There is, I think, something ethereal about i —the square root of minus one. I remember first hearing about it at school. It seemed an odd beast at that time—an intruder hovering on the edge of reality.

Usually familiarity dulls this sense of the bizarre, but in the case of i it was the reverse: over the years the sense of its surreal nature intensified. It seemed that it was impossible to write mathematics that described the real world in …

I and i

다중혈관 관상동맥 환자에서 y-문합을 이용하여 양쪽 내흉동맥만을 사용한 우회술의 조기 성적

Crystalline metal-organic frameworks (MOFs) are formed by reticular synthesis, which creates strong bonds between inorganic and organic units. Careful selection of MOF constituents can yield crystals of ultrahigh porosity and high thermal and chemical stability. These characteristics allow the interior of MOFs to be chemically altered for use in gas separation, gas storage, and catalysis, among other applications. The precision commonly exercised in their chemical modification and the ability to expand their metrics without changing the underlying topology have not been achieved with other solids. MOFs whose chemical composition and shape of building units can be multiply varied within a particular structure already exist and may lead to materials that offer a synergistic combination of properties.

The Chemistry and Applications of Metal-Organic Frameworks

J. Appl. Cryst.の発刊に際して

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

design and synthesis of high-performance hydrogenstorage materials. Although the weakest X-ray scattering amplitude of hydrogen made it difficult to determine their structure, we have succeeded in the first direct observation of elusive H2 molecules adsorbed in the nano-channels of a metal-organic porous material by the in situ synchrotron powder diffraction experiment of gas adsorption and by MEM (maximum entropy method)/Rietveld charge-density analysis [4]. The sample used in this study is microporous coordination polymer 1 with a pillared layer structure (CPL-1) with uniform ordered nano-channels of 4 Å × 6 Å. The in situ synchrotron powder diffraction experiment for hydrogen gas adsorption was carried out using the large Debye-Scherrer camera installed at beamline BL02B2. The hydrogen gas was dosed into the capillary sample through a stainless steel tube connected to the gas-handling system. The amount of adsorbed gas was controlled by adjusting the sample temperature under a constant hydrogen gas pressure of 102 kPa. The structure was investigated by MEM/Rietveld analysis [5]. The amount of H2 molecules adsorbed in CPL-1 at 90 K at 102 kPa was determined to be 0.3 molecules per Cu atom from the hydrogen adsorption isotherm. The reliability (R) factors based on the powder profile RWP and the Bragg integrated intensities RI were 2.45% and 3.33%, respectively. The cell parameters for CPL-1 with H2 gas were determined as a = 4.7101(1) Å, b = 20.0289(2) Å, c = 10.7704(1) Å, and β = 95.472(2)° (space group P21/c). The R factor based on the structure factors in the final MEM analysis RF was 1.86%. In the MEM charge density of CPL-1 without H2 molecules shown in Fig. 1(a), only the nano-channel structure was clearly seen and no electron density was observed in the nano-channels, even at lower electron-density levels. On the other hand, in the MEM charge density of CPL-1 with H2 molecules (Fig. 1(b)), the small peak maxima of the electron densities with an elongated shape distribution, which are due to the adsorbed H2 molecules, were observed in the nano-channels. It should be noted that the posit ion and orientation of the H2 molecules are mean values obtained by statistical analysis. The

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Direct Observation of Hydrogen Molecules Adsorbed onto a Microporous Coordination Polymer

A new three-dimensional (3-D) jungle-gym-like open metal-organic framework has been synthesized from a two-dimensional (2-D) layer compound using a heterogeneous pillar insertion reaction. Both the starting 2-D layer and the resulting 3-D open compounds have been characterized using X-ray crystallography.

Rational design and crystal structure determination of a 3-D metal-organic jungle-gym-like open framework.

Reversible topochemical transformation of a soft crystal of a coordination polymer.

Porous coordination polymers (PCPs) have been recently highlighted because of their high synthetic designability in structure and functions. Because of their ordered nanoporous structures with a large surface area and tunable pore surface functionality, PCPs have emerged as a significant class of nanoporous materials with potential applications in gas storage, separation, catalysis, and chemical sensing. Recent research has shown the utility of PCPs as host materials for the confinement of nanoparticles of inorganic polymers (IPs), such as metals, metal oxides, and metal chalcogenides. The fabrication of IP nanoparticles in PCPs (PCP⊃IP) has been studied for manifesting specific nanosized-dependent properties and host-guest synergistic functions. In this review, we describe the recent progress in the accommodation of IPs in the nanochannels of PCPs and the remarkable functions of the composite materials.

Inorganic nanoparticles in porous coordination polymers

Structural flexibility is a remarkable characteristic of coordination polymers and significant for the attainment of environmental responsivity. We have prepared a 2D cyanide-bridged MnIICrIII coordination polymer, [Mn(NNdmenH)(H2O)][Cr(CN)6]·H2O (1; NNdmen = N,N-dimethylethylenediamine), with sophisticatedly arranged removable water coligands. The compound clearly showed a reversible single-crystal-to-single-crystal transformation between the 2D sheet and a 3D pillared-sheet framework of dehydrated [Mn(NNdmenH)][Cr(CN)6] (1a). The structural change was reversible and accompanied with generation/cleavage of CN−Mn bonds between 2D sheets by dehydration/hydration. Compounds 1 and 1a also exhibited a ferrimagnetic ordering at 35.2 and 60.4 K, respectively, and the magnetic characteristics were reversibly converted by guest adsorption/desorption. In addition, the dehydrated 1a demonstrated a size-selective solvent adsorption linking chemi- and physisorption processes and shrinkage/expansion of its framework. ...

Susumu Kitagawa

Papers

Direct Observation of Hydrogen Molecules Adsorbed onto a Microporous Coordination Polymer

Rational design and crystal structure determination of a 3-D metal-organic jungle-gym-like open framework.

Reversible topochemical transformation of a soft crystal of a coordination polymer.

Inorganic nanoparticles in porous coordination polymers

A flexible coordination polymer crystal providing reversible structural and magnetic conversions.