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Since the discovery of charge disproportionation in the FeO_{2} square-lattice compound Sr_{3}Fe_{2}O_{7} by Mössbauer spectroscopy more than fifty years ago, the spatial ordering pattern of the disproportionated charges has remained "hidden" to conventional diffraction probes, despite numerous x-ray and neutron scattering studies. We have used neutron Larmor diffraction and Fe K-edge resonant x-ray scattering to demonstrate checkerboard charge order in the FeO_{2} planes that vanishes at a sharp second-order phase transition upon heating above 332 K. Stacking disorder of the checkerboard pattern due to frustrated interlayer interactions broadens the corresponding superstructure reflections and greatly reduces their amplitude, thus explaining the difficulty of detecting them by conventional probes. We discuss the implications of these findings for research on "hidden order" in other materials.
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The reaction of cis-blocked, square-planar MII complexes with tetratopic N-donor ligands is known to give metallasupramolecular assemblies of the formula M2nLn. These assemblies typically adopt barrel-like structures, with the ligands paneling the sides of the barrels. However, alternative structures are possible, as demonstrated by the recent discovery of a Pt8L4 cage with unusual gyrobifastigium-like geometry. To date, the factors that govern the assembly of MII2nLn complexes are not well understood. Herein, we provide a geometric analysis of M2nLn complexes, and we discuss how size and geometry of the ligand is expected to influence the self-assembly process. The theoretical analysis is complemented by experimental studies using different cis-blocked PtII complexes and metalloligands with four divergent pyridyl groups. Mononuclear metalloligands gave mainly assemblies of type Pt8L4, which adopt barrel- or gyrobifastigium-like structures. Larger assemblies can also form, as evidenced by the crystallographic characterization of a Pt10L5 complex and a Pt16L8 complex. The former adopts a pentagonal barrel structure, whereas the latter displays a barrel structure with a distorted square orthobicupola geometry. The Pt16L8 complex has a molecular weight of more than 23 kDa and a diameter of 4.5 nm, making it the largest, structurally characterized M2nLn complex described to date. A dinuclear metalloligand was employed for the targeted synthesis of pentagonal Pt10L5 barrels, which are formed in nearly quantitative yields.
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It is possible to control the geometry and the composition of metallasupramolecular assemblies via the aspect ratio of their ligands. This point is demonstrated for a series of iron- and palladium-based coordination cages. Functionalized clathrochelate complexes with variable aspect ratios were used as rod-like metalloligands. A cubic Fe(II)8L12 cage was obtained from a metalloligand with an intermediate aspect ratio. By increasing the length or by decreasing the width of the ligand, the self-assembly process resulted in the clean formation of tetrahedral Fe(II)4L6 cages instead of cubic cages. In a related fashion, it was possible to control the geometry of Pd(II)-based coordination cages. A metalloligand with a large aspect ratio gave an entropically favored tetrahedral Pd(II)4L8 assembly, whereas an octahedral Pd(II)6L12 cage was formed with a ligand of the same length but with an increased width. The aspect ratio can also be used to control the composition of dynamic mixtures of Pd(II) cages. Out of two metalloligands with only marginally different aspect ratios, one gave rise to a self-sorted collection of Pd(II)4L8 and Pd(II)6L12 cages, whereas the other did not.
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The synthesis and characterization of a new class of neutral aminyl radicals is reported. Monoradicals were obtained by reduction of azoimidazolium dyes with potassium. Structural, spectroscopic, and computational data suggest that the spin density is centered on one of the nitrogen atoms of the former azo group. The reduction of a dimeric dye with an octamethylbiphenylene bridge between the azo groups resulted in the formation of a biradical with largely independent unpaired electrons. Both the monoradicals and the biradical were found to display high stability in solution as well as in the solid state.
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The diffraction beamline BM01A at the European Synchrotron Radiation Facility (CRG Swiss-Norwegian beamlines) has been successfully operational for 20 years. Recently, a new multifunctional diffractometer based on the Dectris Pilatus 2M detector has been constructed, commissioned and offered to users. The diffractometer combines a fast and low-noise area detector, which can be tilted and moved horizontally and vertically, together with flexible goniometry for sample positioning and orientation. The diffractometer is controlled by a user-friendly and GUI-based software Pylatus which is also used to control various auxiliary equipment. The latter includes several heating and cooling devices, in situ cells and complimentary spectroscopic tools.
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Polycarboxylate ligands are among the most important building blocks for the synthesis of metal-organic frameworks (MOFs). The ability to access these ligands in an efficient way is of key importance for future applications of MOFs. Here, we demonstrate that mono- and dinuclear clathrochelate complexes are versatile scaffolds for the preparation of polytopic carboxylate ligands. The largely inert clathrochelate complexes have a trigonal-bipyramidal shape. The synthesis of functionalized clathrochelates with two, three, four, or five carboxylic acid groups in the ligand periphery can be achieved in a few steps from simple starting materials. Apart from being easily accessible, the metalloligands display interesting characteristics for applications in metallasupramolecular chemistry and materials science: they are rigid, large (up to 2.2 nm), and robust and they can show additional functions (e.g., fluorescence or extra charge) depending on the metal ion that is present in the clathrochelate core. The utility of these new metalloligands in MOF chemistry is demonstrated by the synthesis of zinc- and zirconium-based coordination polymers. The combination of Zn(NO3)2 with clathrochelates having two or three carboxylic acid groups gives MOFs in which the clathrochelate ligands are connected by Zn4O clusters or zinc paddlewheel links. The structures of the resulting two- and three-dimensional networks could be established by single-crystal X-ray crystallography. The reaction of carboxylic acid functionalized clathrochelates with ZrCl4 gives amorphous powders that display permanent porosity after solvent removal.
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The Hoffman-type coordination compound [Fe(pz)Pt(CN)4]â 2.6 H2O (pz = pyrazine) shows a cooperative thermal spin transition at around 270â K. Synchrotron powder X-Ray diffraction studies reveal that a quantitative photoinduced conversion from the low-spin (LS) state into the high-spin (HS) state, based on the light-induced excited spin-state trapping effect, can be achieved at 10â K in a microcrystalline powder. Time-resolved measurements evidence that the HSâLS relaxation proceeds by a two-step mechanism: a random HSâLS conversion at the beginning of the relaxation is followed by a nucleation and growth process, which proceeds until a quantitative HSâLS transformation has been reached.
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Using a combination of single-crystal and powder X-ray diffraction measurements, we study temperature- and pressure-driven structural distortions in zinc(II) cyanide (Zn(CN)2) and cadmium(II) imidazolate (Cd(im)2), two molecular frameworks with the anticuprite topology. Under a hydrostatic pressure of 1.52 GPa, Zn(CN)2 undergoes a first-order displacive phase transition to an orthorhombic phase, with the corresponding atomic displacements characterized by correlated collective tilts of pairs of Zn-centered tetrahedra. This displacement pattern sheds light on the mechanism of negative thermal expansion in ambient-pressure Zn(CN)2. We find that the fundamental mechanical response exhibited by Zn(CN)2 is mirrored in the temperature-dependent behavior of Cd(im)2. Our results suggest that the thermodynamics of molecular frameworks may be governed by considerations of packing efficiency while also depending on dynamic instabilities of the underlying framework topology.
Assuntos
Cádmio/química , Cianetos/química , Imidazóis/química , Compostos Organometálicos/química , Zinco/química , Modelos Moleculares , Difração de Pó , Difração de Raios XRESUMO
Cerium(III) and cerium(IV) both form formate complexes. However, their species in aqueous solution and the solid-state structures are surprisingly different. The species in aqueous solutions were investigated with Ce K-edge EXAFS spectroscopy. Ce(III) formate shows only mononuclear complexes, which is in agreement with the predicted mononuclear species of Ce(HCOO)(2+) and Ce(HCOO)2(+). In contrast, Ce(IV) formate forms in aqueous solution a stable hexanuclear complex of [Ce6(µ3-O)4(µ3-OH)4(HCOO)x(NO3)y](12-x-y). The structural differences reflect the different influence of hydrolysis, which is weak for Ce(III) and strong for Ce(IV). Hydrolysis of Ce(IV) ions causes initial polymerization while complexation through HCOO(-) results in 12 chelate rings stabilizing the hexanuclear Ce(IV) complex. Crystals were grown from the above-mentioned solutions. Two crystal structures of Ce(IV) formate were determined. Both form a hexanuclear complex with a [Ce6(µ3-O)4(µ3-OH)4](12+) core in aqueous HNO3/HCOOH solution. The pH titration with NaOH resulted in a structure with the composition [Ce6(µ3-O)4(µ3-OH)4(HCOO)10(NO3)2(H2O)3]·(H2O)9.5, while the pH adjustment with NH3 resulted in [Ce6(µ3-O)4(µ3-OH)4(HCOO)10(NO3)4]·(NO3)3(NH4)5(H2O)5. Furthermore, the crystal structure of Ce(III) formate, Ce(HCOO)3, was determined. The coordination polyhedron is a tricapped trigonal prism which is formed exclusively by nine HCOO(-) ligands. The hexanuclear Ce(IV) formate species from aqueous solution is widely preserved in the crystal structure, whereas the mononuclear solution species of Ce(III) formate undergoes a polymerization during the crystallization process.
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Thermal evolution of an organic ferroelectric, namely, glycinium phosphite, was probed by multi-temperature single-crystal diffraction using synchrotron radiation and also by a similar experiment with a laboratory X-ray diffractometer. Both series of measurements showed a transition from the paraelectric to the ferroelectric state at nearly the same temperature, Tc = 225â K. Temperature evolution of the unit-cell parameters and volume are drastically different for the synchrotron and laboratory data. The latter case corresponds to previous reports and shows an expected contraction of the cell on cooling. The data collected with the synchrotron beam show an abnormal nonlinear increase in volume on cooling. Structure analysis shows that this volume increase is accompanied by a suppression of scattering at high angles and an apparent increase of the anisotropic displacement parameters for all atoms; we therefore link these effects to radiation damage accumulated during consecutive data collections. The effects of radiation on the formation of the polar structure of ferroelectric glycinium phosphite is discussed together with the advantages and drawbacks of synchrotron experimentation with fine temperature sampling.
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Protein powder diffraction is shown to be suitable for obtaining de novo solutions to the phase problem at low resolution via phasing methods such as the isomorphous replacement method. Two heavy-atom derivatives (a gadolinium derivative and a holmium derivative) of the tetragonal form of hen egg-white lysozyme were crystallized at room temperature. Using synchrotron radiation, high-quality powder patterns were collected in which pH-induced anisotropic lattice-parameter changes were exploited in order to reduce the challenging and powder-specific problem of overlapping reflections. The phasing power of two heavy-atom derivatives in a multiple isomorphous replacement analysis enabled molecular structural information to be obtained up to approximately 5.3 A resolution. At such a resolution, features of the secondary structure of the lysozyme molecule can be accurately located using programs dedicated to that effect. In addition, the quoted resolution is sufficient to determine the correct hand of the heavy-atom substructure which leads to an electron-density map representing the protein molecule of proper chirality.
Assuntos
Proteínas Aviárias/química , Muramidase/química , Animais , Galinhas , Modelos Moleculares , Difração de Pó , Estrutura Secundária de Proteína , Estrutura Terciária de ProteínaRESUMO
The crystal structure of the neuropeptide proctolin (Arg-Tyr-Leu-Pro-Thr) is reported revealing the solid-state conformation of its molecules and their association in the crystal.
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Insetos/química , Neuropeptídeos/química , Oligopeptídeos/química , Sequência de Aminoácidos , Animais , Cristalografia por Raios X , Ligação de Hidrogênio , Modelos Moleculares , Dados de Sequência Molecular , Nanotubos/química , Polímeros/química , Conformação ProteicaRESUMO
The quest for lead-free light-absorbing perovskite materials has long been the target of researchers to make the 'star' material friendly to the commercial market. After a summary of different lead-free solar absorbers, we demonstrate a zero-dimensional iodobismuthate (MA)3[BiI6]·3MACl (MA: CH3NH3) featuring isolated hexaiodobismuthate(iii) anions in the crystal analysis. The unexpectedly formed material was made via an orthogonal solvent permeation method and the decomposition of the guest solvent. We compare the BiI63- containing compound with a series of more common iodobismuthates, especially the dinuclear Bi2I93- in terms of dimensionalities via single-crystal diffraction and DFT calculations, respectively. An undocumented second-order phase transition was found between 190 K and 160 K for the dimeric MA3Bi2I9. The photovoltaic device from a thermally reorganized polycrystalline film of (MA)3[BiI6]·3MACl, which resembled the structure of (MA)3[Bi2I9] gave a power conversion efficiency of 1.09%.
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The title compound, C(10)H(18), a decalin stereoisomer, crystallizes with Z' = 0.5 in the space group P2(1)/n. The trans-decalin molecule is located on an inversion centre with both rings in a chair conformation, making for a quasi-flat overall shape. Despite the absence of hydrogen bonds, it crystallizes easily. In this work the unknown crystal structure of trans-decalin has been solved and refined using X-ray powder diffraction data.
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Metal-organic frameworks (MOFs) have attracted much attention in the past decade owing to their unprecedented internal surface areas, tunable topologies, designable surfaces, and various potential applications. One bottleneck in the field regarding MOF synthesis is controlling the metal-containing secondary building unit (SBU) incorporated into the structure. In this work we report the synthesis and characterization of five trimeric [M3(µ3-O)(CH3CO2)6]x clusters (where M = Fe3+, Cr3+, Fe3+/Cr3+, Fe3+/Co2+, or Fe3+/Ni2+ and x = +1 or 0). The monocarboxylate capping ligand, acetate in this case, readily undergoes exchange with several difunctional counterparts, including 1,4-benzenedicarboxylic acid (H2-BDC) and biphenyl-4,4'-dicarboxylic acid (H2-BPDC), for the formation of an isostructural series of MOFs, several of which are newly reported (for M = Fe3+/Cr3+, Fe3+/Co2+, and Fe3+/Ni2+) and show excellent CO2 adsorption properties. In this report, a host of techniques including NMR, ICP, and ESI-MS are used to probe the ligand exchange process and composition of the SBUs, and XAS is used to monitor the Fe3+ and Cr3+ environment throughout the reactions, giving strong evidence that the clusters stay intact throughout the MOF synthesis. This work reveals that predefined SBUs is an effective means to create metal-substituted analogues of known frameworks. Further, CO adsorption and in situ IR are used to probe accessibility of the metals after solvent removal. We show for the first time that the incorporation of the neutral clusters, containing weaker Lewis acids like Ni2+ and Co2+, can promote the formation of open metal sites in the MOF frameworks, structural features known to enhance the binding energy of small guest molecules like CO2.
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Donor-π-acceptor dyes containing thiophenyl π-conjugated units and cyanoacrylate acceptor groups are among the best-performing organic chromophores used in dye-sensitized solar cell (DSC) applications. Yet, the molecular origins of their high photovoltaic output have remained unclear until now. This synchrotron-based X-ray diffraction study elucidates these origins for the high-performance thiophenylcyanoacrylate-based dye MK-2 (7.7% DSC device efficiency) and its molecular building block, MK-44. The crystal structures of MK-2 and MK-44 are both determined, while a high-resolution charge-density mapping of the smaller molecule was also possible, enabling the nature of its bonding to be detailed. A strong S···C≡N intramolecular interaction is discovered, which bears a bond critical point, thus proving that this interaction should be formally classified as a chemical bond. A topological analysis of the π-conjugated portion of MK-44 shows that this S···C≡N bonding underpins the highly efficient intramolecular charge transfer (ICT) in thiophenylcyanoacrylate dyes. This manifests as two bipartite ICT pathways bearing carboxylate and nitrile end points. In turn, these pathways dictate a preferred COO/CN anchoring mode for the dye as it adsorbs onto TiO2 surfaces, to form the dye···TiO2 interface that constitutes the DSC working electrode. These results corroborate a recent proposal that all cyanoacrylate groups anchor onto TiO2 in this COO/CN binding configuration. Conformational analysis of the MK-44 and MK-2 crystal structures reveals that this S···C≡N bonding will persist in MK-2. Accordingly, this newly discovered bond affords a rational explanation for the attractive photovoltaic properties of MK-2. More generally, this study provides the first unequivocal evidence for an S···C≡N interaction, confirming previous speculative assignments of such interactions in other compounds.
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A detailed diffraction study of Ca10Cr7O28 is presented which adds significant new insights into the structural and magnetic properties of this compound. A new crystal structure type was used where the a and b axes are doubled compared to previous models providing a more plausible structure where all crystallographic sites are fully occupied. The presence of two different valences of chromium was verified and the locations of the magnetic Cr5+ and non-magnetic Cr6+ ions were identified. The Cr5+ ions have spin-[Formula: see text] and form distorted kagome bilayers which are stacked in an ABC arrangement along the c axis. These results lay the foundation for understanding of the quantum spin liquid behavior in Ca10Cr7O28 which has recently been reported in Balz et al (2016 Nat. Phys. 12 942).
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C70(CF3)16 and C70(CF3)18, the first trifluoromethylated fullerene derivatives to comprise a pair of adjacent CF3 groups, have been isolated from a mixture obtained via reaction of C70 with CF3I, characterized in a single crystal XRD study and theoretically investigated at the DFT level of theory.
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Dinuclear clathrochelate complexes are easily accessible by reaction of zinc(ii) triflate or cobalt(ii) nitrate with arylboronic acids and phenoldioximes. The utilization of brominated arylboronic acids and/or brominated phenoldioximes allows preparing clathrochelates with two, three, five or seven bromine atoms on the outside. These clathrochelates can undergo Pd-catalyzed cross-coupling reactions with 3- and 4-pyridylboronic acid to give new metalloligands featuring up to seven pyridyl groups. The pyridyl-capped clathrochelates display characteristics which make them interesting building blocks for structural supramolecular chemistry: they are rigid, large (up to 2.7 nm), luminescent (for M = Zn), and anionic. The pentatopic pyridyl ligands display an unusual trigonal bipyramidal geometry.
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Dinuclear clathrochelate complexes with two, three, four, or five cyano groups in the ligand periphery were prepared following two distinct synthetic strategies: (a) zinc(ii)- or cobalt(ii)-templated polycondensation reactions of CN-functionalized arylboronic acids and phenoldioximes, or (b) postsynthetic cross-coupling reactions of polybrominated zinc(ii) clathrochelates with 4-cyanophenylboronic acid. The new clathrochelate complexes were used as metalloligands for the construction of heterometallic Zn2+/Ag+ and Co2+/Ag+ coordination polymers (CPs), which were characterized by single crystal X-ray diffraction and FT-IR. A one-dimensional CP was observed for ditopic clathrochelates, whereas two- and three-dimensional CPs were generated from tetra- and pentatopic metalloligands. The three-dimensional network is unique as it displays an unprecedented network topology with the point symbol (8·102)(82·104)(82·10)(83·103). Furthermore, it is a self-catenated net with an extremely high topological density.