I19-Small Molecule Single Crystal Diffraction
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Diamond Proposal Number(s):
[36775, 26668]
Open Access
Abstract: A variable-temperature and pressure single-crystal diffraction study of hybrid improper ferroelectric Sr3Sn2O7 is reported. In combination with symmetry analysis, we reveal that the application of pressure and temperature induce distinct phase transition pathways, driven by a differing response of the octahedral rotations to these stimuli. Contrary to what has been previously predicted, we observe the ferroelectric to paraelectric phase transition between 10.17(18) and 12.13(14) GPa, meaning the hybrid improper ferroelectric phase remains stable to significantly higher pressures than expected.
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Jun 2025
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I19-Small Molecule Single Crystal Diffraction
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Diamond Proposal Number(s):
[36775]
Abstract: Polar metals are an intriguing class of materials that feature a polar crystal structure while also exhibiting metallic conductivity. The unique properties of polar metals challenge expectations, making way for the exploration of exotic phenomena such as unconventional magnetism, hyperferroelectric multiferroicity, and the development of multifunctional devices that can leverage both the material's polar structure and its asymmetry in the spin conductivity, that arises due to the Rashba effect. Here, via a high-pressure single-crystal diffraction study, we report the pressure-induced enhancement of polar distortions in such a metal, Ca3Ru2O7. Our density functional theory calculations highlight that naive assumptions about the linear dependency between polar distortion amplitudes and the magnitude of the Rashba spin splitting may not be generally valid.
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May 2025
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I19-Small Molecule Single Crystal Diffraction
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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
Diamond Proposal Number(s):
[13958, 15190, 29038]
Open Access
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 (0.15 0.9 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.
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Apr 2025
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I19-Small Molecule Single Crystal Diffraction
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Mariya
Aleksich
,
Yeongsu
Cho
,
Daniel W.
Paley
,
Maggie C.
Willson
,
Hawi N.
Nyiera
,
Patience A.
Kotei
,
Vanessa
Oklejas
,
David W.
Mittan-Moreau
,
Elyse A.
Schriber
,
Kara
Christensen
,
Ichiro
Inoue
,
Shigeki
Owada
,
Kensuke
Tono
,
Michihiro
Sugahara
,
Satomi
Inaba-Inoue
,
Mohammad
Vakili
,
Christopher J.
Milne
,
Fabio
Dallantonia
,
Dmitry
Khakhulin
,
Fernando
Ardana-Lamas
,
Frederico
Lima
,
Joana
Valerio
,
Huijong
Han
,
Tamires
Gallo
,
Hazem
Yousef
,
Oleksii
Turkot
,
Ivette J. Bermudez
Macias
,
Thomas
Kluyver
,
Philipp
Schmidt
,
Luca
Gelisio
,
Adam R.
Round
,
Yifeng
Jiang
,
Doriana
Vinci
,
Yohei
Uemura
,
Marco
Kloos
,
Adrian P.
Mancuso
,
Mark
Warren
,
Nicholas K.
Sauter
,
Jing
Zhao
,
Tess
Smidt
,
Heather J.
Kulik
,
Sahar
Sharifzadeh
,
Aaron S.
Brewster
,
J. Nathan
Hohman
Diamond Proposal Number(s):
[35300]
Abstract: X-ray free electron laser (XFEL) microcrystallography and synchrotron single-crystal crystallography are used to evaluate the role of organic substituent position on the optoelectronic properties of metal–organic chalcogenolates (MOChas). MOChas are crystalline 1D and 2D semiconducting hybrid materials that have varying optoelectronic properties depending on composition, topology, and structure. While MOChas have attracted much interest, small crystal sizes impede routine crystal structure determination. A series of constitutional isomers where the aryl thiol is functionalized by either methoxy or methyl ester are solved by small molecule serial femtosecond X-ray crystallography (smSFX) and single crystal rotational crystallography. While all the methoxy examples have a low quantum yield (0-1%), the methyl ester in the ortho position yields a high quantum yield of 22%. The proximity of the oxygen atoms to the silver inorganic core correlates to a considerable enhancement of quantum yield. Four crystal structures are solved at a resolution range of 0.8–1.0 Å revealing a collapse of the 2D topology for functional groups in the 2- and 3- positions, resulting in needle-like crystals. Further analysis using density functional theory (DFT) and many-body perturbation theory (MBPT) enables the exploration of complex excitonic phenomena within easily prepared material systems.
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Dec 2024
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I19-Small Molecule Single Crystal Diffraction
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Diamond Proposal Number(s):
[33014, 35357]
Open Access
Abstract: The increasing availability of ultrabright Light Sources is facilitating the study of smaller crystals at faster timescales but with an increased risk of severe X-ray damage, leading to developments in multi-crystal methods such as serial crystallography (SX). SX studies on crystals with small unit cells are challenging as very few reflections are recorded in a single data image, making it difficult to determine the orientation matrix for each crystal and thus preventing the combination of the data from all crystals for structure solution. We herein present a Small-Rotative Fixed-Target Serial Synchrotron Crystallography (SR-FT-SSX) methodology, in which rotation of the serial target through a small diffraction angle at each crystal delivers high-quality data, facilitating ab initio unit cell determination and atomic-scale structure solution. The method is benchmarked using microcrystals of the small-molecule photoswitch sodium nitroprusside dihydrate, obtaining complete data to dmin = 0.6 Å by combining just 66 partial datasets selected against rigorous quality criteria.
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Nov 2024
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Open Access
Abstract: Over the last three decades, the technology that makes it possible to follow chemical processes in the solid state in real time has grown enormously. These studies have important implications for the design of new functional materials for applications in optoelectronics and sensors. Light–matter interactions are of particular importance, and photocrystallography has proved to be an important tool for studying these interactions. In this technique, the three-dimensional structures of light-activated molecules, in their excited states, are determined using single-crystal X-ray crystallography. With advances in the design of high-power lasers, pulsed LEDs and time-gated X-ray detectors, the increased availability of synchrotron facilities, and most recently, the development of XFELs, it is now possible to determine the structures of molecules with lifetimes ranging from minutes down to picoseconds, within a single crystal, using the photocrystallographic technique. This review discusses the procedures for conducting successful photocrystallographic studies and outlines the different methodologies that have been developed to study structures with specific lifetime ranges. The complexity of the methods required increases considerably as the lifetime of the excited state shortens. The discussion is supported by examples of successful photocrystallographic studies across a range of timescales and emphasises the importance of the use of complementary analytical techniques in order to understand the solid-state processes fully.
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Oct 2024
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I19-Small Molecule Single Crystal Diffraction
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Zhonghang
Chen
,
Peiyu
Fang
,
Jiangnan
Li
,
Xue
Han
,
Wenhao
Huang
,
Wenyue
Cui
,
Zhiwei
Liu
,
Mark R.
Warren
,
David
Allan
,
Peng
Cheng
,
Sihai
Yang
,
Wei
Shi
Diamond Proposal Number(s):
[36394]
Open Access
Abstract: Due to almost identical boiling points of benzene and cyclohexane, the extraction of trace benzene from cyclohexane is currently performed via the energy-intensive extractive distillation method. Their adsorptive separation by porous materials is hampered by their similar dimensions. Metal-organic frameworks (MOFs) with versatile pore environments are capable of molecular discrimination, but the separation of trace substrates in liquid-phase remains extremely challenging. Herein, we report a robust MOF (NKU-300) with triangular channels decorated with crown ether that can discriminate trace benzene from cyclohexane, exhibiting an unprecedented selectivity of 8615(10) for the mixture of benzene/cyclohexane (v/v = 1/1000). Remarkably, NKU-300 demonstrates exceptional selectivities for the extraction of benzene from cyclohexane over a wide range of concentrations of 0.1%–50% with ultrafast sorption kinetics and excellent stability. Single-crystal X-ray diffraction and computational modelling reveal that multiple supramolecular interactions cooperatively immobilise benzene molecules in the triangular channel, enabling the superior separation performance. This study will promote the application of advanced sorbents with tailored binding sites for challenging industrial separations.
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Oct 2024
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I19-Small Molecule Single Crystal Diffraction
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Diamond Proposal Number(s):
[29891, 26668]
Open Access
Abstract: Titanium-oxo clusters can undergo photochemical reactions under UV light, resulting in the reduction of the titanium-oxo core and oxidation of surface ligands. This is an important step in photocatalytic processes in light-absorbing Ti/O-based clusters, metal–organic frameworks, and (nano)material surfaces; however, studying the direct outcome of this photochemical process is challenging due to the fragility of the immediate photoproducts. In this report, titanium-oxo clusters [TiO(OiPr)(L)]n (n = 4, L = O2PPh2, or n = 6, L = O2CCH2tBu) undergo a two-electron photoredox reaction in the single-crystal state via an irreversible single-crystal to single-crystal (SC-SC) transformation initiated by a UV laser. The process is monitored by single crystal X-ray diffraction revealing the photoreduction of the cluster with coproduction of an (oxidized) acetone ligand, which is retained in the structure as a ligand to Ti(3+). The results demonstrate that photochemistry of inorganic molecules can be studied in the single crystal phase, allowing characterization of photoproducts which are unstable in the solution phase.
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Jun 2024
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I11-High Resolution Powder Diffraction
I19-Small Molecule Single Crystal Diffraction
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Joshua J.
Morris
,
Chris R.
Bowen
,
Ben A.
Coulson
,
Mark
Eaton
,
Paul R.
Raithby
,
Lucy K.
Saunders
,
Jonathan M.
Skelton
,
Qingping
Wang
,
Mark R.
Warren
,
Yan
Zhang
,
Lauren
Hatcher
Diamond Proposal Number(s):
[28436, 31624]
Open Access
Abstract: The switching behavior of the novel hybrid material (FA)Na[Fe(CN)5(NO)].H2O (1) in response to temperature (T), light irradiation and electric field (E) is studied using in-situ X-ray diffraction (XRD). Crystals of 1 display piezoelectricity, pyroelectricity, second and third harmonic generation. XRD shows that the FA+ are disordered at room-temperature, but stepwise cooling from 273-100K induces gradual ordering, while cooling under an applied field (E = +40kVcm-1) induces a sudden phase change at 140K. Structural-dynamics calculations suggest the field pushes the system into a region of the structural potential-energy surface that is otherwise inaccessible, demonstrating that application of T and E offers an effective route to manipulating the crystal chemistry of these materials. Photocrystallography also reveals photoinduced linkage isomerism, which coexists with but is not correlated to other switching behaviors. These experiments highlight a new approach to in-situ studies of hybrid materials, providing insight into the structure-property relationships that underpin their functionality.
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Mar 2024
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I19-Small Molecule Single Crystal Diffraction
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Russell M.
Main
,
Simon M.
Vornholt
,
Romy
Ettlinger
,
Philip
Netzsch
,
Maximillian G.
Stanzione
,
Cameron M.
Rice
,
Caroline
Elliott
,
Samantha E.
Russell
,
Mark R.
Warren
,
Sharon E.
Ashbrook
,
Russell E.
Morris
Diamond Proposal Number(s):
[29217, 32865]
Open Access
Abstract: Living on an increasingly polluted planet, the removal of toxic pollutants such as sulfur dioxide (SO2) from the troposphere and power station flue gas is becoming more and more important. The CPO-27/MOF-74 family of metal–organic frameworks (MOFs) with their high densities of open metal sites is well suited for the selective adsorption of gases that, like SO2, bind well to metals and have been extensively researched both practically and through computer simulations. However, until now, focus has centered upon the binding of SO2 to the open metal sites in this MOF (called chemisorption, where the adsorbent–adsorbate interaction is through a chemical bond). The possibility of physisorption (where the adsorbent–adsorbate interaction is only through weak intermolecular forces) has not been identified experimentally. This work presents an in situ single-crystal X-ray diffraction (scXRD) study that identifies discrete adsorption sites within Ni-MOF-74/Ni-CPO-27, where SO2 is both chemisorbed and physisorbed while also probing competitive adsorption of SO2 of these sites when water is present. Further features of this site have been confirmed by variable SO2 pressure scXRD studies, DFT calculations, and IR studies.
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Jan 2024
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