Search Results

You searched for all publications:

with publication states 'Published (Approved)'
published in journal 'Inorganic Chemistry'

Search Again...

These results only include publications that have been reviewed and processed by Diamond Light Source. To also view papers that have not yet been processed click here.

You can use the folder icon under Actions to collate papers as required. You can then click on View Folder in the left-hand navigation to review and/or download your folder.

Exact matches
Related results

210 items found (0 items not approved), displaying 1 to 10.[First/Prev] 1, 2, 3, 4, 5, 6, 7, 8 [Next/Last]

Instruments / Technical Area	Publication Details	Published
I09-Surface and Interface Structural Analysis	High-yield delamination of hydrothermally-etched V2CTx Rose M. Snyder , Sriram Sankar , Prajna Bhatt , Aysha A. Riaz , Pardeep K. Thakur , Tien-Lin Lee , Anna Regoutz , Sandhya Susarla , Christina S. Birkel Inorganic Chemistry DOI: 10.1021/acs.inorgchem.4c04546 Diamond Proposal Number(s): [36180] Show Abstract ▼ Abstract: The delamination of hydrothermally etched V2CTx has presented challenges, with limited reports of an effective delamination process. X-ray diffraction data indicate that excess lithium and lithium salts in the reaction mixture interact with the multilayered MXene surfaces in the interlayer space, impeding intercalants that would separate the nanosheets. The removal of this salt with a dilute acid solution is the key step to enable the synthesis of a delaminated MXene with a markedly higher yield in comparison to that of traditional HF-etched (and delaminated) V2CTx. Because this yield is substantial, the sample can be centrifuged to produce 20 mL of a concentrated (25 mg mL–1) sample. Due to the removal of excess water and dissolved O2, this concentrated sample shows improved stability toward oxidation and can withstand ambient conditions over the course of a year.	Mar 2025
I03-Macromolecular Crystallography I24-Microfocus Macromolecular Crystallography	Crystal structure of ferric recombinant horseradish peroxidase Mst Luthfun Nesa , Suman K. Mandal , Christine Toelzer , Diana Humer , Peter C. E. Moody , Imre Berger , Oliver Spadiut , Emma L. Raven Jbic Journal Of Biological Inorganic Chemistry 2 DOI: 10.1007/s00775-025-02103-2 Diamond Proposal Number(s): [31440] Open Access Show Abstract ▼ Abstract: Horseradish peroxidase (HRP), isolated from horseradish roots, is heavily glycosylated, making it difficult to crystallize. In this work, we produced recombinant HRP in E. coli and obtained an X-ray structure of the ferric enzyme at 1.63 Å resolution. The structure shows that the recombinant HRP contains four disulphide bonds and two calcium ions, which are highly conserved in class III peroxidase enzymes. The heme active site contains histidine residues at the proximal (His 170) and distal (His 42) positions, and an active site arginine (Arg 38). Surprisingly, an ethylene glycol molecule was identified in the active site, forming hydrogen bonds with His 42 and Arg 38 at the δ-heme edge. The high yields obtained from the recombinant expression system, and the successful crystallization of the enzyme pave the way for new structural studies in the future.	Mar 2025
B18-Core EXAFS I10-Beamline for Advanced Dichroism - scattering	Tuning the electronic properties of tetravalent cerium complexes via ligand derivatization Georgilett Pérez Bedwell , Nithin Suryadevara , Zhibo Qi , Robert W. Gable , Peter Bencok , Michael L. Baker , Colette Boskovic Inorganic Chemistry DOI: 10.1021/acs.inorgchem.4c05371 Diamond Proposal Number(s): [34857, 35250] Open Access Show Abstract ▼ Abstract: Molecular cerium complexes are of interest due to their remarkable redox and photophysical properties. We have investigated the ligand tunability of the electronic structure and properties of cerium(IV) complexes with functionalized tetradentate N2O2-donor ligands: [CeIV(LtBu)2] (1), [CeIV(LH)2] (2) and [CeIV(LNO2)2] (3), where H2LtBu = bis(2-hydroxy-3,5-di-tert-butylbenzyl)(2-pyridylmethyl)amine, H2LH = bis(2-hydroxybenzyl)(2-pyridylmethyl)amine and H2LNO2 = bis(2-hydroxy-5-nitrobenzyl)(2-pyridylmethyl)amine. These compounds all exhibit a quasi-reversible one-electron reduction to cerium(III), with the redox potential correlating with the electron donor–acceptor characteristics of the ligand substituents. This correlation is rationalized by energy stabilization of the HOMO, as determined by density functional theory calculations, and is consistent with arene π → Ce 4f* ligand-to-metal charge transfer bands. The L3-edge XANES exhibits minimal variation in Ce 4f occupation for the three compounds, which suggests that the 4f covalent character and composition of the ground-state character do not vary significantly across the series. However, M4,5-edge XAS shows charge transfer satellites that subtly differ in shape and energy, indicating small distinctions in ligand-to-metal charge transfer for the compounds, consistent with small differences in temperature-independent magnetism. The ability to modulate the redox and optical properties of cerium complexes through ligand derivatization highlights the potential for customizable molecular cerium catalysts and photocatalysts.	Mar 2025
E02-JEM ARM 300CF	Design of core@shell nanoparticles based on gold and magnetic NiFe Prussian-blue analogues featuring shape-dependent magnetic and electrochemical activity Shoaib Azeem , Joaquín Soriano-López , Isaac Brotons-Alcázar , Christopher Allen , Ramón Torres-Cavanillas , Roger Sanchis-Gual , Eugenio Coronado Inorganic Chemistry DOI: 10.1021/acs.inorgchem.4c05320 Diamond Proposal Number(s): [35687] Open Access Show Abstract ▼ Abstract: Au@Prussian-Blue analogue (PBA) core@shell nanoparticles (NPs) are highly versatile nanostructures with complementary and shape-dependent properties of interest in the current technologies. However, due to the high reactivity of cyanides toward Au, scarce PBAs have been successfully synthesized in direct contact with Au NPs, leaving the formation of anisotropic Au@PBA NPs as a significant synthetic challenge. Here, we have developed a robust protocol for synthesizing core@shell NPs, composed of a magnetic CsNi[Fe(CN)6] PBA shell grown on individual Au NPs, regardless of the core morphology (spheres, rods, or stars). Specifically, the uniqueness of our protocol lies in the prior Au core functionalization with anchoring molecules that facilitate PBA growth while preventing Au etching and preserving the initial oxidation states of the metals. This has afforded direct growth of ferromagnetic NiIIFeIII PBAs on Au NPs. Moreover, by exploiting the structural mismatch at the Au/PBA interface and the curvature of anisotropic Au templates, we manage to induce a substantial structural strain within the PBA shell. When star-shaped Au nanoparticles are used, a maximum strain of 2.0% is reached. This strain combined with an increased polycrystallinity lead to modifications in the PBA catalytic properties, resulting in a 10-fold improvement in the intrinsic electrocatalytic activity.	Mar 2025
	Cytochromes P460 and c'-β: exploiting a novel fold for multiple functions Hannah R. Adams , Sotaro Fujii , Hans E. Pfalzgraf , Peter Smyth , Colin R. Andrew , Michael A. Hough Jbic Journal Of Biological Inorganic Chemistry 21 DOI: 10.1007/s00775-025-02102-3 Open Access Show Abstract ▼ Abstract: Two related classes of ligand-binding heme c-containing proteins with a high degree of structural homology have been identified and characterized over recent decades: cytochromes P460 (cyts P460), defined by an unusual heme-lysine cross-link, and cytochromes c′-β (cyts c′-β), containing a canonical c-heme without the lysine cross-link. The shared protein fold of the cyt P460-cyt c′-β superfamily can accommodate a variety of heme environments with entirely different reactivities. On the one hand, cyts P460 with polar distal pockets have been shown to oxidize NH2OH to NO and/or N2O via proton-coupled electron transfer. On the other hand, cyts c′-β with hydrophobic distal pockets have a proposed gas binding function similar to the unrelated, but more extensively characterized, alpha helical cytochromes c′. Recent studies have also identified ‘halfway house’ proteins (cyts P460 with non-polar heme pockets and cyts c′-β with polar distal heme pockets) with functions yet to be resolved. Here, we review the structural, spectroscopic and enzymatic properties of the cyt P460-cyt c′-β superfamily with a view to understanding the structural determinants of their different functional properties.	Feb 2025
I11-High Resolution Powder Diffraction	Cyclopropylamine magnesium borohydrides as solid-state electrolytes Mads B. Amdisen , Young-Su Lee , Torben R. Jensen Inorganic Chemistry DOI: 10.1021/acs.inorgchem.4c04287 Show Abstract ▼ Abstract: Solid-state batteries can potentially provide higher energy and power densities than conventional lithium-ion batteries through the utilization of a solid electrolyte instead of a liquid electrolyte. Here we present three cyclopropylamine magnesium borohydride compounds as potential solid-state electrolytes: tricyclopropylamine magnesium borohydride, Mg(BH4)2·3(CH2)2CHNH2, dicyclopropylamine magnesium borohydride, Mg(BH4)2·2(CH2)2CHNH2, and monocyclopropylamine magnesium borohydride, Mg(BH4)2·(CH2)2CHNH2. Additionally, two nanocomposites, Mg(BH4)2·x(CH2)2CHNH2–Al2O3(50 wt %/18 vol %) (x = 1, 2), were investigated. Four crystal structures were determined, Mg(BH4)2·3(CH2)2CHNH2, α-Mg(BH4)2·2(CH2)2CHNH2, α′-Mg(BH4)2·2(CH2)2CHNH2, β-Mg(BH4)2·2(CH2)2CHNH2, and an average effective volume of cyclopropylamine in the crystal structures was determined to be ∼96 Å3. The ionic conductivities of the compounds were determined, and the composite Mg(BH4)2·(CH2)2CHNH2–Al2O3(50 wt %/18 vol %) has the highest value, σ = 1.8 × 10–5 S cm–1, at room temperature and an activation energy of 1.18 eV (114 kJ mol–1). The ionic transference number was determined to Tion = 0.99999. Additionally, the effects on the ionic conductivity associated with the addition of neutral ligands to metal borohydrides are discussed.	Feb 2025
I11-High Resolution Powder Diffraction	Formation of 1D "perovskitoid" (API)2Pb3Br10 instead of layered <110> oriented 2D-perovskite (API)PbBr4 under different dissolution temperatures Walter P. D. Wong , Fangzheng Chen , Xinyun Wang , Xinwei Li , Xiaodong Zou , John V. Hanna , Andrew C. Grimsdale Inorganic Chemistry DOI: 10.1021/acs.inorgchem.4c05327 Diamond Proposal Number(s): [32893] Show Abstract ▼ Abstract: The corrugated <110> oriented layered metal halide perovskites (MHP) are gaining increased attention for a variety of properties including intrinsic white light emission. One prototypical candidate is 1-(3-aminopropyl)imidazole lead bromide, which was reported to crystallize as the <110> oriented perovskite (API)PbBr4 [API = 1-(3-aminopropyl)imidazole]. This work shows that under similar reaction conditions, the same components can instead form (API)2Pb3Br10, which has a “perovskitoid” structure. (API)2Pb3Br10 exhibits a reversible phase transition between 60 and −20 °C from a polar space group I2 to a centrosymmetric space group 𝑃1¯ . The structures and properties of both phases have been characterized by single-crystal and powder X-ray diffraction (XRD) and solid-state nuclear magnetic resonance (ssNMR) accompanied by variable-temperature optical absorption and photoluminescence. In addition, a thermal decomposition of (API)PbBr4 into (API)2Pb3Br10 has been observed between 250 and 300 °C.	Jan 2025
I15-1-X-ray Pair Distribution Function (XPDF)	(RPh3P)[Mn(dca)3]: a family of glass-forming hybrid organic-inorganic materials Bikash Kumar Shaw , Lucia Corti , Joshua M. Tuffnell , Celia Castillo-Blas , Patrick Schlachta , Georgina P. Robertson , Lauren Mchugh , Adam F. Sapnik , Sebastian A. Hallweger , Philip A. Chater , Gregor Kieslich , David A. Keen , Sian E. Dutton , Frédéric Blanc , Thomas D. Bennett Inorganic Chemistry DOI: 10.1021/acs.inorgchem.4c04181 Diamond Proposal Number(s): [20038] Open Access Show Abstract ▼ Abstract: ABX3-type hybrid organic–inorganic structures have recently emerged as a new class of meltable materials. Here, by the use of phenylphosphonium derivatives as A cation, we study liquid- and glass-forming behavior of a new family of hybrid structures, (RPh3P)[Mn(dca)3] (R = Me, Et, Ph; dca = dicyanamide). These new compounds melt at 196–237 °C (Tm) and then vitrify upon cooling to room temperature, forming glasses. In situ glass formation of this new family of materials was probed on a large scale using a variable-temperature PXRD experiment. Structure analyses of the crystalline and the glasses were carried out by solid-state nuclear magnetic resonance spectroscopy and synchrotron X-ray total scattering techniques for using the pair distribution function. The mechanical properties of the glasses produced were evaluated showing promising durability. Thermal and electrical conductivities showed low thermal conductivities (κ ∼ 0.07–0.09 W m–1 K–1) and moderate electrical conductivities (σ ∼ 10–4–10–6 S m–1) at room temperature, suggesting that by the precise control of the A cation, we can tune meltable hybrid structures from moderate conductors to efficient thermal insulators. Our results raise attention on the practical use of this new hybrid material in applications including, e.g., photovoltaic devices to prevent light-deposited heat (owing to low κRT), energy harvesting thermoelectric, etc., and advance the structure–property understanding.	Dec 2024
I19-Small Molecule Single Crystal Diffraction	Lanthanide(III) metal-organic frameworks (Ln = Gd, Tb, Dy) based on a C3 symmetrical tricarboxylate linker Darragh Mchugh , Wenming Tong , Andrey Bezrukov , Pau Farras , Michael J. Zaworotko , Julia Mayans , Jonathan M. Skelton , Sarah Barnett , Anuradha. R. Pallipurath , Constantina Papatriantafyllopoulou European Journal Of Inorganic Chemistry DOI: 10.1002/ejic.202400541 Diamond Proposal Number(s): [31893] Open Access Show Abstract ▼ Abstract: Lanthanide-based metal-organic frameworks have attracted significant interest due to their ability to combine porosity with one or more additional properties, providing an alternative method for the development of multifunctional materials. With this in mind, we report the synthesis and characterisation of the OnG5 family of MOFs with the formula [LnLH(DMF)3][(4-NH2Ph)3C](NO3)(CH3CO2H), where Ln = Gd (OnG5-Gd), Tb (OnG5-Tb), Dy (OnG5-Dy), and LH3-= the trianion of 4,4′,4′′-(1E)-[4,4′,4′′-(methanetriyl)tris(benzene-4,1-diyl)tris(azan-1- yl-1-ylidene)]tris(methan-1-yl-1-ylidene)tribenzoic acid. OnG5 were synthesised in situ from the reaction of Ln(NO3)3.xH2O, pararosaniline base [(4-NH2Ph)3COH] and terephthalaldehydic acid in DMF. Their structure was studied through single crystal x-ray crystallography and confirmed with DFT calculations. OnG5 display a 2D, three-fold interpenetrated structure with a honeycomb lattice topology. They are the first examples bearing the ligand LHH3 and they display photoluminescence originating from an intraligand π-π* or n-π* transition. Dc and ac magnetic susceptibility studies conducted on the OnG5-Gd analogue revealed an absence of magnetic interaction between the metal centres.	Dec 2024
I19-Small Molecule Single Crystal Diffraction	Diiridium(III) complexes with fluorenylpyridyl cyclometalating and μ2-oxamidato bridging ligands and their high efficiency phosphorescent solution-processed OLEDs Ahmed M'Hamedi , Mark Fox , Andrei Batsanov , Hameed Al Attar , Martin R. Bryce European Journal Of Inorganic Chemistry DOI: 10.1002/ejic.202400745 Diamond Proposal Number(s): [11145] Open Access Show Abstract ▼ Abstract: Three neutral diiridium(III) complexes with 2-fluorenylpyridyl (flpy) or 5-fluoro-2-fluorenylpyridyl (flpyF) as C^N cyclometalating ligands and a μ2-oxamidato bridge have been synthesized. NMR spectroscopy shows that the complexes are inseparable mixtures of diastereomers (rac, DD/LL and meso, DL) with bridges in anti and syn configurations. Each isomer was determined using 19F NMR data on the flpyF complex. Single crystal diffraction studies of two complexes revealed meso diastereomers with anti configuration of the bis-(t-butylphenyl)oxamidato bridge but an uncertain configuration of the unsubstituted μ2-oxamidato bridge. The complexes are highly emissive (ΦPL 57-82% in solution) with excited state lifetimes of tp ca. 40 ms. The vibronic emissions with maxima at 553-561 nm and at 587-595 nm in solution are attributed to mixed metal-ligand to ligand charge transfer (3MLLCT). Density functional theory (DFT) and time dependent-DFT (TD-DFT) calculations establish the involvement of the fluorenyl groups and the vibronic structures in the emissions. The bridge mediates intramolecular interactions between iridium centers based on electrochemical measurements Phosphorescent organic light-emitting diodes (PhOLEDs) using these complexes as the emissive dopants with a solution-processed active layer have bright greenish-yellow emission with lmaxEL ca. 560 nm, luminous efficiency up to 26 cd/A and high external quantum efficiency (maximum hext ca. 20%).	Dec 2024

Publications Database

Search Results

You searched for all publications:

Search Again...

Subject Areas (check all that apply) select all

Instruments used to collect data (check all that apply) select all

Collaborations involved (check all that apply) select all

Diamond Offline Facilities used

Relevant Technical Areas (check all that apply) select all

Menu for Anonymous User