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.     

Three-dimensional porous coordination polymer functionalized with amide groups based on tridentate ligand: selective sorption and catalysis

To create a functionalized porous compound, amide group is used in porous framework to produce attractive interactions with guest molecules. To avoid hydrogen-bond formation between these amide groups our strategy was to build a three-dimensional (3D) coordination network using a tridentate amide ligand as the three-connector part. From Cd(NO3)2.4H2O and a three-connector ligand with amide groups a 3D porous coordination polymer (PCP) based on octahedral Cd(II) centers, {[Cd(4-btapa)2(NO3)2].6H2O.2DMF}n (1a), was obtained (4-btapa = 1,3,5-benzene tricarboxylic acid tris[N-(4-pyridyl)amide]). The amide groups, which act as guest interaction sites, occur on the surfaces of channels with dimensions of 4.7 x 7.3 A2. X-ray powder diffraction measurements showed that the desolvated compound (1b) selectively includes guests with a concurrent flexible structural (amorphous-to-crystalline) transformation. The highly ordered amide groups in the channels play an important role in the interaction with the guest molecules, which was confirmed by thermogravimetric analysis, adsorption/desorption measurements, and X-ray crystallography. We also performed a Knoevenagel condensation reaction catalyzed by 1a to demonstrate its selective heterogeneous base catalytic properties, which depend on the sizes of the reactants. The solid catalyst 1a maintains its crystalline framework after the reaction and is easily recycled.     

A Discrete Korovkin Theorem and BKW-Operators

We give a functional Korovkin-type theorem onB(X), the space of bounded complex-valued functions on an arbitrary setXand investigate a BKW-operator onB(X) for a finite collection of test functions with a suitable property and a seminorm defined by a finite subset ofX.     

Ruthenium-catalyzed hydrogenation of alkynylstannanes with migration of the stannyl group

Molecular hydrogen adds to aliphatic and aromatic alkynylstannanes in the presence of a ruthenium catalyst, pushing the stannyl group to the adjacent carbon atom to give alpha-substituted vinylstannanes. This is the first achievement of hydrogenation of alkynylstannanes, which is applicable also to the deuteration affording precursors for an important class of deuterium-labeled compounds.     

Synthesis of multisubstituted 1,3-butadienes using the ruthenium-catalysed double addition of trimethylsilyldiazomethane to alkynylboronates

The ruthenium-catalysed double addition of trimethylsilyldiazomethane to alkynes developed by Dixneuf and co-workers was applied to the synthesis of 2-alkyl- or 2-aryl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1,4-bis(trimethylsilyl)-1,3-butadienes by use of alkynylboronates instead of alkynes. Di- and tetrasubstituted 1,3-butadienes were prepared from a 2-boryl-1,4-disilyl-1,3-butadiene, using the Suzuki-Miyaura coupling reaction, iodolysis of the alkenylsilane moieties with N-iodosuccinimide and hydrolysis of the carbon-silicon bonds with trifluoroacetic acid. The same compound was converted also to a bicyclic compound, a trisubstituted 1,3-butadiene and a dienone through the Diels-Alder reaction, oxidation of the alkenylboronate moiety and the Mukaiyama aldol reaction.     

On the frame of the unit ball of Banach spaces

The notion of the frame of the unit ball of Banach spaces was introduced to construct a new calculation method for the Dunkl-Williams constant. In this paper, we characterize the frame of the unit ball by using k-extreme points and extreme points of the unit ball of two-dimensional subspaces. Furthermore, we show that the frame of the unit ball is always closed, and is connected if the dimension of the space is not less than three. As infinite dimensional examples, the frame of the unit balls of c ₀ and ? _p are determined.     

A solution to Tingley’s problem for isometries between the unit spheres of compact C*-algebras and JB*-triples

Let f : S(E) → S(B) be a surjective isometry between the unit spheres of two weakly compact JB*-triples not containing direct summands of rank less than or equal to 3. Suppose E has rank greater than or equal to 5. Applying techniques developed in JB*-triple theory, we prove that f admits an extension to a surjective real linear isometry T : E → B. Among the consequences, we show that every surjective isometry between the unit spheres of two compact C*-algebras A and B, without assuming any restriction on the rank of their direct summands(and in particular when A = K(H) and B = K(H′)), extends to a surjective real linear isometry from A into B. These results provide new examples of infinite-dimensional Banach spaces where Tingley's problem admits a positive answer.     

A Porous Coordination Polymer with Accessible Metal Sites and its Complementary Coordination Action

Broken switch : Guest‐accessible metal sites are generated on the pore surface of a porous coordination polymer (see figure) through the complementary coordination‐bond rearrangement in a single‐crystal‐to‐single‐crystal fashion, which is triggered by the removal of coordinated water.