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Instruments / Technical Area	Publication Details	Published
I11-High Resolution Powder Diffraction	An adaptable peptide-based porous material Jeremy Rabone , Yan-Feng Yue , Sam Chong , Kyriakos Stylianou , John Bacsa , Darren Bradshaw , George Darling , Neil Berry , Yaroslav Khimyak , Alexey Ganin , Paul Wiper , John Claridge , Matthew Rosseinsky Science 329 (5995), 1053-1057 DOI: 10.1126/science.1190672 PMID: 20798314 Diamond Proposal Number(s): [1732] Show Abstract ▼ Abstract: Porous materials find widespread application in storage, separation, and catalytic technologies. We report a crystalline porous solid with adaptable porosity, in which a simple dipeptide linker is arranged in a regular array by coordination to metal centers. Experiments reinforced by molecular dynamics simulations showed that low-energy torsions and displacements of the peptides enabled the available pore volume to evolve smoothly from zero as the guest loading increased. The observed cooperative feedback in sorption isotherms resembled the response of proteins undergoing conformational selection, suggesting an energy landscape similar to that required for protein folding. The flexible peptide linker was shown to play the pivotal role in changing the pore conformation.	Aug 2010
I19-Small Molecule Single Crystal Diffraction	Cation vacancy order in the K0.8+xFe1.6−ySe2 system: Five-fold cell expansion accommodates 20% tetrahedral vacancies John Bacsa , Alexey Ganin , Yasuhiro Takabayashi , Kirsten Christensen , Kosmas Prassides , Matthew Rosseinsky , John Claridge Chemical Science DOI: 10.1039/c1sc00070e Show Abstract ▼ Abstract: Ordering of the tetrahedral site vacancies in two crystals of refined compositions K0.93(1)Fe1.52(1)Se2 and K0.862(3)Fe1.563(4)Se2 produces a fivefold expansion of the parent ThCr2Si2 unit cell in the ab plane which can accommodate 20% vacancies on a single site within the square FeSe layer. The iron charge state is maintained close to +2 by coupling of the level of alkali metal and iron vacancies, producing a potential doping mechanism which can operate at both average and local structure levels.	Mar 2011
I11-High Resolution Powder Diffraction	Polymorphism control of superconductivity and magnetism in Cs3C60 close to the Mott transition Alexey Y. Ganin , Yasuhiro Takabayashi , Peter Jeglic , Denis Arcon , Anton Potocnik , Peter J. Baker , Yasuo Ohishi , Martin T. Mcdonald , Manolis D. Tzirakis , Alec Mclennan , George R. Darling , Masaki Takata , Matthew J. Rosseinsky , Kosmas Prassides Nature DOI: 10.1038/nature09120 Diamond Proposal Number(s): [731] Show Abstract ▼ Abstract: The crystal structure of a solid controls the interactions between the electronically active units and thus its electronic properties. In the high-temperature superconducting copper oxides, only one spatial arrangement of the electronically active Cu2+ units—a two-dimensional square lattice—is available to study the competition between the cooperative electronic states of magnetic order and superconductivity1. Crystals of the spherical molecular C603- anion support both superconductivity and magnetism but can consist of fundamentally distinct three-dimensional arrangements of the anions. Superconductivity in the A3C60 (A = alkali metal) fullerides has been exclusively associated with face-centred cubic (f.c.c.) packing of C603- (refs 2, 3), but recently the most expanded (and thus having the highest superconducting transition temperature, Tc; ref. 4) composition Cs3C60 has been isolated as a body-centred cubic (b.c.c.) packing, which supports both superconductivity and magnetic order5, 6. Here we isolate the f.c.c. polymorph of Cs3C60 to show how the spatial arrangement of the electronically active units controls the competing superconducting and magnetic electronic ground states. Unlike all the other f.c.c. A3C60 fullerides, f.c.c. Cs3C60 is not a superconductor but a magnetic insulator at ambient pressure, and becomes superconducting under pressure. The magnetic ordering occurs at an order of magnitude lower temperature in the geometrically frustrated f.c.c. polymorph (Néel temperature TN = 2.2 K) than in the b.c.c.-based packing (TN = 46 K). The different lattice packings of C603- change Tc from 38 K in b.c.c. Cs3C60 to 35 K in f.c.c. Cs3C60 (the highest found in the f.c.c. A3C60 family). The existence of two superconducting packings of the same electronically active unit reveals that Tc scales universally in a structure-independent dome-like relationship with proximity to the Mott metal–insulator transition, which is governed by the role of electron correlations characteristic of high-temperature superconducting materials other than fullerides.	May 2010
I11-High Resolution Powder Diffraction	Redox-controlled potassium intercalation into two polyaromatic hydrocarbon solids Fabio Denis Romero , Michael Pitcher , Craig Hiley , George Whitehead , Srotoswini Kar , Alexey Ganin , Dmitro Antypov , Christopher Collins , Matthew Dyer , Gyongyi Klupp , Ross Colman , Kosmas Prassides , Matthew Rosseinsky Nature Chemistry DOI: 10.1038/nchem.2765 Diamond Proposal Number(s): [9282, 12336] Show Abstract ▼ Abstract: Alkali metal intercalation into polyaromatic hydrocarbons (PAHs) has been studied intensely after reports of superconductivity in a number of potassium- and rubidium-intercalated materials. There are, however, no reported crystal structures to inform our understanding of the chemistry and physics because of the complex reactivity of PAHs with strong reducing agents at high temperature. Here we present the synthesis of crystalline K2Pentacene and K2Picene by a solid–solid insertion protocol that uses potassium hydride as a redox-controlled reducing agent to access the PAH dianions, and so enables the determination of their crystal structures. In both cases, the inserted cations expand the parent herringbone packings by reorienting the molecular anions to create multiple potassium sites within initially dense molecular layers, and thus interact with the PAH anion π systems. The synthetic and crystal chemistry of alkali metal intercalation into PAHs differs from that into fullerenes and graphite, in which the cation sites are pre-defined by the host structure.	Apr 2017
I11-High Resolution Powder Diffraction	Synthesis of face-centred cubic Cs3C60 in THF Alec Mclennan , Alexey Ganin , Yasuhiro Takabayashi , Ross H. Colman , Ruth H. Zadik , Matthew Rosseinsky , Kosmas Prassides Faraday Discussions DOI: 10.1039/C4FD00085D Show Abstract ▼ Abstract: A solution chemistry synthetic route yields Cs3C60 with a face-centred cubic structure. The described method uses well-established Schlenk techniques and THF as a solvent. The controlled addition of an organo-metallic salt reducing agent prevents the formation of C604− salts. The final product can be precipitated from the solution using hexane as an anti-solvent.	Jul 2014
B18-Core EXAFS	The rapid electrochemical activation of MoTe2 for the hydrogen evolution reaction Jessica C. Mcglynn , Torben Dankwort , Lorenz Kienle , Nuno A. G. Bandeira , James P. Fraser , Emma K. Gibson , Irene Cascallana-Matias , Katalin Kamarás , Mark D. Symes , Harry N. Miras , Alexey Y. Ganin Nature Communications 10 DOI: 10.1038/s41467-019-12831-0 Diamond Proposal Number(s): [14239] Open Access Show Abstract ▼ Abstract: The electrochemical generation of hydrogen is a key enabling technology for the production of sustainable fuels. Transition metal chalcogenides show considerable promise as catalysts for this reaction, but to date there are very few reports of tellurides in this context, and none of these transition metal telluride catalysts are especially active. Here, we show that the catalytic performance of metallic 1T′-MoTe2 is improved dramatically when the electrode is held at cathodic bias. As a result, the overpotential required to maintain a current density of 10 mA cm−2 decreases from 320 mV to just 178 mV. We show that this rapid and reversible activation process has its origins in adsorption of H onto Te sites on the surface of 1T′-MoTe2. This activation process highlights the importance of subtle changes in the electronic structure of an electrode material and how these can influence the subsequent electrocatalytic activity that is displayed.	Oct 2019

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