Showing papers by "Ryo Kitaura published in 2004"

Functional porous coordination polymers.

Abstract: The chemistry of the coordination polymers has in recent years advanced extensively, affording various architectures, which are constructed from a variety of molecular building blocks with different interactions between them. The next challenge is the chemical and physical functionalization of these architectures, through the porous properties of the frameworks. This review concentrates on three aspects of coordination polymers: 1). the use of crystal engineering to construct porous frameworks from connectors and linkers ("nanospace engineering"), 2). characterizing and cataloging the porous properties by functions for storage, exchange, separation, etc., and 3). the next generation of porous functions based on dynamic crystal transformations caused by guest molecules or physical stimuli. Our aim is to present the state of the art chemistry and physics of and in the micropores of porous coordination polymers.

Funktionale poröse Koordinationspolymere

Abstract: Die Chemie der Koordinationspolymere hat sich in den vergangenen Jahren rasant entwickelt. Strukturen aus einer Vielzahl molekularer Bausteine mit unterschiedlichen Wechselwirkungen sind mittlerweile zuganglich. Die nachste Stufe ist die chemische und physikalische Funktionalisierung dieser Architekturen durch Einstellung ihrer Porositaten. Dieser Aufsatz konzentriert sich auf drei Aspekte von Koordinationspolymeren: 1) Anwendung von Kristall-Engineering zum Aufbau poroser Geruste aus Konnektoren und Linkern (“Nanospace-Engineering”), 2) Charakterisierung und Katalogisierung poros-struktureller Funktionalitat fur Anwendungen in Speicherungs-, Austausch-, Trennprozessen etc. und 3) poros-strukturelle Funktionalitat auf der Basis dynamischer Kristallumwandlungen durch Gastmolekule oder physikalische Reize. Ziel ist es, den aktuellen Stand der Forschung zur Chemie und Physik von und in den Mikroporen poroser Koordinationspolymere vorzustellen.

Guest shape-responsive fitting of porous coordination polymer with shrinkable framework.

Abstract: In situ synchrotron X-ray powder diffraction patterns of porous coordination polymers {[Cu2(pzdc)2(bpy)]·G} have been measured (pzdc = pyrazine-2,3-dicarboxylate, bpy = 4,4‘-bipyridine) (where G = H2O for CPL-2 ⊃ H2O, G = benzene for CPL-2 ⊃ benzene, and G = void for the apohost). The structures of apohost and CPL-2 ⊃ benzene were determined from Rietveld analysis. Adsorption of benzene in the channels induced a remarkable contraction in the crystal (b axis; 6.8%, volume; 4.9%), although the channels were occupied by the benzene molecules. This crystal transformation provides a new pore structure that is well suited for benzene molecules, and we denote it as a “shape-responsive fitting” transformation. This type of pore gives rise to a new guideline: frameworks can be composed of flexible motifs that are linked via strong bond and/or stiff motifs that are connected via weaker bonds.

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

Abstract: 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.

Metal‐Complex Assemblies Constructed from the Flexible Hinge‐Like Ligand H2bhnq: Structural Versatility and Dynamic Behavior in the Solid State

Abstract: Novel metal-complex assemblies constructed from the flexible hinge-like ligand H 2 bhnq (H 2 bhnq= 2,2'-bi(3-hydroxy-1,4-naphthoquinone)) have been synthesized. The X-ray crystal structures of these compounds reveal that four types of architectures are accessible by variation of the metal ions. In copper(II) compounds 1-3, the chelating bhnq 2 - ions bridge copper(II) centers to form one-dimensional zigzag chains. The chains of 1-3 are arranged by hydrogen-bonding interactions and stacking interactions to produce porous structures. Cobalt(II) and zinc(ii) compounds 4 and 5 form one-dimensional helical chains. In 4 and 5, the crystal packing induces spontaneous resolution of the helical chains with chiral cavities formed perpendicular to the helices. Nickel(II) compounds 6 and 7 form cyclic tetramers. The fourth architecture, a dimer (compound 8), is obtained by the reaction of zinc(II) and bhnq 2 - in MeOH. In these compounds, changes of the dihedral angles and the metal-coordination mode of the bhnq 2 - ion induce the structural versatility. The assemblies of the zigzag chains of the copper(II) compounds exhibit reversible vapochromic behavior. UV/Vis, powder X-ray diffraction, EPR, and adsorption isotherm measurements indicate that this vapochromic behavior is based on the hinge-like flexibility of the bhnq 2 - ion.

Functional Porous Coordination Polymers

Abstract: The chemistry of the coordination polymers has in recent years advanced extensively, affording various architectures, which are constructed from a variety of molecular building blocks with different interactions between them. The next challenge is the chemical and physical functionalization of these architectures, through the porous properties of the frameworks. This review concentrates on three aspects of coordination polymers: 1). the use of crystal engineering to construct porous frameworks from connectors and linkers ("nanospace engineering"), 2). characterizing and cataloging the porous properties by functions for storage, exchange, separation, etc., and 3). the next generation of porous functions based on dynamic crystal transformations caused by guest molecules or physical stimuli. Our aim is to present the state of the art chemistry and physics of and in the micropores of porous coordination polymers.