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A series of N-aryl phosphoramidite ligands were synthesized, and the iridium complexes derived from these novel ligands were proven to be efficient catalysts for asymmetric intermolecular allylic amination reactions. This C-N bond forming process readily accommodates a diverse range of amines and allylic carbonates, especially for the previously challenging ortho-substituted cinnamyl substrates. Moreover, isolation and characterization of the corresponding (π-allyl)-iridium complex K1 reveal that the active iridacycle is generated through a C(sp²)-H bond insertion of tetrahydroquinoline of the ligand. [ABSTRACT FROM AUTHOR]

Two nanocage-based metal-organic frameworks respectively built on two and three types of clusters with diisophthalate ligand were constructed, displaying unprecedented (3,4,6)-connected nets, unusual nanocages, and new bipaddle-wheel tetranuclear cluster, as well as highly selective CO2 capture. [ABSTRACT FROM AUTHOR]

The protonolysis reaction of β-iminophosphonamine ligand (NPNdipp = Ph2P(NC6H3iPr2-2,6)2) with one equivalent of rare-earth-metal tris(alkyl)s afforded the corresponding bis(alkyl) complexes NPNdippLn(CH2SiMe3)2(THF) (Ln = Sc (1), Lu (2), Y (3), Er (4)). The bis(4-methylbenzyl) complexes NPNdippLn(CH2Ph-4-Me)2(THF) (Ln = Nd (5), La (6)) were prepared by treatment of the tris(4-methylbenzyl) compounds Ln(CH2Ph-4-Me)3(THF)3 with β-iminophosphonamine ligand. The small-size rare-earth-metal-based complexes 1-4 upon activation with AliBu3 and [Ph3C][B(C6F5)4] showed high 3,4-selectivities up to 98.1% for isoprene polymerization. When the larger size rare-earth-metal-based 4-methylbenzyl complexes 5 and 6 were employed instead, moderate 3,4-selectivities were obtained since the opening coordination environment facilitated the 1,4-enchainment (Nd3+: 76.1%; La3+: 62.9%). Replacing AliBu3 by AlEt3, the 5 and 6 systems exhibited high activity and excellent trans-1,4 selectivity for both isoprene (96.5%, 0 °C) and butadiene (92.8%, 20 °C) polymerizations. [ABSTRACT FROM AUTHOR]

A family of 2,9-di(3-R-1H-imidazolium-1-yl)-1,10-phenanthroline iodides and hexafluorophosphates (R = allyl, benzyl, mesityl, picolyl) were synthesized from 2,9-diiodophenanthroline and imidazole or N-substituted imidazoles. Simple reactions of these diimidazolium salts with copper powder at room temperature have afforded a series of multinuclear copper(I)-NHC complexes in good yields. The structures vary depending on the N substituents and counterions. [Cu4(L1)2(MeCN)4](PF6)4 (R = allyl) exhibits a zigzag Cu4 chain with two terminal [Cu(NHC)(MeCN)2] and two internal [Cu(phen)(NHC)] moieties. [Cu3(L2)2](PF6)3 (R = benzyl) contains a strictly linear Cu3 framework with two [Cu(NHC)2] units and a [Cu(phen)2] located at the center. Both complexes [Cu3(L4)2](PF6)3 (R = mesityl) and [Cu3(L5)2](PF6)3 (R = picolyl) consist of a triangular Cu3 core in which two copper(I) ions are surrounded by a phen and a NHC group and the third copper(I) is coordinated by two NHC groups. [Cu3(L3)2](PF6)3 derived from 2,9-di(3-benzyl-1H-benzimidazolium-1-yl)-1,10-phenanthroline hexafluorophosphate can undergo transannulation of the benzimidazolylidene ring giving [Cu2(L3')2](PF6)2. The decomposition process might involve solvent-induced rearrangement of the ligand and hydrolysis of carbene moieties. Treatment of 2,9-di(3-mesityl-1H-benzimidazolium-1-yl)-1,10-phenanthroline iodide with copper powder generated dinuclear complex [Cu2(L4)2][Cu2(μ-I)2I2] (R = mesityl) possessing a macrocyclic cation and [Cu2(μ-I)2I2]2- anion. Tetranuclear complex [Cu4(L5)2(μ-I)2](CuI3) (R = picolyl) has been obtained from its diimidazolium iodide and copper powder. All Cu(I) complexes have been characterized by X-ray single diffraction analysis, elemental analysis, and NMR spectra. Their redox behavior and fluorescent properties have also been studied. [ABSTRACT FROM AUTHOR]

One transition metal-organic framework [Zn(TBTC)(2,6-pydc)] n ( 1 ), has been assembled from a mixed ligand 4,5,9,14-tetraaza-benzo[b]triphenylene-11-carboxylic acid (HTBTC) with the help of pyridine-2,6-dicarboxylic acid (2,6-pydc)ligand. X-ray single crystal diffraction analysis reveals that compound 1 crystallizes in the space group of P21/c and displays a one-dimensional (1D) zigzag infinite chain, which is extended via the p-p stacking interactions between pyrazine rings and benzene rings to form 2D supramolecular layers. Compound 1 shows an excellent photocatalytic activity through degradation of methyl blue (MB), methyl violet (MV), rhodamine B (RhB) and orange G (OG). The rate of photodegradation for MV can reach 90% under Xe lamp irradiation after 4.5 h. In addition, catalytic mechanism was also discussed. [ABSTRACT FROM AUTHOR]

Four uncommon isostructural nanocage-based 3D Ln-MOFs, 1-Ln (Ln = Eu, Tb, Gd and Dy), were constructed using a new diisophthalate ligand with active pyridyl sites. 1-Eu exhibits highly efficient luminescent sensing for Cu2+ ions and selective CO2 capture. [ABSTRACT FROM AUTHOR]

Two novel hybrid materials based on two kinds of octamolybdate anions and metal–organic frameworks (MOFs), namely, [Ag8(L1)4(α-Mo8O26)(β-Mo8O26)(H2O)3]·H2O (1) and [CuI3.1CuII0.5(β-Mo8O26)0.5(ζ-Mo7VIMoVO26)0.5(L2)2(H0.8L2)0.5] (2), where L1= 1,1′-(1,3-propanediyl)bis[2-(4-pyridyl)benzimidazole] and L2= 1,1′-(1,4-butanediyl)bis[2-(3-pyridyl)benzimidazole], have been successfully synthesized. Crystal structure analysis revealed that 1is a three-dimensional (3D) framework constructed of silver(i)–organic sheets and two types of (Mo8O26)4−isomers. Compound 2is a rare 3D framework containing copper(i,ii)–organic cages and 1D channels occupied by the (ζ-Mo7VIMoVO26)5−and (β-Mo8O26)4−anions. The two compounds were characterized by elemental analysis, IR spectroscopy, diffuse reflectivity spectroscopy, and photoluminescent spectroscopy. In addition, the photocatalytic behavior of 1was investigated. [ABSTRACT FROM AUTHOR]

A new polyoxometalate (POM) based on a flexible bidentate ligand and "inverted Keggin" inorganic building block, namely, [Cu8L8[Mo12O46(AsPh)4]2]∙H2O (1), where L is 1,3-bis(1,2,4-triazol-1-yl)propane, has been synthesized under hydrothermal condition. In 1, the "inverted Keggin" [Mo12O46(AsPh)4]4- building blocks are linked by the one-dimensional (1D) zigzag [CuI(trans-L)]+ chains and [CuI4(cis-L)4]4+ macrocycles to yield a three-dimensional (3D) framework. The compound 1 represents the first 3D "inverted Keggin" polyoxometalate modified by a transition-metal complex. Topologically, the 3D framework can be considered as an 8-connected net with a Schlafli symbol of 422∙66. As far as we know, compound 1 is the highest-connected uninodal network topology presently known for POM-based materials. The compound was characterized by its IR spectrum, UV—vis spectrum, thermogravimetric analysis (TGA), and powder X-ray diffraction (XRD) patterns. Remarkably, compound 1 exhibits photocatalytic activity for dye degradation under visible light irradiation and shows good stability toward visible-light photocatalysis. [ABSTRACT FROM AUTHOR]

Three new cadmium coordination polymers, [CdBr(tmdp)(μ-tmdp)]· n(HO) ( 1), [Cd(SCN)(μ-tmdp)]·2 n(PhS) ( 2) and [Cd(SCN)(μ-tmdp)]· n(PhS)· n(CHCN) ( 3) (tmdp = 4,4′-trimethylenedipyridine), have been synthesized under solvothermal conditions and structurally characterized by single-crystal X-ray diffraction analysis. The geometry around cadmium is a slightly distorted octahedron with four tmdp and two Br or SCN ligands. Complex 1 represents a one-dimensional structure, whereas complexes 2 and 3 are two-dimensional coordination polymers. The rhombic channels of the coordination network of 2 and 3 are occupied by 1D polymeric (PhS) and diphenyl disulfide (PhS) molecules, respectively. The photoluminescent properties of coordination polymers 1- 3 were investigated in solid state at room temperature. The TGA experiments showed that these three complexes were quite thermally stable. Graphical Abstract: Three new cadmium coordination polymers have been synthesized under solvothermal conditions and structurally characterized by single-crystal X-ray diffraction analysis. The rhombic channels of the two-dimensional coordination networks are occupied by one-dimensional polymeric (PhS) and diphenyl disulfide (PhS) molecules. [Figure not available: see fulltext.] [ABSTRACT FROM AUTHOR]

Two Cd(ii)-containing coordination polymers based on a new tri(4-imidazolylphenyl)amine (Tipa) ligand and carboxylates, namely, [Cd(Tipa)(L1)]·2H2O (1) and [Cd3(Tipa)2(L2)2Cl2]·4H2O (2), where H2L1 = 5-OH-1,3-benzenedicarboxylic acid and H2L2 = 1,4-benzendicarboxylic acid, have been synthesized by varying the carboxylates under hydrothermal conditions. In 1, adjacent Cd(ii) centers are linked by L1 anions to generate Cd-carboxylate chains, which are further extended by Tipa ligands to form a puckered double sheet. The most peculiar feature of 1is the entangled fashion between the [Cd2(Tipa)2] loop and the L1 ligand rod. Every [Cd2(Tipa)2] loop of each layer is threaded by one L1 ligand rod of an adjacent layer. In this entangled mode, the 2D → 3D polyrotaxane framework was obtained, which represents an unusual 2D → 3D metal–organic polyrotaxane framework entangled in a highly rare parallel fashion. In 2, two identical 3D self-penetrating frameworks interpenetrate each other in a 2-fold mode. If we regard each Cd2(Tipa)2window as a loop and each L2 ligand as a single rod, undoubtedly, the structure of 2also can be described as a 3D metal–organic polyrotaxane framework. As far as we know, compound 2is the first example of a 2-fold interpenetrating 3D framework with polyrotaxane features. The luminescent properties for the two compounds were also investigated. [ABSTRACT FROM AUTHOR]

Treatment of anilido-phosphinimine-ligated yttrium mono(alkyl) complex 1a, LY(CH2Si(CH3)3)(THF) (L = o-(2,6-C6H3iPr2)NC6H4P(C6H4)(C6H5)N(2,4,6-C6H2Me3)), with 2 equiv of phenylsilane in DME afforded methoxy-bridged complex 2, [LY(μ-OCH3)]2, via the corresponding hydrido intermediate. When excess isoprene was added to the mixture of 1aand phenylsilane, a η3-isopentene product, 3, LY(CH2C(CH3)CHCH3)(THF), was isolated. A lutetium chloride, LLuCl(DME) (4), was generated through the reaction of lutetium mono(alkyl) complex 1b, LLu(CH2Si(CH3)3)(THF), with [Ph3C][B(C6F5)4]·LiCl accompanied by the formation of [Li(DME)3]+[B(C6F5)4]−. Metathesis reaction of 1bwith excess AlMe3at room temperature gave a methyl-terminated counterpart, 5, LLu(CH3)(THF)2. In all these reactions, the Ln−Cphenylbonds of complexes 1remained untouched. However, protonolysis of complex 1bwith 2 equiv of phenylacetylene in DME provided a lutetium bis(acetylide), LHLu(CCPh)2(DME) (6), and the linkage of the Ln−Cphenylbond was cleaved, indicating that the activated C−H bond was recovered. [ABSTRACT FROM AUTHOR]

Highly regio- and enantioselective Ir-catalyzed Friedel–Crafts type allylic alkylation of indoles have been realized using [Ir(COD)Cl] 2/phosphoramidite ligand 1a, affording the branched products with up to >97/3 branched-linear ratio and 92% ee. [ABSTRACT FROM AUTHOR]

The N,N-bidentate ligands 2-(N-2,6-R)iminomethyl)pyrrole (HL1, R dimethylphenyl; HL2, R diisopropylphenyl) have been prepared. HL1reacted readily with 1 equiv of lanthanide tris(alkyl)s, Ln(CH2SiMe3)3(THF)2, affording lanthanide bis(alkyl) complexes L1Ln(CH2SiMe3)2(THF)n(1a, Ln Lu, n2; 1b, Ln Sc, n1) via alkane elimination. Reaction of the bulky ligand HL2with 1 equiv of Ln(CH2SiMe3)3(THF)2gave the bis(pyrrolylaldiminato) lanthanide mono(alkyl) complexes L22Ln(CH2SiMe3)(THF) (2a, Ln Lu; 2b, Ln Sc), selectively. The N,N-bidentate ligand HL3, 2-dimethylaminomethylpyrrole, reacted with Ln(CH2SiMe3)3(THF)2, generating bimetallic bis(alkyl) complexes of central symmetry (3a, Ln Y; 3b, Ln Lu; 3c, Ln Sc). Treatment of the N,N,N,N-tetradentate ligand H2L4, 2,2‘-bis(2,2-dimethylpropyldiimino)methylpyrrole, with equimolar Lu(CH2SiMe3)3(THF)2afforded a C2-symmetric binuclear complex (4). Complexes 3a, 3b, 3c, and 4represent rare examples of THF-free binuclear lanthanide bis(alkyl) complexes supported by non-cyclopentadienyl ligands. All complexes have been tested as initiators for the polymerization of isoprene in the presence of AlEt3and Ph3CB(C6F5)4. Complexes 1a, 1b, and 3ashow activity, and 1bis the most active initiator, whereas 2a, 2b, 3b, 3c, and 4are inert. The microstructure of the resultant polyisoprene has a cis-1,4 or trans-1,4 configuration depending on the initiator applied. [ABSTRACT FROM AUTHOR]

Mercaptoacetic acid (RSH)-capped CdS nanocrystals (NCs) was demonstrated to be electrochemically reduced during potential scan and react with the coreactant S2082 to generate strong electrochemiluminescence (ECL) in aqueous solution. Based on the ECL of CdS NCs, a novel label- free ECL biosensor for the detection of low-density lipo-protein (LDL) has been developed by using self-assembly and gold nanoparticle amplification techniques. The bio- sensor was prepared as follows: The gold nanoparticles were first assembled onto a cysteamine monolayer on the gold electrode surface. This gold nanoparticle-covered electrode was next treated with cysteine and then reacted with CdS NCs to afford a CdS NC-electrode. Finally, apoB-100 (ligand of LDL receptor) was covalently conjugated to the CdS NC-electrode. The modification procedure was characterized by cyclic voltammetry, electrochemical impedance spectroscopy, and atomic force microscopy, respectively. The resulting modified electrode was tested as ECL biosensor for LDL detection. The LDL concentration was measured through the decrease in ECL intensity resulting from the specific binding of LDL to apoB-100. The ECL peak intensity of the biosensor decreased linearly with LDL concentration in the range of 0.025-16 ng mL-1 with a detection limit of 0.006 ng mL-1. The CdS NCs not only showed high ECL intensity and good bio- compatibility but also could provide more binding sites for apoB-100 loading. In addition, the gold nanoparticle amplification for protein ECL analysis was applied to the improvement of the detection sensitivity. Thus, the bio-sensor exhibited high sensitivity, good reproducibility, rapid response, and long-term stability. [ABSTRACT FROM AUTHOR]

To mimic the dynamic regulation of signaling ligands immobilized on extracellular matrices or on the surfaces of neighboring cells for guidance of cell behavior and fate selection, we have harnessed biomolecular recognition in combination with polymer engineering to create dynamic surfaces on which the accessibility of immobilized ligands to cell surface receptors can be reversibly interconverted under physiological conditions. The cell-adhesive RGD peptide is chosen as a model ligand. RGD is fused to the C-terminus of a leucine zipper domain A, and this fusion polypeptide is immobilized on surfaces through a residue at the N-terminus. The immobilized RGD can be converted from a cell-accessible to a cell-inaccessible state by addition of a conjugate of poly(ethylene) glycol (PEG) and another leucirie zipper domain B (B-PEG). Heterodimerization between A and B allows coimmobilization of the PEG, which shields RGD from access by cells. The shielded RGD can be converted back to a cell-accessible state by addition of nonimmobilized polypeptide A, which competes with the immobilized A for binding to B-PEG and removes B-PEG from the surface. This molecular design offers several advantages: the interconversion is reversible; the ligand remains immobilized during dynamic regulation so that cells are not exposed to the soluble form of the ligand that potentially has detrimental effects; the precision of the on/off states is assured by the molecular-level uniformity of the ligand and PEG coimmobilized through leucine zipper heterodimerization. The method can be readily adapted for dynamic regulation of other immobilized bioactive ligands of interest. [ABSTRACT FROM AUTHOR]

In the title compound, {[Zn(C8H4O4)(C24H16N2)]·H2O} n, the Zn center is coordinated by three O atoms from three different benzene-1,3-dicarboxyl­ate dianions and two N atoms from the bidentate 4,7-diphenyl-1,10-phenanthroline ligand to display a distorted trigonal–bipyramidal geometry. The benzene-1,3-dicarboxyl­ate ligand acts as a μ3-bridge, resulting in a two-dimensional coordination polymer with rhombus-shaped channels. [ABSTRACT FROM AUTHOR]

In the title compound, [Cd(C8H4O4)(C17H10N4O)] n, the CdII atom is six-coordinated by four O atoms from three different benzene-1,3-dicarboxyl­ate (C8H4O42−; 1,3-BDC) ligands and two N atoms from the bidentate 2-furan-2-yl-1 H-imidazo[4,5- f]-1,10-phenanthroline (C17H10N4O) ligand in a distorted octa­hedral geometry. The CdII atoms are bridged by the 1,3-BDC ligands to form a double-chain structure. Neighbouring double chains inter­act through π–π inter­actions, resulting in a two-dimensional network. [ABSTRACT FROM AUTHOR]

In the centrosymmetric title compound, [Zn2(C14H9N2O2)4], each ZnII centre is four-coordinated by two N atoms and two O atoms from three 2-(1 H-benzoimidazol-2-yl)benzoate ligands in a tetra­hedral environment. C—H⋯O and N—H⋯O hydrogen bonds stabilize the crystal structure. [ABSTRACT FROM AUTHOR]

In the title complex, [Cu2(C8H4O4)2(C6H6N2O)4]·3H2O, the CuII atom exhibits distorted trigonal–bipyramidal geometry and is coordinated by two N atoms of two isonicotinamide (inta) ligands and three O atoms of three isophthalate (ipt) ligands. C—H⋯O and N—H⋯O hydrogen bonds, as well as π–π stacking inter­actions, are observed between. [ABSTRACT FROM AUTHOR]

In the title compound, {[Pr(C12H15O6)(H2O)]·0.5H2O} n, the central praseodymium(III) cation is nine-coordinated by O atoms from six different chdc2− ligands (chdc2− is the 1,4-cyclo­hexane­dicarboxyl­ate dianion) and one terminal water mol­ecule. An inter­esting feature of the compound is the presence of two strands of cis-chdc2− ligands wrapped around each other, held together by praseodymium(III) cations to form a double-stranded chain. trans-Chdc2− ligands further bridge adjacent double-stranded chains to yield a three-dimensional framework. [ABSTRACT FROM AUTHOR]

In the mol­ecule of the title compound, C18H20N4, the cyclo­hexane ring has a chair conformation. The dihedral angle between the two planar pyridine rings is 68.19 (3)°. [ABSTRACT FROM AUTHOR]

In the title compound, [Cd(C8H4O4)(C7H6N2)2] n, the Cd atom is coordinated by four O atoms from two different benzene-1,4-dicarboxyl­ate (bdc) ligands and two N atoms from two different benzimidazole ligands. The bdc ligands bridge the Cd atoms to form a one-dimensional zigzag chain structure. [ABSTRACT FROM AUTHOR]

In the title compound, bis­(μ-pyridine-2,5-dicarboxyl­ato)bis­[aqua­(pyrazino[2,3- f][1,10]phenanthroline)manganese(II)] dihydrate, [Mn2(C7H3NO4)2(C14H8N4)2(H2O)2]·2H2O, each MnII atom is six-coordinated by three N atoms from one bidentate pyrazino[2,3- f][1,10]phenanthroline and one monodentate pyridine-2,5-dicarboxyl­ate ligand, and three O atoms from two monodentate pyridine-2,5-dicarboxyl­ate ligands and one water mol­ecule. The two MnII atoms are bridged by two pyridine-2,5-dicarboxyl­ate ligands, forming a centrosymmetric dinuclear molecule. Neighboring mol­ecules inter­act through π–π contacts, leading to a one-dimensional supra­molecular structure, and O—H⋯O hydrogen bonds complete the structure. [ABSTRACT FROM AUTHOR]

The structure of the title compound, [Cu2Cl2(C10H8N2)] n, consists of a two-dimensional layer. Each Cl atom bridges three Cu atoms to form a ladder-like structure, whereas the 4,4′-bipyridine ligands form a link between Cu atoms of adjacent ladders, thus building a two-dimensional layer structure. [ABSTRACT FROM AUTHOR]

In the title compound, poly[[(2-phenyl-1 H-1,3,7,8,-tetra­azacyclo­penta­[ l]phenanthrene)manganese(II)]-μ-benzene-1,3-dicarboxyl­ato], [Mn(C8H4O4)(C19H12N4)] n, the MnII atom is hexa­coordinated by two N atoms from the phenanthrene ligand, and four O atoms from three different benzene-1,3-dicarboxyl­ate ( m-BDC) ligands. The MnII atoms are bridged by the m-BDC ligands, forming a double-chain structure. Moreover, neighbouring double chains are in contact through π–π inter­actions, generating a two-dimensional supra­molecular structure. [ABSTRACT FROM AUTHOR]

In the title compound, [Cd( m-BDC)( L)], where m-BDC is the benzene-1,3-dicarboxyl­ate dianion (C8H4O42−) and L is 2-phenyl-1 H-1,3,7,8,-tetra­azacyclo­penta­[ l]phenanthrene (C19H12N4), the CdII atom is six-coordinated by one bidenatate L, one bidentate m-BDC and two monodentate m-BDC ligands, resulting in a very distorted cis-CdN2O4 octa­hedral coordination geometry. The CdII atoms are bridged by the m-BDC ligands to form an unusual double-chain structure. In addition, neighboring double chains inter­act through π–π inter­actions, resulting in a two-dimensional network. [ABSTRACT FROM AUTHOR]

An in situ reaction under hydro­thermal conditions leads to the formation of the title compound, diaqua­(pyridine-2-carboxyl­ato)­(pyridine-2,6-dicarboxyl­ato)indium(II) trihydrate, [In(C6H4NO2)(C7H3NO4)(H2O)2]·3H2O, in which the central InIII atom is seven-coordinated by one pyridine-2,6-di­carboxyl­ate ligand, one pyridine-2-carboxyl­ate ligand and two water mol­ecules in a penta­gonal–bipyramidal coordination environment. An indium(III)–water chain based on an unusual water pentamer is observed. [ABSTRACT FROM AUTHOR]

The title complex, [Hg2Br4(C18H22S2)] n, has a chain structure. Two bridging Br atoms and two terminal Br atoms coordinate to two HgII atoms to form a (HgBr2)2 dimer, and the 1,4-bis­(benzyl­sulfan­yl)butane ligands bridge the (HgBr2)2 dimers to form a one-dimensional chain. The dimer and butane ligand are each located on inversion centers. HgII adopts a tetra­hedral geometry formed by three Br and one S atoms. [ABSTRACT FROM AUTHOR]

The title complex, [Co(C10H6NO2)2(CH4O)2], is a neutral mononuclear complex containing a CoII ion in a six-coordinate environment. The CoII center, located on a crystallographic center of symmetry, displays a slightly distorted octa­hedral geometry, with two quinoline-8-carboxyl­ate and two methanol ligands in trans configurations. The complex mol­ecules are linked together by O—H⋯O and C—H⋯O hydrogen bonds between methanol mol­ecules and carboxyl­ate groups to form a three-dimensional framework. [ABSTRACT FROM AUTHOR]

In the structure of the title complex, [Cu(N3)2(C14H15N3O2)]·H2O, the Cu atom exhibits a CuN5O coordination environment formed by five N atoms, three from the N, N-bis­(2-pyridymeth­yl)glycine (bpg) ligand and two from azide anions, and one O atom belonging to bpg. The Cu—N distances range from 1.931 (3) to 1.960 (3) Å, with an average of 1.945 (3) Å, and the Cu—O distance is 1.900 (2) Å. The azide ligands are almost linear, with both N—N—N angles being 174.7 (4)°. [ABSTRACT FROM AUTHOR]

Two new three-dimensional (3D) porous structures based on the mixed flexible and rigid organic ligands, [Cd1.5(bmip)(tpa)1.5(DMF)1.5]n (1) and [Co1.5(bmip)0.5(bpdc)1.5(DMF)2]n (2) (bmip = 1,3-bis(2-methylimidazolyl)propane, H2tpa = terephthalic acid, H2bpdc = biphenyl-4,4'-dicarboxylic acid, DMF = N,N-dimethylformamide) have been prepared under solvothermal conditions. Complex 1 contains a trinuclear Cd unit, in which the trinuclear Cd cluster acts as an eight-connected node with two pairs of flexible bmip and six rigid tpa ligands. Complex 2 exhibits a two-fold interpenetrated porous network based on a trinuclear Co cluster as eight-connected vertices with two flexible bmip and six rigid tpa ligands. Both 1 and 2 show selective gas adsorption of CO2 over N2 and H2. Furthermore, complex 1 displays an uncommon CO2 adsorption isotherm and hysteretic desorption behaviors at 195 K. [ABSTRACT FROM AUTHOR]

Two novel Cu(II) compounds [Cu2(btb)3.5(C4AS)(H2O)]·2.5(H2O) (1) and [Cu2.5(btp)2(C4AS)(htz)(H2O)3]·4.75(H2O) (2) have been hydrothermally synthesized and structurally determined by single-crystal X-ray diffraction analyses (btb = 1,4-bis(1,2,4-triazol-1-yl)butane, btp = 1,5-bis(1,3,4-triazol-1-yl)pentane, htz = 1,3,4-triazolate, and C4AS = p-sulfonato-calix[4]arene). In 1, the btb ligands connect Cu(II) atoms to form a 3D porous framework. The 1D chains constructed by C4AS and Cu(II) atoms are further bonded to the 3D porous framework through the Cu–O bonds. Topologically, structure 1belongs to a 3D (3,6)-connected net with the Schläfli symbol of (42·6)(46·68·8). In 2, the C4AS links the Cu(II) atoms to form 1D chains, which are further connected by the btp and htz to generate a 3D (3,4,6)-connected framework with the Schläfli symbol of (62·8)(52·62·7·8)(54·62·7·87·9). The two compounds have been further characterized by infrared spectra (IR), elemental analyses, powder X-ray diffraction (PXRD), thermogravimetric (TG) analyses, and UV–vis absorption spectra. [ABSTRACT FROM AUTHOR]

In this article, five new silver(i) coordination polymers constructed from tetrakis(imidazol-1-ylmethyl)methane (L) and various anions have been synthesized, namely, [Ag(L)0.5](NO3)·0.5(H2O) (1), [Ag(L)0.25Br] (2), [Ag2L](mal)·6.25H2O (3), [Ag2L(1,3-bdc)]·4H2O (4), and [Ag2L(1,4-bdc)0.5]·0.5(1,4-bdc)·7.5H2O (5), where H2mal = maleic acid, 1,3-H2bdc = benzene-1,3-dicarboxylic acid, and 1,4-H2bdc = benzene-1,4-dicarboxylic acid. In compound 1, Ag(i) atoms are connected by the L ligands to form a 2D 4-connected square layer (sql) with free NO3−anions in the channels. The resulting layers are extended into 3D supramolecular frameworks through π–π interactions. In compound 2, the L ligands link the Ag4Br4cluster to form a two-fold interpenetrating diamond (dia) architecture. When the dicarboxylate ligands H2mal, 1,3-H2bdc and 1,4-H2bdc were used in the reaction, compounds 3–5were obtained. In compound 3, the Ag(i) atoms are bridged by the L ligands to furnish a 3D trinodal (3,4)-connected (62·8)(4·6·8)(4·62·82·10) net with the mal ligands just as free counteranions. In compound 4, the 1,3-bdc ligand coordinates to the Ag(i) center in a monodentate mode. The L ligands link the Ag(i) atoms to form a 2D double layer structure with point symbol (62·8)2(64.82). In compound 5, the L and 1,4-bdc ligands connect the Ag(i) atoms to form a complicated 3D (3,4)-connected framework with point symbol (4·102)2(42·6)2(42·103·12)(42·6·103)2. The influence of the anions on the structures of the coordination polymers has been discussed. Additionally, the luminescent properties of these compounds were also studied. [ABSTRACT FROM AUTHOR]

A series of structurally diverse metal–organic frameworks (MOFs), [Co4(TPOM)2(L1)4(H2O)4]·H2O (1), [Ni2(TPOM)(L2)2(H2O)2]·2H2O (2), [Co2(TPOM)(L2)2(H2O)2]·H2O (3), [Cu4(TPOM)2(L3)4]·3H2O (4), [Co2(TPOM)0.5(L4)] (5), and [Cd(TPOM)(L3)3]·7H2O (6), where TPOM = tetrakis(4-pyridyloxymethylene)methane, H2L1 = 1,3-benzenedicarboxylic acid, H2L2 = 5-hydroxyisophthalic acid, H3L3 = 1,3,5-benzenetricarboxylic acid, and H4L4 = 1,2,4,5-benzenetetracarboxylic acid, have been hydrothermally synthesized. These complexes were structurally characterized by X-ray diffraction analyses and further characterized by infrared spectra (IR), elemental analyses, powder X-ray diffraction (PXRD), and thermogravimetric (TG) analyses. Compound 1shows a 3D 4-connected framework with a rare (84·62) topology. Compounds 2and 3are isostructural and display 3D 2-fold interpenetrating frameworks with (64·82)(66)2topologies. Compound 4exhibits a 2-fold interpenetrating structure with a scarce trinodal (3,4,5)-connected (4·62)(4·69)66topology. Compound 5possesses a 3D 4-connected net with the TPOM ligands located in the 3D channels. Compound 6features 2D square layers (sql). The free TPOM ligands and L3 anions form discrete fragments through hydrogen bonds and π–π interactions. Interestingly, the fragments penetrate the 2D networks above and below to yield a unique 2D → 3D polythreading framework. The structural differences among such compounds show the effects of the carboxylates and central metals on the complex structures. The UV–vis absorption spectra, optical energy gap, and luminescent properties were also investigated for the compounds. [ABSTRACT FROM AUTHOR]

With 2-methyl-1,2,3,4-tetrahydroquinoline-derived phosphoramidite ligand (R,Ra)-L6, Ir-catalyzed intramolecular C-3 allylic alkylation of indoles has been realized to afford highly enantioenriched spiroindolenine derivatives in 92-98% yields with up to >99/1 dr and 97% ee. [ABSTRACT FROM AUTHOR]

Thirteen new metal–organic frameworks (MOFs), namely, [Zn2(L1)2(biim-4)(H2O)] (1), [Cd(HL1)2(biim-4)] (2), [Cd(HL2)2(biim-4)] (3), [Cd(HL3)2(biim-4)] (4), [Zn2(L4)2(biim-4)(H2O)] (5), [Cd(HL4)2(biim-4)] (6), [Zn2(L5)2(biim-4)(H2O)] (7), [Cd(HL5)2(biim-4)1.5]·H2O (8), [Zn2(L6)2(biim-4)(H2O)] (9), [Cd(HL6)2(biim-4)] (10), [Zn2(L7)2(biim-4)2]·H2O (11), [Cd2(L7)2(biim-4)2(H2O)]·H2O (12), and [Zn(HL8)(biim-4)]·0.5H2O (13), where H2L1 = salicylic acid, H2L2 = 3-methylsalicylic acid, H2L3 = 4-methylsalicylic acid, H2L4 = 4-chlorosalicylic acid, H2L5 = 5-chlorosalicylic acid, H2L6 = 5-bromosalicylic acid, H2L7 = 5-nitrosalicylic acid, H3L8 = 5-sulfosalicylic acid, and biim-4 = 1,1′-(1,4-butanediyl)bis(imidazole), have been synthesized under hydrothermal conditions. Compounds 1and 5are isomorphous, and show the same 3-connected 103-thsnet. Compound 2possesses a meso-helical chain structure. Compound 3shows a zero-dimensional (0D) dimeric molecular structure, which is linked by π–π interactions into a two-dimensional (2D) supramolecular assembly. Compounds 4and 6exhibit similar one-dimensional (1D) chains, which are extended into different 2D supramolecular layers via C–H···O and C–H···Cl hydrogen-bonding interactions, respectively. Compound 9is isomorphous with 7and displays a typical 3D diamond framework. Compound 8shows an unusual 2D → 3D polythreading array. Compound 10furnishes a 2D supramolecular (44)-sqlnetwork formed by C–H···Br hydrogen-bonding interactions. Compounds 11and 12exhibit binodal (4,4)-connected 3D frameworks with (4.53.72)(4.52.83) and (42.62.82)(42.6.82.10) topologies, respectively. Compound 13has a 3D 4-fold interpenetrating diamond framework. The TGA and luminescent properties of 1–13have also been investigated in detail. [ABSTRACT FROM AUTHOR]

Four octamolybdate hybrid materials based on a new flexible multidentate ligand, namely, H4L(γ-Mo8O26)·2H2O (1), [Cu(H2L)(β-Mo8O26)(H2O)2]·3H2O (2), [Cu(H2L)(γ-Mo8O26)]·3H2O (3), and Cu(HL)2(β-Mo8O26) (4), where Lis 1,1′-(1,4-butanediyl)bis[2-(4-pyridyl)benzimidazole], have been synthesized at different pH values under hydrothermal conditions. Compound 1, which is hydrothermally prepared at pH ≈ 1, exhibits a rare one-dimensional (1D) molybdenum oxide chain. Compounds 2and 3are hydrothermally obtained at pH ≈ 2.5. In 2, CuIIcations are bridged by H2L2阨᪝ and (β-Mo8O26)4–anions to form an interesting two-dimensional (2D) layer. In 3, the H2L2阨᪝ and (γ-Mo8O26)4–clusters bridge adjacent CuIIcations to form a 3D framwork. When the pH value is adjusted to 3.5, compound 4is obtained. Because the HL熫抢 acts as a monodentate ligand, compound 4only exhibits a 1D chain structure. The structural diversities of 1–4reveal that the pH value of the reaction system plays a crucial role in the assembly of POM-based metal–organic frameworks (MOFs). In addition, the electrochemical property of compound 4has also been investigated in 1 M H2SO4aqueous solution. [ABSTRACT FROM AUTHOR]

The solvothermal reactions of CuCN with two structure-related flexible 4-pyridyl dithioether ligands, bis(4-pyridylthio)methane (L1) and 1,2-bis(4-pyridylthio)ethane (L2), generated two novel three-dimensional (3D) coordination polymers: [(CuCN)5(L1)2]n(1) and [(CuCN)3(L2)]n(2), respectively. Their structures were determined by single-crystal X-ray diffraction analyses and further characterized by elemental analyses, IR spectra, and thermogravimetric analyses. Complex 1is constructed by the interconnection of CuCN layers with L1 pillars to form an interesting self-penetrating 123topological network with characteristic of four distinct helical chains. In 2, each L2 acting as a quadridentate μ3-bridge connects Cu atoms from three uncommon meso-helical CuCN chains, to give 3D framework containing 1D tubes constructed by two types of helical chains with opposite chirality. 2exhibits a 3-fold interpenetrating network with a rare (62·10)2(6·102) topology. In addition, the solid state samples of 1and 2exhibited different luminescent properties at room temperature. [ABSTRACT FROM AUTHOR]

In the title compound, [Co(C10H7NO2)2(H2O)2], the CoII ion lies on an inversion centre. It has a distorted octa­hedral geometry and is coordinated by two N, O-bidentate 5-phenyl-1 H-pyrazole-3-carboxyl­ate ligands and two water mol­ecules. Inter­molecular O—H⋯O and N—H⋯O hydrogen bonds link mol­ecules into layers parallel to the (010) plane. [ABSTRACT FROM AUTHOR]

In the title compound, [Cd(C8H4O4)(C3H4N2)2(H2O)] n, the Cd center is six-coordinated by three O atoms from two benzene-1,3-dicarboxyl­ate dianions, two N atoms from two imidazole ligands and one water mol­ecule in a distorted octa­hedral geometry. The benzene-1,3-dicarboxyl­ate dianion acts as a bridge, resulting in a one-dimensional chain-like structure. [ABSTRACT FROM AUTHOR]

In the title compound, [Cd(C6H7N2O5)2], the Cd atom lies on an inversion center and has a slightly distorted octa­hedral geometry. The equatorial plane contains two bidentate 5-carb­oxy-2-methyl-1 H-imidazole-4-carboxyl­ate monoanionic ligands. Two coordinated water mol­ecules occupy the axial sites. Inter­molecular N—H⋯O hydrogen bonds link the mol­ecules into chains, which are further connected by inter­molecular O—H⋯O hydrogen bonds, resulting in a three-dimensional supra­molecular framework. [ABSTRACT FROM AUTHOR]

In the title compound, [CuCl(C14H8N4)] n, the central CuI ion displays a distorted tetra­hedral geometry, coordinated by two Cl− ions and two N atoms from a bidentate pyrazino[2,3- f][1,10]phenanthroline (PyPhen) ligand. Each Cl− ion bridges two CuI atoms, forming a zigzag chain structure. Cu and Cl have site symmetry 2; the complete PyPhen molecule is generated by twofold symmetry. [ABSTRACT FROM AUTHOR]

In the title compound, [Mn(C8H4O4)(C19H12N4O)2] n or [Mn(1,4-BDC)( L)2] n, where 1,4-BDC is the benzene-1,4-dicarboxyl­ate dianion and L is 4-(1 H-1,3,7,8-tetra­azacyclo­penta­[ l]phenanthren-2-yl)phenol, the MnII atom is six-coordinated by two bidentate L and two monodentate 1,4-BDC ligands, resulting in a distorted trans-MnO2N4 octa­hedral geometry. The MnII atoms are bridged by the 1,4-BDC ligands, forming a single-chain polymer structure. In addition, neighboring single chains inter­act through π–π inter­actions, generating a two-dimensional network. Mn has site symmetry ; the complete 1,4-BDC unit is also built up by inversion symmetry. [ABSTRACT FROM AUTHOR]

In the title compound, [Zn(C8H4O4)(C17H10N4O)] n, the ZnII atom is five-coordinated by two N atoms from the phenanthroline-derived ligand and three O atoms from one bidentate and one monodentate benzene-1,2-dicarboxyl­ate (1,2-BDC) dianions in a distorted trigonal–bipyramidal geometry. The ZnII atoms are bridged by the 1,2-BDC ligands to form a single-chain structure. Neighboring chains inter­act through π–π inter­actions, leading to a two-dimensional network. [ABSTRACT FROM AUTHOR]

In the title compound, [Fe2(SO4)2(C18H10N4)2(H2O)4]·H2O, the FeII atoms are octa­hedrally coordinated by two N atoms from one bidentate dipyrido[3,2-a:2′,3′-c]phenazine (dppz) ligand, two O atoms belonging to two SO42− anions and two water O atoms. The two crystallographically independent dinuclear complex mol­ecules are both generated by inversion symmetry with the sulfate ions acting as bridges. Neighbouring dinuclear complexes inter­act via O—H⋯O hydrogen bonds, leading to a chain structure. [ABSTRACT FROM AUTHOR]

In the title compound, [CdCl2(C14H8N4)2], the central CdII ion is six-coordinate in an octa­hedral geometry, coordinated by two Cl− ions and four N atoms from two chelating pyrazino[2,3- f][1,10]phenanthroline ligands. The metal atom lies on a twofold rotation axis. [ABSTRACT FROM AUTHOR]

In the title compound, {[Mn(C7H3NO4)(C10H8N2)(H2O)]·H2O} n, the Mn(II) atom has a distorted fac-MnN3O3 octahedral coordination geometry, defined by one N, N′-chelating bipyridine molecule, one N-bonded pyridine-3,4-dicarboxylate (pdb) anion, two monodentate O-bonded pdb anions and one water molecule. Adjacent MnII ions are bridged by pairs of pdb ligands to form distinctive squares, which are further linked by other pdb ligands to result in a layered coordination polymer exhibiting a wave-like structure. Hydrogen bonds involving both the coordinated and uncoordinated water molecules help to consolidate the structure. [ABSTRACT FROM AUTHOR]

The title complex, [Hg2Br4(C7H16S2)]n, has a chain structure. Two bridging Br atoms and two terminal Br atoms coordinate to two HgII atoms, forming an (HgBr2)2 dimer, which is located on an inversion center. The 1,3-bis­(ethyl­sulfan­yl)propane ligands, which lie on a twofold axis, bridge the (HgBr2)2 dimers, forming a one-dimensional chain. The HgII atom adopts a tetra­hedral geometry, formed by three Br and one S atoms. [ABSTRACT FROM AUTHOR]

The title compound, [Cd(C8H4O4)(C18H10N4)] n, was synthesized under mild hydro­thermal conditions. The Cd center is coordinated by four O atoms from three different benzene-1,3-dicarboxyl­ate ligands and two N atoms from the dipyrido[3,2- a:2′,3′- c]phenazine ligand in a distorted octa­hedral geometry. The polymeric chain extends along the c axis, forming a one-dimensional helical structure. [ABSTRACT FROM AUTHOR]