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      Flexibility transition and guest-driven reconstruction in a ferroelastic metal–organic framework†

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          Abstract

          Copper( i) tricyanomethanide shows exceptional mechanical and coordination flexibility in response to temperature and guest sorption.

          Abstract

          The metal–organic framework copper( i) tricyanomethanide, Cu(tcm), undergoes a ferroelastic transition on cooling below T f = 240 K. Thermal expansion measurements reveal an order-of-magnitude variation in framework flexibility across T f. The low-temperature phase α-Cu(tcm) exhibits colossal positive and negative thermal expansion that is the strongest ever reported for a framework material. On exposure to acetonitrile, Cu(tcm) undergoes a reconstructive solid-phase transition to acetonitrilocopper( i) tricyanomethanide. This transition can be reversed by heating under vacuum. Infrared spectroscopy measurements are sensitive to the phase change, suggesting that Cu(tcm) may find application in solid-phase acetonitrile sensing.

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          Rapid planetesimal formation in turbulent circumstellar discs

          The initial stages of planet formation in circumstellar gas discs proceed via dust grains that collide and build up larger and larger bodies (Safronov 1969). How this process continues from metre-sized boulders to kilometre-scale planetesimals is a major unsolved problem (Dominik et al. 2007): boulders stick together poorly (Benz 2000), and spiral into the protostar in a few hundred orbits due to a head wind from the slower rotating gas (Weidenschilling 1977). Gravitational collapse of the solid component has been suggested to overcome this barrier (Safronov 1969, Goldreich & Ward 1973, Youdin & Shu 2002). Even low levels of turbulence, however, inhibit sedimentation of solids to a sufficiently dense midplane layer (Weidenschilling & Cuzzi 1993, Dominik et al. 2007), but turbulence must be present to explain observed gas accretion in protostellar discs (Hartmann 1998). Here we report the discovery of efficient gravitational collapse of boulders in locally overdense regions in the midplane. The boulders concentrate initially in transient high pressures in the turbulent gas (Johansen, Klahr, & Henning 2006), and these concentrations are augmented a further order of magnitude by a streaming instability (Youdin & Goodman 2005, Johansen, Henning, & Klahr 2006, Johansen & Youdin 2007) driven by the relative flow of gas and solids. We find that gravitationally bound clusters form with masses comparable to dwarf planets and containing a distribution of boulder sizes. Gravitational collapse happens much faster than radial drift, offering a possible path to planetesimal formation in accreting circumstellar discs.
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            Versatile Photocatalytic Systems for H2 Generation in Water Based on an Efficient DuBois-Type Nickel Catalyst

            The generation of renewable H2 through an efficient photochemical route requires photoinduced electron transfer (ET) from a light harvester to an efficient electrocatalyst in water. Here, we report on a molecular H2 evolution catalyst (NiP) with a DuBois-type [Ni(P2 R′N2 R″)2]2+ core (P2 R′N2 R″ = bis(1,5-R′-diphospha-3,7-R″-diazacyclooctane), which contains an outer coordination sphere with phosphonic acid groups. The latter functionality allows for good solubility in water and immobilization on metal oxide semiconductors. Electrochemical studies confirm that NiP is a highly active electrocatalyst in aqueous electrolyte solution (overpotential of approximately 200 mV at pH 4.5 with a Faradaic yield of 85 ± 4%). Photocatalytic experiments and investigations on the ET kinetics were carried out in combination with a phosphonated Ru(II) tris(bipyridine) dye (RuP) in homogeneous and heterogeneous environments. Time-resolved luminescence and transient absorption spectroscopy studies confirmed that directed ET from RuP to NiP occurs efficiently in all systems on the nano- to microsecond time scale, through three distinct routes: reductive quenching of RuP in solution or on the surface of ZrO2 (“on particle” system) or oxidative quenching of RuP when the compounds were immobilized on TiO2 (“through particle” system). Our studies show that NiP can be used in a purely aqueous solution and on a semiconductor surface with a high degree of versatility. A high TOF of 460 ± 60 h–1 with a TON of 723 ± 171 for photocatalytic H2 generation with a molecular Ni catalyst in water and a photon-to-H2 quantum yield of approximately 10% were achieved for the homogeneous system.
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              A technique for relativistic spin-polarised calculations

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                Author and article information

                Journal
                CrystEngComm
                CrystEngComm
                Crystengcomm / Rsc
                Royal Society of Chemistry
                1466-8033
                14 January 2015
                14 October 2014
                : 17
                : 2
                : 361-369
                Affiliations
                [a ] Department of Chemistry , University of Oxford , Inorganic Chemistry Laboratory , South Parks Road , Oxford , OX1 3QR , UK . Email: andrew.goodwin@ 123456chem.ox.ac.uk
                Article
                c4ce01572j
                10.1039/c4ce01572j
                4304274
                25632268
                This journal is © The Royal Society of Chemistry 2014

                This is an Open Access article distributed under the terms of the Creative Commons Attribution Non-Commercial License ( http://creativecommons.org/licenses/by-nc/2.0/uk/) which permits unrestricted non-commercial use, distribution, and reproduction in any medium, provided the original work is properly cited.

                Categories
                Chemistry

                Notes

                †Electronic supplementary information (ESI) available: Atomic coordinates and lattice parameter data. CCDC 1016797. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c4ce01572j

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