenetrated 8,3-connected zirconium MOF with the the-i topology type, STA-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 it possesses Im-3m symmetry compared with the Pm-3m 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 13C MAS NMR is also found to be remarkably sensitive to the structural transition. Furthermore, heating STA-26(Zr) in vacuum dehydroxylates the Zr6 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 cm3 g−1 while CO2 adsorption at 196 K reaches 300 cm3 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.",
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AU - Burnstead,Alice

AU - Cordes,David

AU - Dawson,Daniel

AU - Chakarova,Krisina

AU - Mihaylov,Mihail

AU - Hobday,Claire

AU - Duren,Tina

AU - Hadjiivanov,Konstantin

AU - Slawin,Alexandra M.z.

AU - Ashbrook,Sharon E.

AU - Prasad,Ram

AU - Wright,Paul A.

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N2 - A fully interpenetrated 8,3-connected zirconium MOF with the the-i topology type, STA-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 it possesses Im-3m symmetry compared with the Pm-3m 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 13C MAS NMR is also found to be remarkably sensitive to the structural transition. Furthermore, heating STA-26(Zr) in vacuum dehydroxylates the Zr6 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 cm3 g−1 while CO2 adsorption at 196 K reaches 300 cm3 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.

AB - A fully interpenetrated 8,3-connected zirconium MOF with the the-i topology type, STA-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 it possesses Im-3m symmetry compared with the Pm-3m 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 13C MAS NMR is also found to be remarkably sensitive to the structural transition. Furthermore, heating STA-26(Zr) in vacuum dehydroxylates the Zr6 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 cm3 g−1 while CO2 adsorption at 196 K reaches 300 cm3 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.

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