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Susumu Kitagawa

Publications and source records attributed to Susumu Kitagawa.

At least 55 records · Page 3Linked to original sources
PubMed2005

Framework control by a metalloligand having multicoordination ability: new synthetic approach for crystal structures and magnetic properties.

By utilizing the novel metalloligand l(Cu), [Cu(2,4-pydca)(2)](2)(-) (2,4-pydca(2)(-) = pyridine-2,4-dicarboxylate), which possesses two kinds of coordination groups, selective bond formation with the series of the first-period transition metal ions (Mn(ii), Fe(ii), Co(ii), Cu(ii), and Zn(ii)) has been accomplished. depending on the coordination mode of 4-carboxylate with Co(ii), Cu(ii), and Zn(ii) ions, L(Cu) forms a one-dimensional (1-d) assembly with a repeating motif of [-M-O(2)C-(py)N-Cu-N(py)-Co(2)-]: {[ZnL(Cu)(H(2)O)(3)(DMF)].DMF}(N)() (2), [ZnL(Cu)(H(2)O)(2)(MeOH)(2)](N)() (3), and {[ML(Cu)(H(2)O)(4)].2H(2)O}(N)() (M = Co (4), Cu (5), Zn (6)). the use of a terminal ligand of 2,2'-bipyridine (2,2'-bpy), in addition to the cu(ii) ion, gives a zigzag 1-d assembly with the similar repeating unit as 4-6: {[Cu(2,2'-bpy)L(Cu)].3H(2)O}(N)() (9). on the other hand, for Mn(ii) and Fe(ii) ions, L(Cu) shows a 2-carboxylate bridging mode to form an another 1-d assembly with a repeating motif of [-M-O-C-O-CU-O-C-O-]: [ML(Cu)(H(2)O)(4)](N)() (M = Mn (7), Fe (8)). this selectivity is related to the strength of lewis basicity and the electrostatic effect of L(Cu) and the irving-williams order on the present metal ions. according to their bridging modes, a variety of magnetic properties are obtained: 4, 5, and 9, which have the 4-carboxypyridinate bridge between magnetic centers, have weak antiferromagnetic interaction, whereas 7 and 8 with the carboxylate bridge between magnetic centers reveal 1-d ferromagnetic behavior (Cu(II)-M(II); M(II) = Mn(II), J/k(B) = 0.69 K for 7; M(II) = Fe(II), J/k(B) = 0.71 K for 8).

Journal Article↗
PubMed2005

Dynamic porous properties of coordination polymers inspired by hydrogen bonds.

In a decade, many porous coordination polymers have been synthesized, providing a variety of properties ranging from storage, separation, exchange of guests in their cavities, magnetism, conductivity and catalysis by their frameworks. In this tutorial review, we focus on the hydrogen bonding type arrangements for dynamic porous coordination polymers exhibiting elastic guest accommodations, in contrast to rigid three-dimensional (3-D) frameworks. Such dynamic porous properties induce highly-selective guest accommodation and magnetic modulation, and could now be considered a new class of practical materials.

Hydrogen Bonding↗
PubMed2004

A novel high-spin heterometallic Ni12K4 cluster incorporating large Ni-azide circles and an in situ cyanomethylated di-2-pyridyl ketone.

Reaction of di-2-pyridyl ketone (dpk) with nickel acetate and azide in the presence of potassium tert-butylate as a catalytic base generates the title compound, which contains the largest [Ni(mu(1,1)-N3)]6 circles in the discrete ferromagnetically-coupled M(II)-azide cluster family, and shows an unprecedented in situ cyanomethylation of ketone.

Journal Article↗
PubMed2004

Size and surface effects of prussian blue nanoparticles protected by organic polymers.

Prussian blue (PB) nanoparticles protected by organic polymers such as poly(vinylpyrrolidone) (PVP) and poly(diallyldimethylammonium chloride) (PDDA) were prepared. Different experimental conditions (concentrations of Fe ions and feed ratios of Fe to the polymers) have been investigated to control the size of the PB nanoparticles. For example, the averaged dimensions of the PB nanoparticles were tuned from 12 to 27 nm by use of PVP in the different conditions. Addition of PDDA produced the PB nanoparticles with very small dimensions (5-8 nm) by an effective electrostatic interaction. We found that the surface environments of the PB nanoparticles affect the inherent properties of PB. The shifts of charge transfer (CT) absorptions from Fe(2+) to Fe(3+) in the PB nanoparticles resulted from the surface-protecting polymers. Especially, the PB nanoparticles with the PVP protection show high solubility in a variety of organic solvents and a solvent-dependent CT absorption. Measurement of the magnetic properties of the PB nanoparticles showed unprecedented size-dependency, surface effect, and superparamagnetic properties.

Journal Article↗
PubMed2004

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

In situ synchrotron X-ray powder diffraction patterns of porous coordination polymers [[Cu(2)(pzdc)(2)(bpy)].G] have been measured (pzdc = pyrazine-2,3-dicarboxylate, bpy = 4,4'-bipyridine) (where G = H(2)O for CPL-2 superset H(2)()O, G = benzene for CPL-2 superset benzene, and G = void for the apohost). The structures of apohost and CPL-2 superset 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.

Journal Article↗
PubMed2004

Neutral paddlewheel diruthenium complexes with tetracarboxylates of large pi-conjugated substituents: facile one-pot synthesis, crystal structures, and electrochemical studies.

A one-pot reaction of a cationic diruthenium complex, [Ru(2)(II,III)(O(2)CCH(3))(4)(THF)(2)](BF(4)), with arylcarboxylic acids, ArCO(2)H, (PhCO(2)H = benzoic acid, NapCO(2)H = 1-naphthoic acid, AntCO(2)H = 9-anthracenecarboxylic acid) in NDMA (NDMA = N,N-dimethylaniline) has led to isolation of neutral paddlewheel-type diruthenium complexes, [Ru(II)(2)(O(2)CAr)(4)(THF)(2)] (Ar = Ph (1), Nap (2), Ant (3)). Paramagnetic variable temperature (VT) (1)H NMR studies and GC-MS studies show that the reaction consists of two steps: a one-electron reduction of the Ru(2) core by NDMA and a simple carboxylate-exchange reaction. All compounds 1-3 were structurally characterized by X-ray crystallography. While the structural features of the Ru(2) core are very similar in all the compounds, the dihedral angles between the carboxylate plane and the aromatic ring are larger with the expanding of aryl groups from phenyl to anthracene. The effect of pi-pi stacking leads to the formation of a 1-D chain structure in compound 3, whereas compounds 1 and 2 are fully isolated from each other. The electrochemical measurements show that the quasireversible one-electron oxidation step is observed at +0.06, +0.09, and +0.17 V (vs Ag/Ag(+)) for 1-3, respectively, assigned to the Ru(II)(2)/Ru(II,III)(2) redox couple. These potentials are found to demonstrate a linear relationship with the substituent constants for aryl compounds,.

Carboxylic Acids↗
PubMed2004

Metal-complex assemblies constructed from the flexible hinge-like ligand H2bhnq: structural versatility and dynamic behavior in the solid state.

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.

Crystallography, X-Ray↗
PubMed2004

Functional porous coordination polymers.

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.

Journal Article↗
PubMed2004

A contrivance for a dynamic porous framework: cooperative guest adsorption based on square grids connected by amide-amide hydrogen bonds.

Flexible porous coordination polymers containing amide groups as a function origin have been synthesized and categorized as "Coordination Polymer with Amide Groups". Bispyridyl ligands with a spacer of amide group afford two-dimensional (2-D) motifs with a deformed square grid, resulting in three-dimensional (3-D) frameworks of [Co(NO(3))(2)(3-pna)(2)](n)(1), [Co(Br)(2)(3-pna)(2)](n)(2), and [[Co(NCS)(2)(4-peia)(2)].4Me(2)CO](n)(3 subset 4Me(2)CO) (3-pna = N-3-pyridylnicotinamide, 4-peia = N-(2-pyridin-4-yl-ethyl)-isonicotinamide), where the 2-D motifs are bound by complementary hydrogen bond between the amide groups. In the case of the 3 subset 4Me(2)CO, the amide groups form a contrivance for a dynamic porous framework because of their relevant position and orientation in the mutual nearest neighboring motifs. Consequently, 3 subset 4Me(2)CO shows amorphous (nonporous)-to-crystal (porous) structural rearrangement in the Me(2)CO adsorption and desorption process, where the framework of the 2-D motif is maintained. The adsorption isotherm has threshold pressure (P(th)), a sort of gate pressure. The heat of Me(2)CO adsorption (DeltaH(ad) = -25 kJ/mol) is obtained from the temperature dependence of threshold pressure (P(th)), which is close to acetone vaporization enthalpy (DeltaH(vap) = 30.99 kJ/mol).

Journal Article↗
PubMed2004

Preparation of acentric porous coordination frameworks from an interpenetrated diamondoid array through anion-exchange procedures: crystal structures and properties.

The formation, crystal structures, and properties of a series of three-dimensional (3-D) Cu(II) coordination polymers, [[Cu(L)2(H2O)2](PF6)2(H2O)(1.25)]n (1), [[CuL(N3)2](H2O)(1.5)]n (2), and [[CuL(H2O)(SO4)](H2O)2]n (3), with an angular bridging ligand 2,5-bis(4-pyridyl)-1,3,4-oxadiazole (L) are reported. Complex 1 crystallizes in the tetragonal I4(1)/a space group (a = b = 13.462(2) A, c = 46.47(1) A, Z = 8), complex 2 in the orthorhombic Pna2(1) space group (a = 6.379(2) A, b = 10.060(3) A, c = 27.232(9) A, Z = 4), and complex 3 in the orthorhombic P2(1)2(1)2(1) space group (a = 5.510(2) A, b = 10.576(4) A, c = 28.34(1) A, Z = 4). Different polymeric frameworks are obtained by only varying the counterions. These include the 2-fold interpenetrated diamondoid structure of 1, the acentric alpha-Po network of 2, and the chiral open framework of 3 with (6(3)).(6(9).8) topology. The interesting anion-exchange, porous, and magnetic properties of these coordination supramolecules have been investigated in detail.

Journal Article↗
PubMed2004

Module-based assembly of copper(II) chloranilate compounds: syntheses, crystal structures, and magnetic properties of [[Cu(2)(CA)(terpy)(2)][Cu(CA)(2)]](n)() and [[Cu(2)(CA)(terpy)(2)(dmso)(2)][Cu(CA)(2)(dmso)(2)](EtOH)](n)(H(2)CA = chloranilic acid, terpy = 2,2':6',2' '-terpyridine, dmso = dimethyl sulfoxide).

Two new copper(II) compounds of chloranilate and 2,2':6',2' '-terpyridine have been synthesized, and the structures have been solved by the single-crystal X-ray diffraction method. The crystal structure of [[Cu(2)(CA)(terpy)(2)][Cu(CA)(2)]](n)(1), where H(2)CA = chloranilic acid and terpy = 2,2':6',2' '-terpyridine, consists of two modules, the dimer unit [Cu(2)(CA)(terpy)(2)](2+) and the anionic mononuclear unit [Cu(CA)(2)](2)(-), forming an alternated chain. The chain is stabilized by semicoordinating and additional but efficient secondary bonding interactions. The crystal structure of [[Cu(2)(CA)(terpy)(2)(dmso)(2)][Cu(CA)(2)(dmso)(2)](EtOH)](n)(2), where dmso = dimethyl sulfoxide, consists of solvent molecules and two discrete modules, the dimer unit [Cu(2)(CA)(terpy)(2)(dmso)(2)](2+) and the anionic mononuclear unit [Cu(CA)(2)(dmso)(2)](2)(-). The dimer units form a layer by secondary bonding interactions, and the monomer units and ethanol molecules are introduced between the layers. The magnetic properties of 1 and 2 have been investigated in the temperature range 2.0-300 K. A weak ferromagnetic interaction was observed in 1, J(a) = 2.36 cm(-)(1) and zJ(b) = -0.68 cm(-)(1) while no exchange coupling was observed in 2.

Journal Article↗