The long-standing challenge of designing and constructing new crystalline solid-state materials from molecular building blocks is just beginning to be addressed with success. A conceptual approach that requires the use of secondary building units to direct the assembly of ordered frameworks epitomizes this process: we call this approach reticular synthesis. This chemistry has yielded materials designed to have predetermined structures, compositions and properties. In particular, highly porous frameworks held together by strong metal-oxygen-carbon bonds and with exceptionally large surface area and capacity for gas storage have been prepared and their pore metrics systematically varied and functionalized.

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Reticular synthesis and the design of new materials

A cross-platform program, VESTA, has been developed to visualize both structural and volumetric data in multiple windows with tabs. VESTA represents crystal structures by ball-and-stick, space-filling, polyhedral, wireframe, stick, dot-surface and thermal-ellipsoid models. A variety of crystal-chemical information is extractable from fractional coordinates, occupancies and oxidation states of sites. Volumetric data such as electron and nuclear densities, Patterson functions, and wavefunctions are displayed as isosurfaces, bird's-eye views and two-dimensional maps. Isosurfaces can be colored according to other physical quantities. Translucent isosurfaces and/or slices can be overlapped with a structural model. Collaboration with external programs enables the user to locate bonds and bond angles in the `graphics area', simulate powder diffraction patterns, and calculate site potentials and Madelung energies. Electron densities determined experimentally are convertible into their Laplacians and electronic energy densities.

VESTA: a three-dimensional visualization system for electronic and structural analysis

Infrared spectroscopy of proteins.

The development in the field of coordination polymers or metal-organic coordination networks, MOCNs (metal-organic frameworks, MOFs) is assessed in terms of property investigations in the areas of catalysis, chirality, conductivity, luminescence, magnetism, spin-transition (spin-crossover), non-linear optics (NLO) and porosity or zeolitic behavior upon which potential applications could be based.

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Engineering coordination polymers towards applications

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Metal–Organic Frameworks and Self-Assembled Supramolecular Coordination Complexes: Comparing and Contrasting the Design, Synthesis, and Functionality of Metal–Organic Materials

Magnets synthesized from molecules have contributed to the renaissance in the study of magnetic materials. Three-dimensional network solids exhibiting magnetic ordering have been made from several first-row metal ions and bridging unsaturated cyanide, tricyanomethanide, and/or dicyanamide ligands. These materials possess several different structural motifs, and the shorter the bridge, the stronger the interaction (i.e., C⋮N > N⋮CN ≫ N⋮CNC⋮N = N⋮CCC⋮N). Cyanide additionally has the ability to discriminate between C- and N-bonding to form ordered heterobimetallic magnets, and the strong coupling can lead to ferro- or ferrimagnetic ordering substantially above room temperature. Tricoordination of tricyanomethanide results in spin-frustrated systems, which possess interpenetrating rutile-like networks. In contrast, single rutile-like frameworks are formed by μ3-bonded dicyanamide, which leads to ferromagnetics and weak ferromagnetics.

Designer magnets containing cyanides and nitriles.

Enhancement of the magnetic ordering temperature and air stability of a mixed valent vanadium hexacyanochromate(iii) magnet to 99 c (372 k)

The reaction of [MII(OH2)6](NO3)2 (M = Co, Ni) and [N(CN)2]- leads to formation of isomorphous M[N(CN)2]2 [M = Co (2a), Ni (3)], respectively, while the reaction of [CoII(OH2)6](NO3)2 in 1% pyridin...

Structure and Magnetic Ordering of MII[N(CN)2]2 (M = Co, Ni)†

The supramolecular chemistry and crystal structures of five bis(imidazolium 2,6-pyridinedicarboxylate)M(II) trihydrate complexes, where M = Mn2+, Co2+, Ni2+, Cu2+, or Zn2+ (1−5, respectively), are reported. These complexes serve as supramolecular building blocks that self-assemble when crystallized to generate a single, well-defined, predictable structure in the solid state. 2,6-Pyridinedicarboxylate anions and imidazolium cations form strong ionic hydrogen bonds that dominate crystal packing in compounds 1−5 by forming two-dimensional networks, or layers of molecules. This layer motif serves as a platform with which to control and predict molecular packing by design for engineering the structures of crystals. Moreover, compounds 1−5 create a robust organic host lattice that accommodates five different transition metals without significantly altering molecular packing. Growth of crystals from solutions that contain two or more different metal complexes produces mixed crystals in which mixtures of the diff...

Design of Layered Crystalline Materials Using Coordination Chemistry and Hydrogen Bonds

The dynamic susceptibility study of photoinduced magnetism in a molecule-based magnet, K1-2xCo1+x[Fe(CN)(6)];yH(2)O (0.2</=x</=0.4,y approximately 5), is reported. Upon excitation with visible light the material has substantial changes in linear and nonlinear ac susceptibility and dc magnetization. The results demonstrate cooperative freezing of magnetic moments and absence of true long-range magnetic order. The ground and photoexcited states are described within a cluster glass model, with photoinduced increase in spin concentration leading to a shift of the dynamics to longer length and time scales and higher temperatures.

Jamie L. Manson

Papers

Designer magnets containing cyanides and nitriles.

Enhancement of the magnetic ordering temperature and air stability of a mixed valent vanadium hexacyanochromate(iii) magnet to 99 c (372 k)

Structure and Magnetic Ordering of MII[N(CN)2]2 (M = Co, Ni)†

Design of Layered Crystalline Materials Using Coordination Chemistry and Hydrogen Bonds

Photoinduced magnetism, dynamics, and cluster glass behavior of a molecule-based magnet