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33 items found (0 items not approved), displaying 1 to 10.[First/Prev] 1, 2, 3, 4 [Next/Last]

Instruments / Technical Area	Publication Details	Published
I19-Small Molecule Single Crystal Diffraction	Decoupled MOF breathing: pressure-induced reversal of correlation between orthogonal motions in a diamondoid framework Lee Brammer , David Ashworth , Elliot J. Carrington , Thomas M. Roseveare , Charles J. Mcmonagle , Martin R. Ward , Ashleigh J. Fletcher , Tina Düren , Mark R. Warren , Stephen A. Moggach , Iain D. H. Oswald Angewandte Chemie International Edition DOI: 10.1002/anie.202504297 Diamond Proposal Number(s): [13958, 15190, 29038] Open Access Show Abstract ▼ Abstract: Responsive porous materials can outperform more rigid analogues in applications requiring precise triggering of molecular uptake/release, switching or gradual change in properties. We have uncovered an unprecedented dynamic response in the diamondoid MOF SHF-62, (Me2NH2)[In(BDC-NHC(O)Me)2] (BDC=1,4-benzenedicarboxylate), by using pressure as a stimulus. SHF-62 exhibits two distinct framework “breathing” motions involving changes in (1) cross-section and (2) length of its 1D pores. Our study using synchrotron single-crystal X-ray diffraction in sapphire-capillary (p<0.15 GPa) and diamond-anvil (0.150.9 GPa while pore length contracts for all pressure increases, revealing decoupling of the two framework deformations. By contrast, non-penetrating medium FC-70 imposes correlated compression (p<1.4 GPa) of pore cross-section and length, resembling framework activation/desolvation motions but of greater magnitude. Similar behaviour occurs for SHF-62-CHCl3 in CHCl3 (p<0.14 GPa), suggesting minimal ingress of CHCl3. These findings change our understanding of MOF dynamic responses and provide a platform for future responsive materials development.	Apr 2025
I19-Small Molecule Single Crystal Diffraction	Pressure-induced postsynthetic cluster anion substitution in a MIL-53 topology scandium metal-organic framework Alexander J. R. Thom , Gemma F. Turner , Zachary H. Davis , Martin R. Ward , Ignas Pakamore , Claire L. Hobday , David R. Allan , Mark R. Warren , Wai L. W. Leung , Iain D. H. Oswald , Russell E. Morris , Stephen A. Moggach , Sharon E. Ashbrook , Ross S. Forgan Chemical Science DOI: 10.1039/D3SC00904A Diamond Proposal Number(s): [24020] Open Access Show Abstract ▼ Abstract: Postsynthetic modification of metal-organic frameworks (MOFs) has proven a hugely powerful tool to tune physical properties and introduce functionality, by exploiting reactive sites on both the MOF linkers and their inorganic secondary building units (SBUs), and so has facilitated a wide range of applications. Studies into the reactivity of MOF SBUs have focussed solely on removal of neutral coordinating solvents, or direct exchange of linkers such as carboxylates, despite the prevalence of ancillary charge-balancing oxide and hydroxide ligands found in many SBUs. Herein, we show that the µ2-OH ligands in the MIL-53 topology Sc MOF, GUF-1, are labile, and can be substituted for µ2-OCH3 units through reaction with pore-bound methanol molecules in a very rare example of pressure-induced postsynthetic modification. Using comprehensive solid-state NMR spectroscopic analysis, we show an order of magnitude increase in this cluster anion substitution process after exposing bulk samples suspended in methanol to a pressure of 0.8 GPa in a large volume press. Additionally, single crystals compressed in diamond anvil cells with methanol as the pressure-transmitting medium have enabled full structural characterisation of the process across a range of pressures, leading to a quantitative single-crystal to single-crystal conversion at 4.98 GPa. This unexpected SBU reactivity – in this case chemisorption of methanol – has implications across a range of MOF chemistry, from activation of small molecules for heterogeneous catalysis to chemical stability, and we expect cluster anion substitution to be developed into a highly convenient novel method for modifying the internal pore surface and chemistry of a range of porous materials.	Jun 2023
I19-Small Molecule Single Crystal Diffraction	Pressure and guest-mediated pore shape modification in a small pore MOF to 1200 bar Charles J. Mcmonagle , Gemma F. Turner , Isabelle Jones , David R. Allan , Mark R. Warren , Konstantin V. Kamenev , Simon Parsons , Paul A. Wright , Stephen A. Moggach Chemical Communications 3 DOI: 10.1039/D2CC04649K Diamond Proposal Number(s): [14164] Show Abstract ▼ Abstract: Guest-mediated pore-shape modification of the metal–organic framework, Sc2BDC3 upon adsorption of n-pentane and isopentane is examined from 50–1200 bar. Rotation of the BDC linker responsible for the change in pore shape occurs at much lower pressures than previously reported, with distinct adsorption behaviour observed between pentane isomers.	Sep 2022
I11-High Resolution Powder Diffraction	Modulated self-assembly of an interpenetrated MIL-53 Sc metal–organic framework with excellent volumetric H2 storage and working capacity A. J. R. Thom , D. G. Madden , R. Bueno-Perez , A.n. Al Shakhs , C. T. Lennon , R. J. Marshall , C. A. Walshe , C. Wilson , C. A. Murray , S. P. Thompson , G. F. Turner , D. Bara , S. A. Moggach , D. Fairen-Jimenez , R. S. Forgan Materials Today Chemistry 24 DOI: 10.1016/j.mtchem.2022.100887 Diamond Proposal Number(s): [22028] Open Access Show Abstract ▼ Abstract: To achieve optimal performance in gas storage and delivery applications, metal–organic frameworks (MOFs) must combine high gravimetric and volumetric capacities. One potential route to balancing high pore volume with suitable crystal density is interpenetration, where identical nets sit within the void space of one another. Herein, we report an interpenetrated MIL-53 topology MOF, named GUF-1, where one-dimensional Sc(μ2-OH) chains are connected by 4,4′-(ethyne-1,2-diyl)dibenzoate linkers into a material that is an unusual example of an interpenetrated MOF with a rod-like secondary building unit. A combination of modulated self-assembly and grand canonical Monte Carlo simulations are used to optimise the porosity of GUF-1; H2 adsorption isotherms reveal a moderately high Qst for H2 of 7.6 kJ/mol and a working capacity of 41 g/L in a temperature–pressure swing system, which is comparable to benchmark MOFs. These results show that interpenetration is a potentially viable route to high-performance gas storage materials comprised of relatively simple building blocks.	Jun 2022
I19-Small Molecule Single Crystal Diffraction	Guest-mediated phase transitions in a flexible pillared-layered metal-organic framework under high-pressure Gemma F. Turner , Scott C. Mckellar , David Robert Allan , Anthony K. Cheetham , Sebastian Henke , Stephen A. Moggach Chemical Science DOI: 10.1039/D1SC03108B Open Access Show Abstract ▼ Abstract: The guest-dependent flexibility of the pillared-layered metal-organic framework (MOF), Zn2bdc2dabco·X(guest), where guest = EtOH, DMF or benzene, has been examined by high-pressure single crystal X-ray diffraction. A pressure-induced structural phase transition is found for the EtOH- and DMF-included frameworks during compression in a hydrostatic medium of the guest species, which is dependent upon the nature and quantity of the guest in the channels. The EtOH-included material undergoes a phase transition from P4/mmm to C2/m at 0.69 GPa, which is accompanied by a change in the pore shape from square to rhombus via super-filling of the pores. The DMF-included material undergoes a guest-medaited phase transition from I4/mcm to P4/mmm at 0.32 GPa via disordering of the DMF guest. In contrast, the benzene-included framework features a structure with rhombus-shaped channels at ambient pressure and shows direct compression as well as negative linear compressibility parallel to the long diagonal of the channels under hydrostatic pressure. These results demonstrate the large influence of guest molecules on the phase behavior of flexible MOFs. Thus, guest-mediated framework flexibility is useful to engineering MOFs with bespoke pore shapes and compressibility.	Sep 2021
I19-Small Molecule Single Crystal Diffraction	Evaluating the high-pressure structural response and crystal lattice interactions of the magnetically-bistable organic radical TTTA Jonathan G. Richardson , Asato Mizuno , Yoshiaki Shuku , Kunio Awaga , Neil Robertson , Carole A. Morrison , Mark R. Warren , David R. Allan , Stephen A. Moggach Crystengcomm 2 DOI: 10.1039/D1CE00577D Diamond Proposal Number(s): [19178] Show Abstract ▼ Abstract: Magnetic bistability has previously been observed and evaluated in an organic thiazyl radical 1,3,5-triathia-2,4,6-triazapentalenyl (TTTA). Herein, the structure-pressure response of TTTA has been evaluated by X-ray diffraction, where a lack of a structural phase transition up to 4.6 GPa certifies that the paramagnetic suppression is caused by a steady decrease in the separation between the moieties containing the radical electron along the π-stacking chains. The intermolecular interactions throughout the crystal lattice have also been calculated using the PIXEL method, and highlight the relative strength of the inter-column interactions in the two known polymorphs of TTTA, which provides extra justification for the cause of the wide magnetic hysteresis and its response to pressure.	May 2021
I19-Small Molecule Single Crystal Diffraction	High-pressure sapphire capillary cell for synchrotron single-crystal X-ray diffraction measurements to 1500 bar Charles J. Mcmonagle , David R. Allan , Mark R. Warren , Konstantin V. Kamenev , Gemma F. Turner , Stephen A. Moggach Journal Of Applied Crystallography 53 DOI: 10.1107/S1600576720013710 Diamond Proposal Number(s): [15190, 14164] Show Abstract ▼ Abstract: A new sapphire capillary pressure cell for single-crystal X-ray diffraction measurements at moderate pressures (200−1500 bar; 1 bar = 100 kPa) has been developed and optimized for use on beamline I19 at Diamond Light Source. The three-component cell permits optical centring of the crystal and in situ pressure modification to a precision of 1 bar. Compression of hexamethylenetetramine and its deuterated analogue to 1000 bar was performed, showcasing the accuracy and precision of the measurements, and highlighting evidence of a geometric isotope effect.	Dec 2020
	Pressure-and temperature induced phase transitions, piezochromism, NLC behaviour and pressure controlled Jahn–Teller switching in a Cu-based framework Charles J. Mcmonagle , Priyanka Comar , Gary S. Nichol , David R. Allan , Jesús González , José A. Barreda-Argüeso , Fernando Rodríguez , Rafael Valiente , Gemma F. Turner , Euan K. Brechin , Stephen A. Moggach Chemical Science 11, 8793 - 8799 DOI: 10.1039/D0SC03229H Open Access Show Abstract ▼ Abstract: In situ single-crystal diffraction and spectroscopic techniques have been used to study a previously unreported Cu-framework bis[1-(4-pyridyl)butane-1,3-dione]copper(II) (CuPyr-I). CuPyr-I was found to exhibit high-pressure and low-temperature phase transitions, piezochromism, negative linear compressibility, and a pressure induced Jahn–Teller switch, where the switching pressure was hydrostatic media dependent.	Aug 2020
I19-Small Molecule Single Crystal Diffraction	Probing the structural and electronic response of Magnus green salt compounds [Pt(NH2R)4][PtCl4] (R=H, CH3) to pressure Jonathan G. Richardson , Helen Benjamin , Stephen A. Moggach , Lisette R Warren , Mark R. Warren , David R. Allan , Lucy K. Saunders , Carole A. Morrison , Neil Robertson Physical Chemistry Chemical Physics DOI: 10.1039/D0CP03280H Diamond Proposal Number(s): [19178] Open Access Show Abstract ▼ Abstract: Despite possessing the desirable crystal packing and short Pt···Pt stacking distances required for a large piezoresistive response, the conductivity-pressure response of the Magnus green salt [Pt(NH3)4][PtCl4] is extremely sluggish. Through a combination of high-pressure X-ray diffraction and hybrid-DFT solid state calculations this study demonstrates that the poor conductivity-pressure response is due to a low volumetric compression anisotropy, a relatively large ambient pressure band gap and a lack of dispersion in the conduction band. Ligand modification (from NH3 to NH2CH3) does not enhance the piezoresistive response, causing even lower anisotropy of the volumetric compression and an unexpected phase transition at above 2 GPa. This study demonstrates that consideration of frontier band dispersion is a key design criterion, alongside crystal packing and Pt···Pt stacking distances for piezoresistive materials.	Jul 2020
I19-Small Molecule Single Crystal Diffraction	Pressure-induced non-innocence in bis(1,2-dionedioximato)Pt( ii ) complexes: an experimental and theoretical study of their insulator–metal transitions Helen Benjamin , Jonathan G. Richardson , Stephen A. Moggach , Sergejs Afanasjevs , Lisette Warren , Mark Warren , David R. Allan , Carole A. Morrison , Konstantin V. Kamenev , Neil Robertson Physical Chemistry Chemical Physics 134 DOI: 10.1039/C9CP06749C Diamond Proposal Number(s): [19178] Open Access Show Abstract ▼ Abstract: Bis(1,2-dionedioximato) complexes of Pt(II) are known for their propensity to form linear chains of metal complexes in the solid state, and under the application of pressure members of the family display interesting optical and conductive properties. Two examples, Pt(bqd)2 and Pt(dmg)2, are known to undergo insulator-to-metal-to-insulator transitions, with the metallic state reached at 0.8–1.4 GPa and 5 GPa, respectively. Previous interpretations of these materials’ behaviour focused on the role of the filled dz2 and vacant p orbitals on platinum, with little consideration to the role of the ligand. Here, the pressure-structural behaviour of Pt(bqd)2 is investigated through single crystal X-ray diffraction, the first such study on this material. The difference in conductive behaviour under pressure between Pt(bqd)2 and Pt(dmg)2 is then interpreted through a combination of experimental and computational methods, including conductivity measurements under high pressure and electronic structure calculations. Our computational work reveals the significant contribution from ligand low-lying vacant π-orbitals to the frontier orbitals and bands in these complexes, and provides an explanation for the experimentally observed re-entrant insulator-to-metal-to-insulator transitions, and the differences in behaviour between the two compounds.	Mar 2020

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