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The 3 : 1 reaction of [Cu(C2H4)n]ClO4 with 2,4-bis(2-pyridyl)pyrimidine (bpprd) in Me2CO under C2H4 afforded yellow prism crystals of the dinuclear Cu(I)–C2H4 complex [Cu2(bpprd)(η2-C2H4)2(ClO4)2] (1). The 3 : 1 reaction of [Cu(C2H4)n]NO3 with bpprd in Me2CO under C2H4 afforded yellow plate crystals of the tetranuclear Cu(I)–C2H4 complex [Cu4(bpprd)2(η2-C2H4)4(μ-NO3)2](NO3)2 (2). The 10 : 1 reaction of [Cu(C2H4)n]BF4 with bpprd in Me2CO under C2H4 afforded yellow plate crystals of the dinuclear Cu(I)–C2H4 complex [Cu2(bpprd)(η2-C2H4)2(BF4)]BF4 (3). The 3 : 1 reaction of [Cu(C2H4)n]BF4 with bpprd in Me2CO under C2H4 afforded red prism crystals of the polymeric Cu(I)–C2H4 complex {[Cu6(bpprd)4(η2-C2H4)2(μ–η2:η2-C2H4)(μ-BF4)2](BF4)4}n (4). The X-ray crystal structures of complexes 1–4 have been determined. The structural diversity of Cu(I)–C2H4 complexes bridged by bpprd with different anions was demonstrated. The 1D Cu(I)–bpprd/C2H4 coordination polymer 4 bridged by unusual μ–η2:η2-C2H4 and the μ-BF4− anion is of particular significance. Complex 1 exhibited relatively well-resolved 1H NMR signals of bpprd and C2H4 (δ = 4.97 ppm) in (CD3)2CO at 23 °C. [ABSTRACT FROM AUTHOR]

In this paper, bis-monodentate Schiff base ligand (2,4-Cl-ba)2bn and its 1D copper(I) coordination polymer [Cu2(μ-(2,4-Cl-ba)2bn)(μ-I2)]n are synthesized and characterized by the elemental analysis (CHN), FT-IR and 1H NMR spectroscopy. Their crystal structure is determined from the single crystal X-ray diffraction analysis. The thermal behavior of the complex is studied using thermogravimetry in order to evaluate its thermal stability and thermal decomposition pathway. The X-ray results show that the free Schiff base ligand (2,4-Cl-ba)2bn is centrosymmetric and coordinated to copper(I) ions via two iminic nitrogen atoms as a bis-monodentate bridging ligand. The coordination geometry around the copper ions is a distorted triangle formed by one nitrogen and two iodine atoms. The distance between the two symmetry-related copper atoms is very short: 2.4756(8) Å. [ABSTRACT FROM AUTHOR]

[Display omitted] A selenoantimonate (C 4 H 14 N 2) 0.5 Cu 2 SbSe 3 (1) (C 4 H 12 N 2 = 1, 4-butanediamine) was synthesized by solvothermal synthesis using 1, 4-butanediamine as solvent. By single-crystal X-ray diffraction, compound 1 has a two-dimensional (2-D) layered structure composed of a protonated organic amine [(C 4 H 14 N 2) 0.5 ]+ and an anionic layer [Cu 2 SbSe 3 ]- containing the 6-membered rings (6-MR) Cu 2 SbSe 3 and the 10-membered rings (10-MR) Cu 3 Sb 2 Se 5. Solid-state UV-diffuse reflectance analysis showed that 1 has a band gap value of 1.85 eV, indicating its potential semiconducting properties. This paper studied the photodegradation properties of selenoantimonate containing the transition metal Cu for the first time, and found that its degradation rate methylene blue (MB) was 68.5 %. In addition, a series of characterizations were also performed. [ABSTRACT FROM AUTHOR]

The effect of chalcogen bonding interaction led to the interesting crystal packing and coordination geometry of copper(II) in novel organic-inorganic hybrids. The reactions of organic bridging ligands 1,2,5- benzothiadiazole (btd) and 1,2,5-benzoselenazadiazole (bsed) with CuCl2 and CuBr2 by slow diffusion of two miscible solvents afforded three isomorphic 2D-network polymers, [CuCl2(btd)]n (1), [CuBr2(btd)]n (2), and [CuCl2(bsed)]n (3), and one molecular hybrid, CuBr2(bsed)2 (4). The crystal structures of these novel hybrids were determined by single X-ray crystallography. The three isomorphic hybrids consist of 2-D sheets in which [Cu(µ-X)2]n infinite linear chains running along the a axis are linked through N-coordinated molecules of btd and bsed along the b axis. On the other hand, the crystal packing of 4 is strongly influenced by the presence of the [Se...N]2 supramolecular synthon and Se···Br short interactions, all based on chalcogen bonding, that link the dimeric complex molecules into two-dimensional arrays parallel to the ac plane. [ABSTRACT FROM AUTHOR]

Peculiar coordination compound Cu(Hbpt)(CH3CN)2PF6 (1) derived from 3,5-bis(4-pyridyl)-1H-1,2,4-triazole (Hbpt) is synthesized by the layer diffusion method and structurally characterized by single crystal and powder X-ray diffraction, elemental analysis, and infrared spectroscopy. Compound 1 exhibits a structure formed by cationic chains and anions with abundant supramolecular interactions. Solid-state photoluminescence experiments show that compound 1 exhibits relatively strong red emission with a peak around 656 nm, and the origin of the emission band may be ascribed to the metal-to-ligand charge transfer according to the calculation of the density of states. [ABSTRACT FROM AUTHOR]

Herein, we report the synthesis and crystal structure determination of a new Cu(II) coordination polymer (CP) with the formula [Cu(L -tryp)(azpy)1/2(H2O)(NO3)]∝ (CP1), which exhibits an unusual tryptophan coordination mode with copper(II) via carboxylate monodentate binding as well as chelation via Namino and Ocarbonyl groups. CP1 was prepared using the ligand L -tryptophan (L -tryp) and the co-ligand 4,4′-azopyridine (azpy), adapting the mixed-ligand approach and a solvothermal protocol. Single crystal X-ray structural analysis revealed that in CP1, Cu(II) sites show a distorted octahedral geometry, wherein the ligand L -tryp is coordinated through the carboxylate and amine groups, whereas the co-ligand azpy is coordinated to Cu(II) ions through the Npyridyl atom and thus maintains a distorted octahedral geometry around the Cu(II) ions. FT-IR and EPR spectra were also recorded to corroborate the structural analysis. Finally, CP1 was employed as a heterogeneous catalyst for the Suzuki cross-coupling reaction and afforded ∼98% yield under normal reaction conditions. [ABSTRACT FROM AUTHOR]

The thioether-functionalized 2-azabutadiene (iPrS)2C=C(H)-N=CPh2 L ligates to CdI2 and HgI2 to form the chelate compounds [CdI2{(iPrS)2C=C(H)-N=CPh2] (1) and [HgI2(iPrS)2C=C(H)-N=CPh2] (2). Their crystal structures were solved via X-ray diffraction. Both crystallize in the non-centrosymmetric space groups: monoclinic P21 (1) and orthorhombic P212121 (2), respectively. The closed-shell d10 metal centers are four-coordinated (two iodides and S and N coordinating atoms from the ligand L) in both complexes. The geometrical indexes τ indicate that a highly distorted trigonal pyramidal is adopted for 1 and a seesaw geometry for 2. The comparative nature of metal–ligand bonds is discussed on the basis of metric parameters and of QT-AIM (quantum theory of atoms in molecules) calculations. L was also treated with CuI to obtain the dinuclear species [LCu(μ2-I2)CuL] (3), in which the two Cu(I) centers are linked by a short metal–metal bond. The geometric and electronic properties of 3 are compared with those of 1 and 2. [ABSTRACT FROM AUTHOR]

In the present work, novel polymeric copper(II) coordination compounds, namely [Cu2(cpida)(H2O)4][Cu(cpida)]·3H2O (1) (cpida3− = 2-(carboxyphenyl)iminodiacetate anion) and Na[Cu(cpida)] (3), were synthesized and characterized using infrared spectroscopy, thermogravimetric analysis, elemental analysis, and single-crystal X-ray diffraction. Compound 1 was obtained by slowly evaporating an aqueous solution of H3cpida, copper(II) sulfate, and NaOH at room temperature. The structural characterization revealed that 1 is an ionic entity formed by the [Cu(cpida)]− anion and the [Cu2(cpida)(H2O)4]+ cation, both of polymeric 1D structure. Compound 3 was prepared under similar conditions from copper perchlorate and crystallized via acetone diffusion. It is a coordination polymer formed by the [Cu(cpida)]− units, and the sodium cation is present in the structure, counterbalancing the anion charge. Depending on the crystallization conditions, it was possible to obtain other solvation forms of these structures. Starting from the conditions of compound 1, via the diffusion of ethanol, [Cu2(cpida)(H2O)4][Cu(cpida)]·H2O·1/2EtOH (2) was precipitated, while a hydrate form of compound 3 with the formula Na[Cu(cpida)]·2H2O (4) was obtained via methanol diffusion. [ABSTRACT FROM AUTHOR]

Two one-dimensional copper(II) coordination polymers with different dissymmetrical N,N′- bis(substituted)oxamide ligands were synthesized, namely {[Cu(dmaepox)(dabt)]pic·HO} (1) and {[Cu(dmapob)(dabt)]NO·0.6HO} (2), where Hdmaepox and Hdmapob stand for N-(2-carboxylatophenyl)- N′-[3-(methylamino)propyl]oxamidate and N-(2-carboxylatophenyl)- N′-[3-(dimethylamino)propyl]oxamidate, respectively, and dabt is 2'2′-diamino-4'4′-bithiazole. Polymer 1 was characterized by elemental analyses, IR and electronic spectra and single-crystal X-ray diffraction. The crystal structure reveals that polymer 1 consists of many binuclear copper(II) units bridged by cis-oxamide and carboxylate groups. The two copper(II) ions are located in square-planar and square-pyramidal coordination environments, respectively. The separations of the Cu(II) atoms bridged by oxamide and carboxylate groups are 5.2035(7) and 5.1196(7) Å, respectively. The crystal structure of polymer 2 has been reported in our previous paper. However, its relative properties were not studied. In order to compare the influence of different bridging ligands on the cytotoxicities and DNA-binding properties, the cytotoxicities and reactivities towards DNA of polymers 1 and 2 were investigated. The results suggest that the two polymers can interact with herring sperm DNA in the mode of intercalation with binding affinities following the order of 1 > 2, and this is consistent with their in vitro cytotoxicities. [ABSTRACT FROM AUTHOR]

The electrostatic self-assembly reaction of the [Cu(HL)]2+ cation, where HL = 2-(2-aminoethylamino) ethanol, and the N3− or [Fe(CN)6]4− anion leads to the formation of two coordination polymers with the general formula of [Cu6(μ1,1-N3)6(μ1,3-N3)2(μ1,1,3-N3)2(μ1,1,1,3-N3)2(HL)2]n (1) and {[Cu(HL)]2[Fe(CN)6]·H2O}n (2), respectively. The resulting compounds have been structurally characterized by a single-crystal X-ray diffraction technique. Compound 1 possesses a rare 3D structure. It contains centrosymmetric hexanuclear repeating units, which act as six-connected nodes in the final network and copper(ii) ions are joined together by azide anions with four different types of bridging modes, μ1,1, μ1,1,3, μ1,1,1,3, and μ1,3. The structure of compound 2 is a 2D heterometallic CuII/FeII layer in which the [Cu(HL)]2 nodes and the octahedral [Fe(CN)6]4− linkers are joined by μ2- and unusual μ3-CN bridging modes. Detailed static and dynamic magnetic analyses of 1 reveal a dominant ferromagnetic intracluster interaction and a ferromagnetic 3D ordering transition below Tc = 5 K. The variable temperature magnetic susceptibility measurements of compound 2 show a very weak ferromagnetic coupling between the nearest Cu(ii) ions. Also, EPR spectroscopy of these compounds has been investigated in the solid state. Nanocrystals of compound 2 have also been synthesized by a sonochemical process under different reaction conditions. The results show that the crystallinity degree and uniform distribution of nanosheets are inversely dependent on the irradiation time. [ABSTRACT FROM AUTHOR]

We report the synthesis and structural, spectroscopic and magnetic properties of new 1D coordination polymeric complex {[Cu(μ-l-Arg)2]SO4⋅1.5H2O}n (1) that contains asymmetric μ−O,O' carboxylic bridge linking distorted square-pyramidal [Cu(μ-l-Arg)2]2+ coordination units. In 1D, the syn−anti−μ2−η1:η1zigzag polymer conformation, the adjacent Cu(II) ions are distanced by 5.707 Å, and the subsequent Cu∙∙∙Cu proximity in 1D-coordination chain equals 6.978 Å. Detailed interpretation of IR and Raman spectra of l-arginine and 1 was performed. The principal components of the g tensor determined from EPR experiments (gx = 2.059, gy = 2.075, gz = 2.228) indicate nearly axial symmetry of Cu(II) coordination sphere and correspond to the unpaired electron occupying the dx2–y2 orbital. The single broad band at 16,200 cm–1, characteristic of d−d transition, is assigned to the dominant dublet-dublet 2B1g(dx2–y2)→ 2Eg(dyz≈dxz) transition. Magnetic susceptibility measurements have revealed ferromagnetic coupling between the Cu(II) ions within the 1D-coordination chain, while the intermolecular coupling is antiferromagnetic. [ABSTRACT FROM AUTHOR]

A combination of 4-styrylpyridine (spy) and 1-adamantanecarboxylic acid (Hadc) was employed in the assembly reactions with Zn(II) and Cu(II) nitrates. The photoreactivity of the products was compared and discussed on the basis of the structure–function relationship. Zinc(II) complex 1 is a trinuclear species of type [Zn3(spy)2(adc)6] in which three zinc(II) atoms are linearly arranged, with two adjacent zinc(II) atoms linked by three bridging carboxylates. Two spy ligands occupy both terminal positions, yielding the overall structure of a six-bladed windmill. Copper(II) complex 2, [Cu(spy)2(adc)2][Cu2(spy)2(adc)4]·2DMF, is an inorganic cocrystal comprising a mononuclear complex with a trans square planar geometry and a dinuclear complex with a paddle-wheel structure. In the photoreaction experiments characterized by 1H NMR spectroscopy, the zinc(II) complex was found to be photoinert, while the copper(II) complex was photoreactive to form a cyclobutene ring via the [2+2] photodimerization between two spy ligands, resulting in the preparation of a one-dimensional chain as a coordination polymer. The separations of the C=C bond pair obtained from the crystal structures for both products also support their photoreactivity. For example, the spy ligands from two adjacent monocopper(II) complexes are aligned in a head-to-tail manner with the separation of 3.899 Å between the C=C bond pair, satisfying the so-called Schmidt criteria (<4.2 Å). However, no other products satisfy this condition. [ABSTRACT FROM AUTHOR]

Two modified Calix[6]arene‐like polyoxometalates of the Keggin type with similar structures were synthesized under hydrothermal conditions by H3PMo12O40. H3PW12O40, 4H‐1,2,4‐triazol‐3‐amine (3‐atrz) and copper ions were used as precursors, respectively, bridging organic ligand and transition metals. The result of single‐crystal X‐ray diffraction and elemental analysis showed that the structural formulas of the two crystalline compounds were: [2(C6H12N12Cu3PW12O40)] (3‐atrz‐Cu‐PW12), and [2(C6H12N12Cu3PMo12O40)] ⋅ 0.5H2O (3‐atrz‐Cu‐PMo12). They were composed of two classic Keggin‐type polyoxometalate anions and six [Cu(C2H4N4)]+ coordination polymers similar to Calix[6]arene. The catalytic studies represented that the two heterogeneous catalysts catalyzed the oxidation of iodide ions in hydrogen peroxide. The catalytic reaction of 3‐atrz‐Cu‐PW12 only took 30 min and 15 s to complete the reaction. The rate of iodine generation was 6.86×10−7 mol L−1 s−1. The 3‐atrz‐Cu‐PMo12 catalytic reaction needed only 1 min and 51 s, in which the rate of iodine generation was 1.126×10−5 mol L−1 s−1. The catalytic reaction rate of 3‐atrz‐Cu‐PMo12 was 16.35 times higher than 3‐atrz‐Cu‐PW12. Both catalysts were reused nine times, and the conversion rate was still 99.96 %, showing excellent catalytic activity and repeatability. [ABSTRACT FROM AUTHOR]

The reaction of Cu(II) and pyrazole-3,5-dicarboxylic acid (H3pzdc) with 1,2-di(4-pyridyl)ethane (bpa) at various temperatures and solvents results in the formation of seven new Cu(II) complexes, namely, [Cu2(pzdc)2(H2O)2](H2bpa)(H2O)6 (1), [Cu2(pzdc)2(H2O)2](H2bpa)(H2O)4 (2), [Cu3(pzdc)2(H2O)4(bpa)]n (3), [Cu4(pzdc)4(H3pzdc)2(H2O)2](H2bpa)2(H2O)2 (4), {[Cu4(pzdc)4(bpa)2](DMF)(NH2(CH3)2)4}n (5), {[Cu2(pzdc)2](H2bpa)}n (6), and {[Cu2(pzdc)(bpa)2](BF4)}n (7). Complexes 1 and 2 were prepared in an aqueous solution at different temperatures. Similar cyclic dinuclear Cu(II) anionic units are present in both complexes, but their crystal structures and lattice water molecule contents are different. When the aqueous medium was replaced with different solvent mixtures under the same hydrothermal conditions as 2, a variety of Cu(II) complexes 3–7 were generated. A one-dimensional (1D) coordination chain containing a [Cu3(pzdc)2] secondary building unit of 3 was obtained in a water and N,N′-dimethylformamide (DMF) mixture. An anionic tetranuclear Cu(II) complex of 4 was formed in water and an ethanolic mixture. When using pure DMF, an anionic 1D zigzag coordination chain of 5 was obtained. Whereas a 1D ladder-like coordination chain of 6 was formed in a DMF and acetonitrile (MeCN) mixture. Upon using EtOH or MeCN, a 3D pillar-layer cationic coordination framework of 7 was produced. Moreover, the temperature and solvent induced structural transformation of complex 1 was revealed. [ABSTRACT FROM AUTHOR]

A coordination polymer Cu(3-CP)3(NO3) (1) was synthesized from copper(II) sulfate and 3-cyanopyridine (3-CP) with in-situ reduction by hydroxylamine sulfate via the solvent evaporation method at room temperature, and structurally characterized by single-crystal X-ray diffraction and elemental analysis. Complex 1 exhibits a structure formed by cationic [Cu(3-CP)3]nn+ chains and NO3− anions with abundant supramolecular interactions. Solid-state photoluminescence experiments show that complex 1 exhibits a relatively strong blue-green emission, and its possible emission mechanism was investigated in detail based on theoretical calculations. [ABSTRACT FROM AUTHOR]

A new coordination polymer of coper (II), [tetra-azido)tris(2-pyridyl)amine)dicopper(II)] (1) has been synthesized by the reaction between copper(II) nitrate hexahydrate, sodium azide and tris(2-pyridyl)amine under solvothermal conditions in aqueous methanol. The structure has been characterized by single-crystal X-ray diffraction. An analysis of Hirschfeld surfaces was examined. Single-crystal results reveals that the structure contains two independent copper(II) centers, both having approximately square pyramidal coordination: in one, two of the basal sites are occupied by bidentate tris-(2-pyridyl)amine and two azido ligands, with a third azido ligand at the apical site, while the other center is coordinated only by azido ligands. All azido ligands bind two copper centers, forming a coordination polymer chain with two types of Cu2N2 rings and one type of Cu4N4 ring, and in which all azido ligands form a bridge between two metal centers in mode µ-1,1. The Hirshfeld analysis revealed an azido··· (pyridyl) interaction in the coordination polymer chain, as well as weak C-H···N interactions, one of which links the chains into sheets. A new dinuclear copper (II) polymer [tetra-azido(tris(2-pyridyl)amine)dicopper(II)] (1) has been synthesized under solvothermal conditions and been characterized by single-crystal X-ray diffraction and Hirshfeld surface analysis. [ABSTRACT FROM AUTHOR]

Employing the new nitronyl nitroxide biradical ligand biNIT-3Py-5-Ph (2-(5-phenyl-3-pyridyl)-bis(4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide)), a 16-spin Cu-radical complex, [Cu8(biNIT-3Py-5-Ph)4(hfac)16] 1, and three 2p-3d-4f chain complexes, {[Ln(hfac)3][Cu(hfac)2]2(biNIT-3Py-5-Ph)2}n (LnⅢ= Gd 2, Tb 3, Dy 4; hfac = hexafluoroacetylacetonate), have been prepared and characterized. X-ray crystallographic analysis revealed in all derivatives a common cyclic [Cu-biNIT]2 secondary building unit in which two bi-NIT-3Py-5-Ph biradical ligands and two CuII ions are associated via the pyridine N atoms and NO units. For complex 1, two such units assemble with four additional CuII ions to form a discrete complex involving 16 S = 1/2 spin centers. For complexes 2–4, the [Cu-biNIT]2 units are linked by LnIII ions via NO groups in a 1D coordination polymer. Magnetic studies show that the coordination of the aminoxyl groups with Cu or Ln ions results in behaviors combining ferromagnetic and antiferromagnetic interactions. No slow magnetic relaxation behavior was observed for Tb and Dy derivatives. [ABSTRACT FROM AUTHOR]

Chain coordination polymer [Cu(bpy)3][{Cu(bpy)}2Re4Se4(CN)12]·3.5H2O (1) is obtained by the reaction of K4[Re4Se4(CN)12]·6H2O with CuCN and 2,2′-bipyridilne (bpy) under hydrothermal synthesis conditions. The compound crystallizes in the orthorhombic system, space group Fdd2, with unit cell parameters a = 67.102(4) Å, b = 38.374(2) Å, c = 11.3329(5) Å, V = 29182(3) Å3, Z = 16, dcalc = 2.192 g/cm3. The crystal structure is composed of [{Cu(bpy)}2Re4Se4(CN)12]2– anionic polymer chains and [Cu(bpy)3]2+ complex cations located in cavities. The prepared compound is characterized by single crystal XRD, IR, and elemental analysis. [ABSTRACT FROM AUTHOR]

Employment of N,N′‐bis(2‐hydroxy‐4‐carboxyphenyl)oxalamide (H6L) in Cu2+ chemistry afforded the mononuclear complex (Et4N)4[CuL] ⋅ 13H2O (A) which comprises a square planar [CuL]4− complex with several O donor atoms in its periphery. The 1 : 1 reaction between complex A and Ln(NO3)3 ⋅ xH2O (Ln=La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er and Yb, x=6 or 9) in 1 : 4 mixture of ethanol/water in the presence of excess of KCl yielded two families of isomorphous 3d/4f coordination polymers, namely (Et4N)0.5[K0.5(H2O)Ln(H2O)4(CuL)] ⋅ 3H2O [Ln=La(1), Ce(2), Pr(3), Nd(4), Sm(5), Eu(6) and Gd(7)] and [K(H2O)Ln(H2O)4(CuL)] ⋅ ⋅6H2O [Ln=Tb(8), Dy(9), Ho(10), Er(11) and Yb(12)]. The crystal structures of 2–4 revealed the presence of 3D coordination polymers while the crystal structure of 9 the presence of a 2D coordination polymer. In both 3d/4f families, complex A retains its original structure and serves as a "metallo‐ligand". The magnetic properties of 2–4, 7–9, 11 and 12 are discussed. [ABSTRACT FROM AUTHOR]

The title complex, [Cu(C6H4N3)] n, was synthesized by the reaction of cupric nitrate, 1 H-benzotriazole (BTAH) and aqueous ammonia under hydrothermal conditions. The asymmetric unit contains three crystallographically independent CuI cations and two 1 H-benzotriazolate ligands. Two of the CuI cations, one with a linear two-coordinated geometry and one with a four-coordinated tetrahedral geometry, are located on sites with crystallographically imposed twofold symmetry. The third CuI cation, with a planar three-coordinated geometry, is on a general position. Two CuI cations are doubly bridged by two BTA− ligands to afford a noncentrosymmetric planar [Cu2(BTA)2] subunit, and two [Cu2(BTA)2] subunits are arranged in an antiparallel manner to form a centrosymmetric [Cu2(BTA)2]2 secondary building unit (SBU). The SBUs are connected in a crosswise manner via the sharing of four-coordinated CuI cations, Cu-N bonding and bridging by two-coordinate CuI cations, resulting in a one-dimensional chain along the c axis. These one-dimensional chains are further linked by C-H...π and weak van der Waals interactions to form a three-dimensional supramolecular architecture. [ABSTRACT FROM AUTHOR]

d-Block transition metal(II)-lanthanide(III) (3d-4f) hetero‐trinuclear [Cu(II)2Ln(III)] (Ln = La and Ce) complexes [Cu2La(L)(ƞ2-NO3)3(CH3OH)2]·2CH3OH (1) and [Cu2Ce(L)(ƞ2-NO3)3(CH3OH)2]·2CH3OH (2) are described, both of which are formed by a flexible symmetrical bis(salamo)-type ligand H4L. The two 3d-4f complexes have been synthesized and characterized by elemental analyses, IR spectra and UV–Vis spectroscopy. The crystal structures of 1 and 2 were determined by single-crystal X-ray diffraction analyses. In 1 and 2, each Cu(II) ion (Cu1 or Cu2) is located in the N2O2 cavity of an (L)4− unit, while the apex is occupied by one oxygen atom of the coordinated methanol molecule, forming a penta-coordinated square pyramidal geometry. The lanthanide(III) (La or Ce) ion is located in the O6-donor coordination sphere of the completely deprotonated (L)4− unit and coordinated with the other six oxygen atoms of the three nitrate ligands to form a twelve-coordinated icosahedron. At the same time, the supramolecular structures are formed by intermolecular hydrogen bonding interactions and quantitatively determined by Hirshfeld surfaces analyses. Fluorescence properties and DFT calculations of 1 and 2 were also studied. [ABSTRACT FROM AUTHOR]

A new coordination polymer, {[Na 2Cu(Ac) 4(H 2O)]·H 2O} n (HAc = acetic acid), has been synthesized and structurally characterized by IR spectroscopy and X-ray crystallography. The compound crystallizes in the orthorhombic system, space group Pccn with a = 16.9076(17) Å, b = 11.8375(12) Å, c = 15.7567(16) Å, V = 3153.6(6) Å 3. Four oxygen atoms from different Ac − groups coordinate to the copper atom in a square-planar arrangement. Each sodium ion is in a distorted octahedral environment, being coordinated by one aqua ligand and five acetate oxygen atoms from two adjacent [Cu(Ac) 4] units. An alternating arrangement of metal ions and bridging acetate ligands results in the formation of two-dimensional sheets which are further linked into a three-dimensional network by the water molecules between the layers through rich hydrogen bonds. Graphical Abstract: The title compound {[Na 2Cu(Ac) 4(H 2O)]·H 2O} n (HAc = acetic acid) was synthesized and structurally characterized by X-ray crystallography. Four oxygen atoms from different Ac– groups coordinate to the copper atom in a square-planar arrangement. Each sodium ion is in a distorted octahedral environment, being coordinated by one aqua ligand and five acetate oxygen atoms from two adjacent [Cu(Ac) 4] units. An alternating arrangement of metal ions and bridging acetate ligands results in the formation of two-dimensional sheets which are further linked into a three-dimensional network by the water molecules between the layers through rich hydrogen bonds.[Figure not available: see fulltext.] [ABSTRACT FROM AUTHOR]

Two metal organic frameworks involving α, ω-dicarboxylates and 2,2′-bpy, [Cu(2,2Bpy)(μ-adipate-H2)] n·2·H 2O 1 and [Cu 2 (2,2′-bpy) 2(μ-adipate-H) 2(μ-adipate-H2)]·3H 2O 2 have been synthesized by one pot reaction and structurally characterized. Pentacoordinated Cu(II) zigzag polymeric chain of 1 is composed of linking the adjacent Cu(2,2′-bpy)(H 2O) units through terminal craboxylate oxygens of two different adipate dianion in cis coordination pattern with the metal center. Both the Complexes were crystallized in triclinic system, P-1 space group with cell parameters a = 6.8948(5), b = 10.7098(7), c = 12.4332(8) Å; α = 82.1120(10), β = 80.4950(10), γ = 72.9560(10)°, V = 861.87(10) Å 3 for 1, a = 9.5058(6), b = 9.9341(7), c = 12.6460(8) Å; α = 70.5080(10), β = 73.5740(10), γ = 75.0720(10)°, V = 1062.05(12) Å 3 for 2 respectively. Extensive hydrogen bonding interaction is observed between the lattice water molecules and the coordination network. Compound 2 is a layered architecture, where the neutral framework is constructed by two different adipate anions (in monoanionic and dianionic form) coordinating to the metal center. Interestingly, three water molecules present in the lattice of compound 2 are involved in hydrogen bonding network among themselves, creating a centro-symmetric hexameric water cluster composed of a tetracyclic ring with dangling water molecules attached at alternate positions of the rectangle, which interact with the carboxylate oxygen, thereby extending the hydrogen bonded water network. Graphical Abstract: Two ternary Cu(II) metal-organic coordination networks involving N-donor ligand and adipic acid have been synthesized by one pot reaction . Single crystal investigation revealed that 1 is a zigzag and 2 is a layered network with Cu(II) possessing a distorted square pyramidal geometry . In both the complexes, intricate hydrogen bonding interaction exists between the lattice water molecules with the coordination framework. However, in complex 2, a new topology of hexameric water cluster residing between the adjacent layers of the coordination polymeric network involving hydrogen bonding interactions with the carboxylate oxygens has been observed.[Figure not available: see fulltext.] [ABSTRACT FROM AUTHOR]

Porous framework coordination polymer (enH)(enH2)[{Cu2(μ-CN)}Re6S8(CN)6] (1) is obtained by a reaction of Cs2.67K1.33[Re6S8(CN)2(OH)4]·4H2O, CuCN, and ethylenediamine (en) under hydrothermal conditions at 150 °С. The compound crystallizes in the cubic crystal system, space group , unit cell parameters a = 16.5097(2) Å, V = 4500.05(9) Å3, Z = 4, dcal = 2.664 g/cm3. The crystal structure is composed of the [{Cu2(μ-CN)}Re6S8(CN)6]3– anionic framework and protonated en molecules located in cavities. The compound obtained is characterized by X-ray crystallography, IR spectroscopy, and the elemental analysis. [ABSTRACT FROM AUTHOR]

Two new coordination polymers, namely, [Cu2(L)2(4,4′-bpy)]n (1) and [Cd(HL)Cl(1,10′-phen)]n (2) (H2L = 1H-pyrazole-3-carboxylic acid, 4,4′-bpy = 4,4′-bipyridine, 1,10′-phen = 1,10-phenanthroline) have been synthesized via solvothermal method and were structurally characterized by single-crystal X-ray diffraction, FT-IR, elemental analysis and PXRD. The two complexes are both infinite 1D chain structures, in complex 1 the H2L ligands are completely deprotonated and chelating the metal centers, and 4,4′-bipyridine link adjacent metal units to form a 1D chain structure. While, in complex 2, the auxiliary ligands chelating the metal center and H2L ligands play a role in chelating-bridging the metal centers to help build an infinite 1D chain structure. What's more, the two complexes further extended to 3D supramolecular networks by hydrogen bonds and weak C–H⋯π interactions. The weak intermolecular interactions existed in the complexes structures were further studied by Hirshfeld surface analysis and 2D fingerprint plots. In addition, these two transition metal complexes exhibit high intense electrochemiluminescence (ECL) in N,N-dimethylformamide (DMF) and after ten circulations the ECL intensity still remains stable, which can be a useful guide for the construct of new polymers ECL materials. [ABSTRACT FROM AUTHOR]

Chain coordination polymer [Cu(NH3)2]2[{Cu(NH3)}2{Cu(NH3)(OH)}Re6Se8(CN)6] (1) is obtained by a reaction of Cs2.75K1.25[Re6Se8(CN)4(OH)2]·H2O with CuCN in the concentrated aqueous ammonia solution under hydrothermal conditions. The compound crystallizes in the hexagonal crystal system with the P63/m space group and unit cell parameters a = 9.9902(2) Å, b = 9.9902(2) Å, c = 19.4469(7) Å, γ = 120.00°, V = 1680.85(8) Å3, Z = 2, dcalc= 4.661 g/cm3. The crystal structure is composed of anionic polymer chains [{Cu(NH3)}2{Cu(NH3)(OH)}Re6Se8(CN)6]2– and complex [Cu(NH3)2]+ cations located in cavities. The obtained compound is characterized by single crystal X-ray diffraction, IR spectroscopy, and the elemental analysis. [ABSTRACT FROM AUTHOR]

Crystal structure of [diaqua[2,2'-(1,2-phenylene)bis(1H-imidazole-4-carboxylato-5-carboxy)- 4N,N',O,O']nickel(II)] tetrahydrate, C16H12N4NiO10-4H2O There are O-H---O intramolecular hydrogen bonds between carboxyl and carboxylate groups, N-H---O intermolecular hydrogen bonds between imidazole units and solvent water molecules and O-H---O intermolecular hydrogen bonds involving coordination water molecules, solvent water molecules and carboxylate groups. Each Ni1 ion is six-coordinated and located in a distorted octahedral NiN SB 2 sb O SB 4 sb coordination environment formed by two N atoms (N1 and N1#1) and two O atoms (O1 and O1#1) from one H SB 4 sb Phbidc SP 2- sp anion and by two water molecules (O5 and O6). [Extracted from the article]

Complex [Cu(tbt)Cl2]n (tbt = 1‐tert‐butyl‐1H‐tetrazole) was prepared by reaction of tbt with copper(II) chloride in solution. According to single‐crystal X‐ray analysis, this complex presents 1D coordination polymer, formed at the expense of double chlorido bridges between neighboring pentacoordinate copper(II) cations. 1‐tert‐Butyl‐1H‐tetrazole acts as monodentate ligand coordinated by CuII cations via the heteroring N4 atoms. The temperature‐dependent magnetic susceptibility measurements of novel complex [Cu(tbt)Cl2]n as well as described previously 1D coordination polymer [Cu(tbt)2Cl2]n, and linear trinuclear complex [Cu3(tbt)6Br6], were carried out. Magnetic studies revealed that the copper(II) ions were weakly ferromagnetically coupled in polymeric copper(II) chloride complexes, whereas complex [Cu3(tbt)6Br6] showed antiferromagnetic coupling. [ABSTRACT FROM AUTHOR]

A newly synthesized coordination polymer, [(CH3)3NH]2[CuZn(CN)5], was investigated using 13C and 63Cu solid‐state NMR techniques and single‐crystal X‐ray diffractometry. It consists of a three‐dimensional (3D) net composed of tetrahedral CuI and ZnII ions and CN– ligands bridging between the two metal ions. (CH3)3NH+ ions are trapped in the inner space of the 3D net. Three coordination sites of each metal ion are used for the formation of the 3D net and the remaining site is occupied by a unidentate CN– ligand. The structure of the 3D net is chiral and categorized as srs in the notation of the Reticular Chemistry Structure Resource (RCSR). In water vapor or open air at room temperature under ambient pressure, a powder of [(CH3)3NH]2[CuZn(CN)5] showed a structural transformation to [(CH3)3NH][CuZn(CN)4]·1.5H2O, which is a known compound with a diamond‐like 3D net of [CuZn(CN)4]– composed of tetrahedral CuI and ZnII ions and bridging CN– ligands. 63Cu solid‐state NMR spectroscopy revealed that the Cu‐CN‐Zn orientation of the bridging CN– ligands was conserved after the structural transformation. [ABSTRACT FROM AUTHOR]

Combustion of fuels containing organosulfur compounds has resulted in the emission of sulfur oxides (SOx) into the atmosphere, therefore, causing serious environmental and health hazards. Herein, slightly distorted octahedral zig-zag 1D coordination polymer of copper(II) [Cu(4-mba)2(H2O)3] was synthesized by reacting copper sulfate pentahydrate with a carboxylate-containing ligand (H-4mba = 4-methoxybenzoic acid) and employed for sulfur compound uptake. The ligand coordinates to the copper(II) atom via two pairs of deprotonated ligating atoms (carboxylate oxygens) and two water molecules. Structural characterization also reveals that interplay of O-H···O, N-H···O, C-H···O and C-H···π interactions between lattice and coordinated water and ligands significantly contribute to the crystal packing leading to the formation and strengthening of three-dimensional supramolecular assembly. The complex, [Cu(4-mba)2(H2O)3], show potential for desulfurization of fuel with an observed adsorption capacity of 9.6 mg/g at 32°C for 6 h. DFT calculations further revealed a transfer of electron sulfur-containing compounds and the complex, [Cu(4-mba)2(H2O)3], thus leading to a stronger pi-pi interaction. [ABSTRACT FROM AUTHOR]

Two new Cu(ii) coorclination polymers [Cu(Fbtx)(H2btec)(H2O2)n and {[Cu(Fbtx)(btec)0.5(H2O2)]·H2O·}nhave been synthesised by hydrothermal reactions of Cu(ii) nitrate with 1,4-bis(1,2,4-triazole-1-ylmethyl)-2,3,5,6-tetrafluorobenzene (Fbtx) and 1,2,4,5-benzenetetracarboxylic acid (H4btec) under different pH conditions. The first complex has a two-dimensional four-connected layer structure with a 44-sql topology, whereas the second has a two-dimensional three-connected brick-wall network. The luminescence properties of the complexes in the solid state and their thermal stabilities have also been studied. [ABSTRACT FROM AUTHOR]

Abstract: By utilizing the flexible quadritopic ligand, tetrakis(3-pyridyloxymethyl)methane (L), two novel coordination polymers have been synthesized and structurally characterized. {[Cu3(L)2(acetate)6]·10(H2O)}n has a 1D chain crystal structure with a SP 2-periodic net with the Schläfli symbol {36·46·53} modeled by acetate ions. In {[Cu2(L)(benzoate)4]·2(CH3OH)·H2O}n, we substituted the acetate with benzoate and obtained 2D crystal structure with an novel 2, 3, 4 net with the Schläfli symbol {4·82}2{42·82·102}{8}. The structural results show that utilizing a flexible ligand is a good approach to achieve diversity in coordination polymer structures and could be easily affected by the carboxylate anions.Graphical Abstract: Two novel coordination polymers assembled from the tetrakis(3-pyridyloxymethylene) methane(L) with copper(II) ions and different carboxylate. Crystal structures and topological analyses of these compounds are presented. [ABSTRACT FROM AUTHOR]

Green crystals of the coordination polymer (CP) [CdN3(en)(n)], 1, was obtained by reaction of CdSO4 · 5H2O with ethyl nicotinate (en) in the presence of NaN3. The structure of the CP 1 was characterized by elemental analysis, IR, 1H-NMR, UV-Visible and X-ray single crystal analysis. The ORTEP plot of CP 1 consists of [(Cd)4(N3)4(en)4(n)4] structure exhibiting 14-atom V-shaped cyclic configuration, which contains 8-atoms ring [(Cd)4(N3)4]. The structure of CP 1 creates 1D-chain where the cyclic structures are connected by two nicotinate ligands (n). The chains are extended in three directions forming 3D-network structure via extensive H-bonds. The CP 1 was tested as corrosion inhibitor for copper in 1 M HCl solution using potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) techniques. The results of polarization indicated that CP 1 acts as mixed type inhibitor. Adsorption of CP 1 obeyed Langmuir adsorption isotherm. Effect of temperature on the corrosion process was studied and activation parameters were calculated and discussed. The results obtained from the two different electrochemical techniques are in good agreement. [ABSTRACT FROM AUTHOR]

Blue single crystals of Cu[μ3-O3P(CH2)2COOH]·2H2O (1) and Cu[(RS)-μ3-O3PCH(C2H5)COOH]·3H2O (2) were prepared in aqueous solutions (pH = 2.5-3.5). 1 crystallizes in space group Pbca (no. 61) with a = 812.5(2), b = 919.00(9), and c = 2102.3(2) pm. Cu2+ is fivefold coordinated by three oxygen atoms stemming from [O3P(CH2)2COOH]2- anions and two water molecules. The Cu-O bond lengths range from 194.0(3) to 231.8(4) pm. The connection between the [O3P(CH2)2COOH]2- anions and the Cu2+ cations yields a polymeric structure with layers parallel to (001). The layers are linked by hydrogen bonds. 2 crystallizes in space group Pbca (no. 61) with a = 1007.17(14), b = 961.2(3), c = 2180.9(4) pm. The copper cations are surrounded by five oxygen atoms in a square pyramidal fashion with Cu-O bonds between 193.6(4) and 236.9(4) pm. The coordination between [O3PCH(C2H5)COOH]2- and Cu2+ results in infinite puckered layers parallel to (001). The layers are not connected by any hydrogen bonds. Each layer contains both R and S isomers of the [O3PCH(C2H5)COOH]2- dianion. Water molecules not bound to Cu2+ are intercalated between the layers. UV/Vis spectra suggest three d-d transition bands at 743, 892, 1016 nm for 1 and four bands at 741, 838, 957, and 1151 nm for 2, respectively. Magnetic measurements suggest a weak antiferromagnetic coupling between Cu2+ due to a super-superexchange interaction. Thermoanalytical investigations in air show that the compounds are stable up to 95 °C (1) and 65 °C (2), respectively. [ABSTRACT FROM AUTHOR]

Three new copper azide compounds, [Cu5(N3)10-(N-2AE-1,3-DAP)2] (I), [Cu5(N3)10(N-3AP-1,3-DAP)2] (II), and [Cu7(N3)16(1-(2-AE)PIP-H)2] (III) {where N-2AE-1,3-DAP = N-2-aminoethyl-1,3-propanediamine, N-3AP-1,3-DAP = N-3-amino-propyl-1,3-propanediamine, and 1-(2-AE)PIP = 1-(2-amino-ethyl)piperazine} have been prepared by employing aliphatic amine molecules as coordination blocking amines. All the structures are built up by copper azide units linked through a copper–amine metalloligand, forming two-dimensional layers. Compounds I and II have linear copper azide chains, whereas compound III has Cu5 linear units. The structures of I and II are identical except for the blocking amine molecule. The blocking amine molecule in III is protonated, which is rarely observed. Magnetic studies indicate antiferromagnetic behavior with possible metamagnet-like features in all the compounds. [ABSTRACT FROM AUTHOR]

This mini-review surveys 23 structures of 3D coordination polymers built upon mono-, di- as well as cyclic and acylic polythioethers. An emphasis is put on the Secondary Building Units (SBU) and the physical properties. Importantly, the key feature is that the dominant SBU is not the rhomboid (CuXS), but an inorganic polymer containing at least the chain of the type (CuX). In the latter type of SBU, these chain formations are observed for X = I, but predominantly for X = CN. In addition, a large portion of the surveyed materials exhibit rich photophysical properties, but on several occasions, these materials exhibit properties often attributed to MOFs, mainly solvent exchange. [ABSTRACT FROM AUTHOR]

The identification of the antibacterial action of nalidixic acid (nx) was central to the development of the quinolone antibacterial compounds. The ability of the nx naphthyridyl ring to interact with and inhibit some proteins has encouraged the investigation of similar structures in the search for more active compounds with less adverse effects. The possibility of structural modification by attachment of other biologically active moieties to the naphthyridyl ring of nx allowed the development of new active antimicrobial molecules. Hydrazone derivatives of nx can be synthesized easily based on the condensation of the hydrazide derivative of nx with the desired aldehyde or ketone. Only a few complexes with nx hydrazone derivatives have been described but for none were the crystal structures elucidated. The synthesis of a new one-dimensional CuII coordination polymer, namely catena-poly[[copper(II)-di-μ-chlorido-copper(II)-{μ-1-ethyl-N'-[(1H-imidazol-4-yl)methylidene]-7-methyl-4-oxo-1,4-dihydro-1,8-naphthyridine-3-carbohydrazidato}-[dimethanolcopper(II)]-{μ-1-ethyl-N'-[(1H-imidazol-3-yl)methylidene]-7-methyl-4-oxo-1,4-dihydro-1,8-naphthyridine-3-carbohydrazidato}] dichloride methanol tetrasolvate], {[Cu3(C16H15N6O2)2Cl2(CH3OH)2]-Cl2·4CH3OH}n, with the (1H-imidazol-4-yl)methylidene carbohydrazide derivative of nalidixic acid (denoted h4imi), is presented and its structure is compared to the density functional theory (DFT) optimized structure of free h4imi. The title structure presents an octahedral CuII ion on an inversion centre alternating along a polymer chain with a square-pyramidal CuII ion, with the two CuII centres bridged by two chloride ligands. Hydrogen bonds involving chloride counter-ions and methanol solvent molecules mediate the three-dimensional packing of the polymer. Comparison of the geometrical results from the structure analysis with those derived from a DFT study of the free ligand reveal the differences that arise upon coordination. [ABSTRACT FROM AUTHOR]

A three-dimensional copper-organic coordination polymer based on 3-(4-hydroxypyridinium-1-yl) phthalic acid (H2L) and μ-4,4′-bipyridine (bpy), [Cu(L)(bpy)1/2(H2O)]n(1), has been obtained by hydrothermal synthesis and characterized by elemental analysis, the powder X-ray diffraction (PXRD), UV–vis absorption spectra, and also by single-crystal X-ray diffraction. The crystal is triclinic, space groupPī. The L2–anions of complex1as a bridging ligand connect Cu(II) ions to form one-dimensional (Cu2(L)2)nchains, which are linked to build a 2D layer by the bpy ligands. The 3D supramolecular framework of complex1are guided or controlled by weak directional interlayer hydrogen bond interactions. [ABSTRACT FROM PUBLISHER]

The coordination polymers, {[Cu(Hbidc)(2, 2′-bpy)(H2O)] ·2H2O} n ( 1) and {[Mn(Hbidc)(2, 2′-bpy) (H2O)2] ·2H2O} n ( 2) (H3bidc = benzimidazole-5, 6-dicarboxylic acid, 2, 2′-bpy = 2, 2′-bipyridine), were synthesized in solution and characterized by elemental analysis, IR spectroscopy, thermogravimetric analysis (TGA), and single-crystal X-ray diffraction. Complexes 1 and 2 consist of different 1D chain structures. In both compounds, 2, 2′-bpy is chelating in a bidentate manner, whereas the Hbidc ligands in complexes 1 and 2 display chelating-bridging tridentate and bridging bidentate coordination modes. The two complexes are further extended into 3D supramolecular structures through O-H ···O and N-H ···O hydrogen bonds. The thermal stabilities of complexes 1 and 2 were studied by thermogravimetric analyses (TGA). [ABSTRACT FROM AUTHOR]

We report on the synthesis of a new metal-organic framework (MOF) composed of Sn(OCH3)2-tetrakis(pyridin-4-yl)porphyrin linkers, Cu+ connecting nodes and [CuCl2]− counter-ions, namely poly[[bis(methanolato-κ O)[μ5-5,10,15,20-tetrakis(pyridin-4-yl)porphyrin-κ81κ N5:1′κ N10:1′′κ N15:1′′′κ N20:2κ4 N21, N22, N23, N24]copper(I)tin(II)] dichloridocuprate(I)], [CuSn(C40H24N8)(CH3O)2][CuCl2]. Its crystal structure consists of a single-framework coordination polymer of the organic ligand and the CuI ions. The latter are characterized by a tetrahedral coordination geometry [with CN (coordination number) = 4], linking to the pyridyl N-atom sites of four different ligands and imparting to the positively charged polymeric assembly a diamondoid PtS-type topology. Correspondingly, every porphyrin unit is coordinated to four different CuI connectors. The [CuCl2]− anions occupy the intra-lattice voids, along with disordered molecules of the water crystallization solvent. The asymmetric unit of this structure consists of two halves of the porphyrin scaffold, located on centres of crystallographic inversion, and the Cu+ and [CuCl2]− ions. This report provides unique structural evidence for the formation of tetrapyridylporphyrin-based three-dimensional MOFs with a diamondoid architecture that have been observed earlier only on rare occasions. [ABSTRACT FROM AUTHOR]

Hydrothermal reaction of the requisite metal nitrate, carboxycinnamic acid (H2cca), and the long-spanning dipyridylamide bis(4-pyridylformyl)piperazine (4-bpfp) generate crystalline coordination polymers whose topology depends critically on the metal coordination geometric preference. These two new phases were structurally characterized by single-crystal X-ray diffraction. {[Cu(cca)(4-bpfp)] ·2.5H2O} n ( 1) manifests a non-interpenetrated 6-connected pcu net based on chain motifs featuring carboxylate-bridged {Cu2(OCO)2} dinuclear units, with embedded D(5) water molecule chains. {[Ni(cca)(4-bpfp)(H2O)2] ·3H2O} n ( 2) displays an acentric twofold interpenetrated 4-connected 66 dia network topology with entrapped R(4)A(1) water molecule rings. Variable temperature magnetic studies performed on 1 revealed very weak antiferromagnetic coupling within its dinuclear units. Thermal properties of these two new materials are also discussed. [ABSTRACT FROM AUTHOR]

Two double-chain chiral coordination polymers [Cu(bpy)(phlac)](NO)·HO ( 1) and [Cu(bpy)(clman)](NO)·HO ( 2) were obtained by heating a DMF/HO solution of copper(II) nitrate, 4,4′-bipyridyl (bpy), S-3-phenyllactic (Hphlac) or R-3-chloromandelic (Hclman) acid. The compounds were structurally characterized by X-ray crystallography. [ABSTRACT FROM AUTHOR]

The complexes [Co(L1)(mpy)] ( 1), [Ni(L1)(mpy)] ( 2), [Co(L1)(tbpy)] ·2H2O ( 3), [Ni2(L1)2(tbpy)2] ·5H2O ( 4), [Mn2(L1)2(tbpy)2] ·3H2O ( 5), [Mn(L1)(biim-3)] ( 6), [Ni2(L1)2(btb)2(H2O)] ·2H2O ( 7), [Cu(L2)(mpy)] ·7H2O ( 8), [Co(L2)(tbpy)(H2O)] ( 9), [Ni(L2)(tbpy)(H2O)] ·H2O ( 10), [Cu(L2)(bib)] ·2H2O ( 11), and [Cu(L2)(btb)] ·2H2O ( 12) [H2L1 = (3-carboxyl-phenyl)-(4-(2′-carboxyl-phenyl)-benzyl)ether, H2L2 = 3-carboxy-1-(4′-carboxybenzyl)-2-oxidopyridinium, mpy = 2-(4-(4′-methylphenyl)-6-(pyrindin-2-yl)pyridin-2-yl)pyridine), tbpy = 2-(4-(4′-tert-butylphenyl)-6-(pyrindin-2-yl)pyridin-2-yl)pyridine), biim-3 = 1,3-bis(imidazol-1′-yl)propane, btb = 1,4-bis(1,2,4-triazol-1-ylmethyl)benzene, bib = 1,4-bis(imidazol-1′-ylmethyl)benzene] were synthesized. Compounds 1- 6 have similar 1D chain structures, which are further linked by π-π interactions to generate supramolecular double chains for 1 and 2, and supramolecular layers for 3- 6. Compound 7 displays a 3D 6-connected framework with (44 ·611) topology. Compound 8 features a monomolecular structure, which is further linked by hydrogen bonds between the lattice water molecules and carboxylate oxygen atoms of L2 anions to form a 2D supramolecular layer. The monomolecular structures of 9 and 10 are connected by hydrogen bonds and π-π interactions simultaneously to generate supramolecular layers. Compounds 11 and 12 show layer structures. [ABSTRACT FROM AUTHOR]

Two 2D 3d-4f heterometallic coordination polymers, [ Ln2Cu4Br3(IN)6(OH)(H2O)4] n [ Ln = Ho ( 1) and Yb ( 2), HIN = isonicotinic acid], were synthesized by hydrothermal reaction of Ln2O3, CuBr2, and HIN with HNO3, and characterized by elemental analyses, IR spectroscopy, PXRD, and single-crystal X-ray diffraction. Structural analyses revealed that 1 and 2 are isostructural and have a 2D structure, which consists [Cu4Br3] nn+ chains linked by dinuclear [ Ln2(IN)6(OH)]- clusters. Additionally, the thermogravimetric analysis and luminescent properties of 1 were investigated and discussed. [ABSTRACT FROM AUTHOR]

Two metalloporphyrin octacarboxylates were used to link copper(II) nodes for the formation of two novel porous mixed-metal metal–organic frameworks (M'MOFs) containing nanopore cages (2.1 nm in diameter) or nanotubular channels (1.5 nm in diameter). The highly active Cu2+ sites on the nanotubular surfaces of the stable porous M'MOF ZJU-22, stabilized by three-connected nets, lead to the superior catalytic activity for the cross-dehydrogenative coupling (CDC) reaction. [ABSTRACT FROM AUTHOR]

Two-dimensional (2D) grid coordination polymers were prepared by the reaction of 1,4-bis(4-pyridylmethyl)tetrafluorobenzene (bpf) with Cu(NO3)2 in the presence of aromatic compounds. Crystal structures of {[Cu(bpf)2(NO3)2]·(biphenyl)2}n (1), {[Cu(bpf)2(NO3)2]·(m-C6H4(OMe)2)2}n (2), {[Cu(bpf)2(NO3)2]·PhtBu}n (3) and {[Cu(bpf)2(NO3)(H2O)]NO3·(bpf)0.5}n (4) were determined. The grid networks were held together by C-H⋯O and C-H⋯F hydrogen bonds via the NO3- anions and the tetrafluorophenylene rings of bpf, respectively. Biphenyl, m-dimethoxybenzene, t-butylbenzene, and bpf molecules were clathrated in cyclic cavities of the grid networks through arene-perfluoroarene interactions. These coordination networks have remarkable clathration ability for aromatic compounds. [ABSTRACT FROM AUTHOR]

Two metal-organic coordination polymers [Cu(bpy)(HO)](NO)·4.5CHOH (1) and [Cu(bpy)(HO)( L-pha) ](NO)·HO (2) ( L-Hpha = L-phenylalanine, bpy = 4,4′-bipyridyl) are prepared by slow evaporation of an aqueous alcoholic solution of copper nitrate, L-phenylalanine, and 4,4′-bipyridyl. The structure and composition of the obtained compounds are determined by single crystal XRD. The framework of compound 1 is positively charged and forms two types of intersecting channels. Compound 2 is a homochiral metal-organic coordination polymer whose structure contains L-phenylalanine anions. [ABSTRACT FROM AUTHOR]

A new 3-D copper(II) complex, formulated as [Cu2(btec)(en)2]n (1) [H4btec = benzene-1,2,4,5-tetracarboxylate, and en = ethylenediamine], was hydrothermally synthesized and structurally characterized by elemental analysis, IR spectroscopy, thermal gravimetric analysis, and single crystal X-ray diffraction. The structural analysis of 1 reveals that copper(II) connect by μ6-bridging btec to form a 3-D coordination polymer, in which four carboxylates of btec show monodentate and bidentate coordination. Complex 1 was used as solid bulkmodifier to fabricate renewable carbon paste electrode (1-CPE) by direct mixing method. The cyclic voltammogram of 1-CPE displayed one-electron quasi-reversible redox waves in potential range 300 to -300 mV due to Cu(II)/Cu(I). Moreover, 1-CPE showed electrocatalytic activity toward the reduction of nitrite. [ABSTRACT FROM AUTHOR]

new inorganic-organic vanadate coordination polymer [Cu(bbi)(VO)] · 4HO (bbi = 1,1-(1,4-butanediyl)bis(imidazole)) ( 1) has been synthesized under hydrothermal condition and characterized by elemental analyses, IR spectra and single crystal X-ray diffraction. Structure analysis revealed that the three-dimensional structure of compound 1 is constructed from two-dimensional [Cu(bbi)] layers linked through {VO} building blocks. Compound 1 represents the first example of metal-organic frameworks with non-interpenetrated five-connected topological network (4·6) based on Cu(II) as nodes, bbi and {VO} as mixed spacers. The electrochemical behavior of 1 modified carbon paste electrode ( 1-CPE) in 1M HSO aqueous solution has been studied. [ABSTRACT FROM AUTHOR]