Boosting Activity and Selectivity of UiO-66 through Acidity/Alkalinity Functionalization in Dimethyl Carbonate Catalysis.

The acid-base properties of supports have an enormous impact on catalytic reactions to regulate the selectivity and activity of supported catalysts. Herein, a train of Pd-X-UiO-66 (X = NO , NH , and CH ) catalysts with different acidity/alkalinity functional groups and encapsulated Pd(II) species is first developed, whose activities in dimethyl carbonate (DMC) catalysis are then investigated in details. Thereinto, the Pd-NO -UiO-66 catalyst with acidity functionalization exhibits the best catalytic behavior: the DMC selectivity stemmed from methyl nitrite (MN) is up to 68%, the conversion of CO is 73.

Tuning different kinds of entangled metal-organic frameworks by modifying the spacer group of aliphatic dicarboxylate ligands and the reactant ratio.

Taking advantage of the conformational flexibility of the bpp ligand and aliphatic dicarboxylic acids, six interesting entangled coordination polymers, {[Cd(fum)(bpp)(H2O)]·(H2O)}n (), {[Cd(fum)(bpp)2]·(H2O)5}n (), {[Cd2(suc)1.5(bpp)2(NO3)(H2O)2]·6H2O}n (), {[Cd(suc)(bpp)2]·(H2O)1.5}n (), {[Cd2(glu)2(bpp)3]·10H2O}n (), and {Cd(adp)(bpp)(H2O)}n () have been prepared and structurally characterized (bpp = 1,3-bi(4-pyridyl)propane, fum = fumaric, suc = succinate, glu = glutaric, adp = adipic).

Ag(I)-mediated in situ dehydrogenative coupling of 3-amino-1,2,4-triazole into 3,3'-azobis(1,2,4-triazole) in Cd(II) coordination polymers.

Ag(I)-mediated in situ generation of 3,3'-azobis(1,2,4-triazole) (AzTAZ) from 3-amino-1,2,4-triazole (AmTAZ) through dehydrogenative coupling has been realized during the crystallization process of two Cd(II) coordination polymers with novel topological architectures: a (3, 4, 5)-connected (4 x 6(2))(2)(4 x 6(7) x 8(2))(2)(6(5) x 10) net for [Cd(2)(AmTAZ)(2)(AzTAZ)](n) (1) and a 4-connected (6(2) x 8(4))(6(4) x 8(2))(6(5) x 8)(2) net for [Cd(AzTAZ)(2)(H(2)O)](n) (2), whereas AmTAZ retains its original form in a heterometallic complex, [Ag(2)Cd(AmTAZ)(4)](n) (3).

Synthesis, structure, and luminescent properties of hybrid inorganic-organic framework materials formed by lead aromatic carboxylates: inorganic connectivity variation from 0D to 3D.

The hydro(solvo)thermal reactions of Pb(OAc)(2).3H(2)O with the aromatic carboxylic ligands 1,3,5-benzenetricarboxylic and 1,4-, 1,2-, and 1,3-benzenedicarboxylic acids (1,3,5-H(3)BTC; 1,4-, 1,2-, and 1,3-H(2)BDC) have yielded a family of inorganic-organic framework materials: [Pb(2)(1,3,5-BTC)(mu(3)-OH)(H(2)O)](n) (Iota), [NaPb(1,3,5-BTC)(H(2)O)](n) (IotaIota), [Pb(1,4-BDC)](n) (IotaIotaIota), [Pb(5)(1,2-BDC)(4)(OAc)(2)](n) (IV), and {[Pb(5)(1,3-BDC)(5)(H(2)O)(2)](2).H(2)O}(n) (V).

Breaking the mirror: pH-controlled chirality generation from a meso ligand to a racemic ligand.

To study the conversion from a meso form to a racemic form of tetrahydrofurantetracarboxylic acid (H(4)L), seven novel coordination polymers were synthesized by the hydrothermal reaction of Zn(NO(3))(2)6 H(2)O with (2S,3S,4R,5R)-H(4)L in the presence of 1,10-phenanthroline (phen), 2,2'-bipyridine (2,2'-bpy), or 4,4'-bipyridine (4,4'-bpy): [Zn(2){(2S,3S,4R,5R)-L}(phen)(2)(H(2)O)]2 H(2)O (1), [Zn(4){(2S,3R,4R,5R)-L}{(2S,3S,4S,5R)-L}(phen)(2)(H(2)O)(2)] (2), [Zn(2){(2S,3S,4R,5R)-L}(H(2)O)(2)]H(2)O (3), [Zn(4){(2S,3R,4R,5R)-L}{(2S,3S,4S,5R)-L} (2,2'-bpy)(2)(H(2)O)(2)]2 H(2)O (4), [Zn(2) {(2S,3S,4R,5R)-L}(2,2'-bpy)(H(2)O)] (5), [Zn(4){(2S,3R,4R,5R)-L}{(2S,3S,4S,5R)-L} (4,4'-bpy)(2)(H(2)O)(2)] (6), and [Zn(2) {(2S,3S,4R,5R)-L}(4,4'-bpy)(H(2)O)] 2 H(2)O (7). These complexes were obtained by control of the pH values of reaction mixtures, with an initial of pH 2.0 for 1, 2.

Controlled generation of acentric and homochiral coordination compounds from a versatile asymmetric ligand 4-(1H-1,2,4-triazol-3-yl)-4H-1,2,4-triazole.

Luminescent acentric and homochiral coordination compounds, which possess new topological networks, multiple helical structures and NLO properties, have been generated through the control of a versatile asymmetric ligand as well as inorganic anions, and this suggests a new protocol for preparing acentric and chiral materials.

Topology analysis and nonlinear-optical-active properties of luminescent metal-organic framework materials based on zinc/lead isophthalates.

Two 3D Zn(II) and Pb(II) isophthalates, [Zn(ip)]n (1) and [Pb4(mu4-O)(ip)3(H2O)]n (2) (H2ip = isophthalic acid), have been prepared under hydro(solvo)thermal conditions and characterized by single-crystal X-ray diffraction. The two complexes crystallize in different space groups (P4(3)2(1)2 for 1 and P2(1)/c for 2) and have different bridging modes of the ip ligand. The 3D framework of 1 is constructed by the interconnection of ZnO4 polyhedra via ip ligands, which represents a chiral net with PtS-type topology.

Organically templated metal-organic framework with 2-fold interpenetrated {3(3).5(9).6(3)}-lcy net.

A new organic cation templated Zn(II) complex (Et3NH)[Zn4(ip)3(bta)3] (, ip = isophthalate, Hbta = benzotriazole) which consists of plate-like Zn4(bta)3 units bridged by ip ligands is reported; it is the first example of a 6-connected uninodal {3(3).5(9).6(3)}-lcy net which has never been observed previously in MOFs but has been theoretically anticipated.

Synthesis, structure, and physical properties of a new anions-controlled Cd(II)-guanazole (3,5-diamino-1,2,4-triazole) hybrid family.

Nine members of a new anions-controlled Cd(II)-guanazole (3,5-diamino-1,2,4-triazole=Hdatrz) hybrid family, that is, [Cd3(datrz)6(H2O)2] (1), [Cd3(datrz)4F2] (2), [Cd5(datrz)4Cl4(OH)2] (3), [Cd5(datrz)4Br4(OH)2] (4), [Cd3(datrz)2(SO3)2].(H2O) (5), [Cd3(datrz)2(O2CMe)4] (6), [Cd(datrz)(O2CEt)] (7), [Cd(Hdatrz)(O2CtBu)2] (8), and [Cd(Hdatrz)2(H2Edta)] (9) have been synthesized by exploiting hydrothermal reactions of guanazole with suitable cadmium salts under appropriate reaction conditions. With effective control of inorganic or organic anions, the coordination diversity of the guanazole ligand in 1-9 manifests an unprecedented enrichment with five bridging modes varying from bidentate to quadridentate, two of which are first reported.

Poly[mu2-trans-1,2-di-4-pyridylethylene-kappa2N:N'-mu2-sulfato-kappa2O:O'-zinc(II)].

The title compound, [Zn(SO(4))(C(12)H(10)N(2))](n), features a layered structure based on [Zn(SO(4))](n) spirals linked by 1,2-di-4-pyridylethylene (bpe) ligands, with the tetrahedral Zn and S atoms lying on twofold axes. The bpe ligands are centrosymmetric. The layers are linked by weak C-H.

A simultaneous redox, alkylation, self-assembly reaction under solvothermal conditions afforded a luminescent copper(I) chain polymer constructed of Cu3I4- and EtS-4-C5H4N+Et components (Et = CH3CH2).

A simultaneous redox, alkylation, self-assembly reaction under solvothermal conditions afforded a novel copper(I) chain polymer constructed of luminescent Cu3I4- and unprecedented EtS-4-C5H4N+Et components (Et = CH3CH2).

Polymeric (mu2-nitrato-kappa2O:O')(mu2-nitrato-kappa2O:O)(mu4-pyridinium-4-thiolato-kappa4S:S:S:S)disilver(I).

The title compound, [Ag(2)(NO(3))(2)(C(5)H(5)NS)](n), was obtained from the reaction of silver nitrate with bis(4-pyridyl) disufide (4-PDS) in a mixture of ethanol and water, which suggests that the disulfide bond of 4-PDS can be cleaved under mild conditions. The structure of the title compound is a two-dimensional infinite array in which the asymmetric unit contains two Ag atoms, a pyridinium-4-thiolate molecule and two nitrate groups. Each pyridinium-4-thiolate molecule acts as a mu(4) bridge, linking four Ag atoms, with Ag-S bond distances of 2.

Tetrakis(pyridinium-2-thiolato)zinc(II) dinitrate.

The crystal structure of the title compound, [Zn(C(5)H(5)NS)(4)](NO(3))(2), consists of a [Zn(C(5)H(5)NS)(4)](2+) (C(5)H(5)NS is pyridinium-2-thiolate) cation and two nitrate anions. The central Zn(II) atom lies at a site with imposed -4 symmetry and is surrounded by four S atoms [Zn-S = 2.3371 (5) A] from four symmetrical pyridinium-2-thiolate ligands in a distorted tetrahedral geometry.

A novel ligand-unsupported 3D framework polymer of trimeric copper(I) and its NLO property.

A novel 3-D coordination polymer with trimeric copper (I) unit, [Cu(3)(CN)(IN)(2)](n)(IN = isonicotinate), was hydrothermally synthesized by the reaction of Cu(NO(3))(2).3H(2)O with isonicotinic and terephthalic acids. The structure was characterized to be a twofold interpenetrated 3-D coordination network polymer with two-coordinated copper(I).

Catena-poly[[dichlorozinc(II)]-micro-1,3-di-4-pyridylpropane-kappa(2)N:N'].

The title compound, [ZnCl(2)(bpp)](n) (where bpp is 1,3-di-4-pyridylpropane, C(13)H(14)N(2)), has been prepared by the hydrothermal reaction of ZnCl(2) and bpp at 433 K. The Zn, Cl and central propyl C atom lie on the mirrors of the P2(1)/m space group. The molecular structure shows a weave-like polymeric chain.