1D Infinite Chain Structure Research Articles

High Efficiency Electrochemiluminescence for Copper(II) and Cadmium(II) Pyrazolate Polymers

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.

Synthesis, Crystal Structures and Catalytic Activities of Two Copper Coordination Compounds Bearing an N,N’-Dibenzylethylenediamine Ligand

Two copper coordination compounds bearing an N,N’-dibenzylethylenediamine ligand, namely [Cu3L(CH3COO)6]n (1) and [(CuCl4)∙(C6H5CH2NH2CH2)2] (2) (L = N,N’-dibenzylethylenediamine) were synthesized by the ethanol refluxing method. Powder X-ray diffraction (PXRD), infrared spectra (IR), elemental analyses, and single crystal X-ray diffraction were used to characterize and verify their structures. Structural analyses showed that the asymmetric unit of compound (1), composed of two Cu(II) cations, three acetate anions, and half of the ligand, was bridged by one acetate to obtain an infinite 1D chain structure. The analyses further showed that the asymmetric unit of compound (2), composed of two crystallographically independent [C6H5CH2NH2CH2]+ units, four chloride anions, and one central Cu(II) cation is connected into an infinite 2D network structure by the hydrogen bonding interactions. The copper compounds were used to catalyze the decomposition of H2O2, and the results showed that both of the compounds exhibited excellent catalytic activities under optimized conditions.

Two Coordination Compounds Bearing Bis(2-dimethylaminoethyl) Ether: Syntheses, Crystal Structures and Catalytic Application to the Henry Reaction

Two novel coordination compounds, namely [Cu2(BDMAEE)(CH3COO)4] n (1) and [Ni(BDMAEE)Cl2](2) [BDMAEE=bis(2-dimethylaminoethyl) ether], have been synthesized and characterized by IR, elemental analysis, PXRD and X-ray single crystal diffraction. In compound 1, the central Cu(II) ion is coordinated with four oxygen atoms and one nitrogen atom, forming a distorted square pyramidal geometry. The asymmetric units composed of one Cu(II) ion, two acetates and a half of BDMAEE are connected to form an infinite 1D chain structure by the bridging acetate and the BDMAEE. In compound 2, the central Ni(II) ion is coordinated with one oxygen atom, two chlorine anions and two nitrogen atoms, forming a distorted square pyramidal geometry. The compounds exhibited excellent catalytic properties in the Henry reaction of nitromethane with some aromatic aldehydes, and the optimized reaction conditions were obtained.

Cu(II) coordination polymers constructed by tetrafluoroterephthalic acid and varied imidazole-containing ligands: Syntheses, structures and properties

Six new copper(II) coordination polymers combining 2,3,5,6-tetrafluoroterephthalatic acid (H2tfBDC) and diverse imidazole-containing ligands, {[Cu(tfBDC)(1,2-bix)2]·2(H2O)}n (1), {Cu(tfBDC)(Im)2}n (2), {[Cu(1,4-bmimb)2(H2O)]·(tfBDC)·2(H2O)}n (3), {Cu(1,4-bimb)2(H2O)2·(tfBDC)}n (4), {[Cu(1,3-bix)2(H2O)2]·(tfBDC)·6(H2O)}n (5) and {[Cu(1,4-bix)2(H2O)2]·(tfBDC)·(1,4-bix)·4(H2O)}n (6) (1,2-bix = 1,2-bis(imidazole-1-ylmethyl)-benzene, Im = imidazole, 1,4-bmimb = 1,4-bis((2-methyl-1H-imidazol-1-yl)methyl)benzene, 1,4-bimb = 1,4-bis(imidazol-1-yl)-butane, 1,3-bix = 1,3-bis(imidazole-1-ylmethyl)-benzene, 1,4-bix = 1,4-bis(imidazole-1-ylmethyl)-benzene), have been obtained and structurally verified by single-crystal X-ray diffraction analyses and further characterized by powder X-ray diffraction (PXRD), elemental analyses and infrared spectroscopy (IR). Single crystal X-ray diffraction analysis revealed that 1 is 2D 4-connected sql topology (point symbol: {44·62}) based on a single metal ion node. Compound 2 is characterized as an infinite 1D chain structure, which is further extended into a 2D layer through N-H···O hydrogen bonds and then a 3D supramolecular architecture via π···π stacking interactions. Note that 2 was prepared through an in situ ligand reaction in which N,N’-carbonyldiimidazole (cdi) broke up into imidazole ligand. Compound 3 possesses a 3D 4-fold interpenetrated architecture with 4-connected dia topology (Schläfli symbol: {66}) in which tfBDC2- is stabilized in the channel by hydrogen bonds. Compounds 4–6 are all linear 1D coordination polymers. In 4, the free tfBDC2- ligand acts as a μ4-bridge to link four coordinated water molecules from the chain to construct a 2D structure via hydrogen bonds. While in 5 and 6, the uncoordinated tfBDC2- ligands and multimeric water clusters is responsible for the conversion of these 1D coordination polymers into 3D supramolecular assemblies through O–H⋯O hydrogen bonding interactions. Moreover, the UV–vis spectra and thermal stability of 1–6 are discussed in detail.

Organic–inorganic hybrids based on polyoxometalates and copper coordination complexes

Two new hybrids based on Keggin polyoxometalates have been hydrothermally synthesized and characterized by elemental analysis, IR spectroscopy, TG analysis, and single-crystal X-ray diffraction. The crystal structure analyses reveal that complex 1 has an infinite 1D chain structure, constructed from [Cu(2,2′-bpy)(4,4′-bpy)(H2O)] fragments and [H2PMo11VO40]2− building blocks. Complex 2 has a 2D molecular ladder structure, with a basic structural unit composed of one bis(µ-OH) dicopper(II) [Cu2(OH)2(H2O)2(4,4′-bpy)3] fragment, one [HPMo12O40], and four water molecules. The [Cu2(OH)2(H2O)2(4,4′-bpy)3] units connect alternately to form edge rails. The [HPMo12O40] clusters act as rungs of the ladder, linking pairs of Cu atoms from the two adjacent edge rails. The electrochemical behavior of the complexes in modified carbon paste electrodes and their electrocatalytic reduction of nitrite were investigated.

1D Structure Sodium Coordination Anion based on [5‐(Dinitromethylene)‐4,5‐dihydro‐1H‐tetrazole]: Syntheses, Structures, and Thermal Behavior

AbstractThe ten‐coordinate complex, (HATr)[Na(DNMz)]·H2O (1) was synthesized by reaction of 5‐(dinitromethylene)‐4,5‐dihydro‐1H‐tetrazole (DNMz), sodium hydroxide, and 3‐hydrazinium‐4‐amino‐1,2,4‐1H‐triazolium dichloride (HATr) in aqueous solution and characterized by various physico‐chemical techniques. Complex 1 is an energetic material with a nitrogen content of 51.2 % and a decomposition temperature of 128.9 °C. The molecular structure of complex 1 crystallizes in the monoclinic system with P2(1)/c group and shows an infinite 1D chain structure. The heat of formation was determined as –122.27 kJ·mol–1 by using bomb calorimetry. In addition, the kinetic parameters were studied by Kissinger's and Ozawa‐Doyle's methods.

The synthesis, structure and properties of a new compound with 1D linear chain arsenomolybdate anion building block

The new inorganic–organic hybrid arsenomolybdate {Cu(2,2′-bpy)}2{H2As2Mo2O14} (2,2′-bpy=2,2′-bipyridine) (1) has been hydrothermally synthesized and characterized by single-crystal X-ray diffraction analysis, elemental analyses, X-ray powder diffraction (XRPD), IR spectroscopy, UV spectroscopy, XPS spectroscopy and thermogravimetric analysis (TG). Compound 1 presents an infinite 1D chain structure based on the unprecedented {H2As2Mo2O14}4− fragment and transition-metal complex {Cu(2,2′-bpy)}2+. Compound 1 displays obvious electrocatalytic activities toward the reduction of nitrite and better photocatalytic activities for the degradation of methylene blue.

One-Pot Synthesis, Crystal Structures and Thermal Properties of Two Three-Dimensional Cobalt(II) Complexes

Two cobalt(II) compounds (1) and (2) (2,2'-bipy = 2,2'-bipyridine, = 1,2,4,5-benzenetetracarboxylic acid), have been simultaneously synthesized by a one-pot slow solvent evaporation reaction. Their structures were determined by single-crystal X-ray diffraction and further characterized by X-ray powder diffraction (XRPD), IR, elemental and thermogravimetric analysis (TGA). The structural analysis reveals that compound 1 exhibits an infinite 1D chain structure with the octahedral Co(II) centers bridging by the tetrahedral ligands, while compound 2 possesses a dinuclear unit and the two adjacent octahedral Co(II) ions are linked by the bismonodentately coordinated btec ligand. Additionally, compound 2 exhibits blue fluorescent emission in the solid state at room temperature.

Synthesis and crystal structure of one-dimensional heterotrimetallic coordination polymer {[(Dipic)2Cu]4 · Mg(H2O)2Na4(H2O)14} n · nNa2(H2O)10 · 2nCH3OH

A novel heterotrimetallic complex {[(Dipic)2Cu]4 · Mg(H2O)2Na4(H2O)14n · nNa2(H2O)10 · 2nCH3OH (H2Dipic = pyridine-2,6-dicarboxylic acid) has been synthesized and structurally determined by X-ray diffraction method. The compound crystallizes in the triclinic system, space group P\(\bar 1\), with a = 13.5523(13), b = 14.1859(13), c = 14.3213(14) A, α = 62.6160(10)°, β = 68.2540(10)°, γ = 89.7110(10)°, V = 2224.7(4)A3, F(000) = 1144, Mr = 2237.70, Z = 1, ρc = 1.670 g cm−3, μ = 1.095 mm−1, final R = 0.0507, wR = 0.1418 for 8042 independent reflections with Rint = 0.0228. According to the structure determination, the complex is composed of novel one-dimensional (1D) alternating chains, dinuclear Na(I) units, and lattice methanol molecules. The infinite 1D chain structure is built up with many of polymeric [(Dipic)2Cu]4 · Mg(H2O)2Na4(H2O)14 units, which consists of four six-coordinated Cu2+ ions, one six-coordinated Mg2+ ion, two five-coordinated Na+ ions, and two six-coordinated Na+ ions. The 1D alternating chains are linked with another dinuclear Na(I) units by extensive hydrogen bonds to form a three-dimensional (3D) supramolecular structure in which uncoordinated methanol molecules act as space filling particles.

Synthesis and characterization of coordination polymers of a carboxylato cyclophane with metal [Zn(II) and Cd(II)]-2,2′-bipyridines

N,N′,N′′,N′′′-Tetrakis(3-carboxy-propionyl)-1,6,20,25-tetraaza-[6.1.6.1] paracyclophane, H 4cp has been complexed with metal (Zn(II) and Cd(II)) 2,2 ′ -bipyridyls. The resulting complexes of the composition [{Zn(2,2 ′-bpy)} 2(cp)] n ·4H 2O 1 and [{Cd(2,2 ′-bpy)} 2(cp)] n ·5H 2O 2 (2,2 ′-bpy = 2,2 ′-bipyridine) have been characterized using spectroscopic (IR, solid state UV–Vis), elemental analysis and single-crystal X-ray diffraction measurements. In these complexes the cyclophane coordinates in different modes, and in complex 2, Cd(II) is hepta-coordinated. However, under harsh reaction conditions (using excess nitric acid and a longer reaction time) debranching of the cyclophane is observed in the reaction of Zn(2,2 ′-bpy)(NO 3) 2 with H 4cp, and a complex of the composition [Zn(2,2 ′-bpy)(Suc)] n 3 (suc = succinate) is isolated. Using non-covalent interactions, complexes 1 and 2 provide 3D supramolecular structures, whereas an infinite 1D chain structure is observed for complex 3. The thermal and photoluminescence properties of the complexes have also been studied.

New metal complexes with 5-(1H-imidazol-4-ylmethyl)aminoisophthalic acid: Syntheses, structures, electrochemistry and electrocatalysis

Three new coordination polymers {[Cu(HL)(H 2O)]·H 2O} n ( 1), [Ag(H 2L)] n ( 2), and {[Co(HL)(phen)(H 2O)]·8H 2O} n ( 3) [H 3L = 5-(1H-imidazol-4-ylmethyl)aminoisophthalic acid, phen = 1,10-phenanthroline] have been synthesized under hydrothermal conditions. The results of X-ray diffraction analysis revealed that complex 1 displays (3, 3)-connected 2D network with (4, 8 2) topology, while complexes 2 and 3 have infinite 1D chain structure, in which one of the two carboxylic groups of H 2L −/HL 2− is uncoordinated. The 2D layers of 1 or the 1D chains of 2 and 3 are further linked together by hydrogen bonds and π–π interactions to form 3D supramolecular frameworks. Moreover, the electrochemical properties of complexes 1 and 2 have been studied by modified glassy carbon electrodes of 1 (Cu-GCE) and 2 (Ag-GCE), and the results indicate that the Cu-GCE and Ag-GCE show one-electron redox peaks. In addition, both Cu-GCE and Ag-GCE have good electrocatalytic activities toward the reduction of H 2O 2 in phosphate buffer (pH 5.5) solution.

New types of di-, tetra-, hexa- and octanuclear Ag(i) complexes containing 1,3-adamantanedicarboxylic acid

This article represents a systematical investigation on the structures of silver(I) dicarboxylate incorporating secondary ligands, revealing that the secondary interactions could play an important role in interlinking low-dimensional entities to high-dimensional supramolecular frameworks. A new 2D silver(I) crystalline dicarboxylate, {[Ag(6)(ADC)(3)(H(2)O)(1.5)](2).5.18H(2)O}(n) (1) (H(2)ADC = 1,3-adamantanedicarboxylic acid), has been obtained by slow diffusion of corresponding precursors. To investigate the influence of the properties of pyridylic neutral ligands on the complex structures based on compound 1, five kinds of neutral ligands (bipy = 4,4'-bipyridine; bpa = 1,2-bis(4-pyridyl)ethane; bpe = 1,2-bis(4-pyridyl)ethene; bpp = 1,3-bis(4-pyridyl)propane; bpdap = N,N'-bis(3-pyridyl)-2,6-diaminopyridine) were selected, and a series of new silver(I) dicarboxylate have been synthesized: {[Ag(bpa)(HADC)]}(n) (2), {[Ag(bpp)(HADC)].CH(3)OH}(n) (3), {[Ag(4)(bpe)(3)(ADC)(2)].2H(2)O}(n) (4), {[Ag(bipy)(HADC)].H(2)O}(n) (5), {[Ag(2)(bipy)(2)(ADC)].6H(2)O}(n) (6), and [Ag(8)(bpdap)(4)(ADC)(4)].2C(2)H(5)OH.6H(2)O (7). Single-crystal X-ray structural analysis shows that complexes 1 and 4 are formed by hexanuclear and tetranuclear Ag(I) clusters with weak Ag-Ag interactions. Complexes 2 and 3 are dinuclear structures, 5 and 6 exhibit an infinite 1D chain structure, whereas 7 is a discrete octanuclear Ag(I) unit. The structures of 1-7 span from dinuclear, tetranuclear, hexanuclear, to octanuclear Ag(I) complexes, which indicates that secondary ligands do play important roles in the formation of such coordination architectures. Thermal stability, X-ray powder diffraction and luminescent properties of the compounds are also discussed.

Tuning silver(I) coordination architectures by ligands design: from dinuclear, trinuclear, to 1D and 3D frameworks

In our efforts to tune the structures of AgI complexes by ligand modification, six structurally related ligands: 1,2-bis(triazol-1-ylmethyl)benzene (L1), 1,3-bis(triazol-1-ylmethyl)benzene (L2), 1,4-bis(triazol-1-ylmethyl)benzene (L3), 1,3,5-tri(triazol-1-ylmethyl)-2,4,6-trimethylbenzene (L4), 1,4-bis[3-(2-pyridyl)-pyrazol-1-ylmethyl]naphthalene (L5), and 9,10-bis(benzimidazol-1-ylmethyl)anthracene (L6) have been designed and used to react with AgI salts to form six new complexes: {[Ag2(L1)2](BF4)2(H2O)} (1), [Ag2(L2)(NO3)2]n (2), [Ag(L3)(NO3)]n (3), {[Ag3(L4)2](SiF6)1.5(H2O)3.5} (4), {[Ag2(L5)2](NO3)2(H2O)} (5), and {[Ag2(L6)2](NO3)2(CH3OH)2} (6). All the complexes have been structurally characterized by IR and X-ray diffraction. Structural analyses show that complexes 1, 5, and 6 possess dinuclear structures, which extend to infinite coordination networks linked by Ag⋯N, C–H⋯O, or π–π weak interactions. 2 is a 3D chiral coordination polymer with (10,3)-a topology, and 4 forms a trinuclear cage structure, which further connected by Ag⋯Ag weak interactions to form a 1D supramolecule, while 3 exhibits an infinite 1D chain structure. The structures of complexes 1–6 span from dinuclear, trinuclear, 1D, to 3D network, which indicates that ligands play important roles in the formation of such coordination architectures. Furthermore, the CD spectrum, thermal, and fluorescent properties of the chiral complex 2 have been investigated in the solid state.

Syntheses, characterization and crystal structures of diorganotin compounds with 2-mercaptopyrimidine and 4-amino-2-mercaptopyrimidine

Six diorganotin compounds with 4-amino-2-mercaptopyrimidine (HSapym) and 2-mercaptopyrimidine (HSpym) of the type, [R 2SnCl m L n ] · Y (when n = m = 1: L = Spym, R = CH 3, Y = 0, 1; R = Bu, Y = 0, 2; L = Sapym, R = Ph, Y = EtOH, 3; when n = 2, m = 0: L = Spym, R = PhCH 2, Y = 0, 4; L = Sapym, R = Bu, Y = 2MeOH, 5; R = PhCH 2, Y = 3MeOH, 6) have been synthesized. X-ray analysis revealed that the tin environmental in 1– 3 is trigonal bipyramidal while that in 4– 6 is distorted octahedral. Two coordination modes are found in the organotin(IV) derivatives for HSapym. Additionally the intermolecular Sn⋯S non-bonded interaction was recognized to benefit the construction of an infinite 1D chain structure of compound 1. For the dimer in compound 3, intermolecular N⋯H hydrogen bonding was found.

Syntheses, crystal structures and anion-exchange properties of novel coordination polymers with imidazole-containing tripodal ligands

Six novel coordination polymers, [Cu(tib) 2(N 3) 2] · 2H 2O ( 1), [Cd(tib) 2(H 2O) 2](NO 3) 2 ( 2), [Cu(dien)(tib)](ClO 4) 2 · tib · CH 3CN ( 3), [Mn(ibimb) 2(H 2O) 2]Cl 2 · 2H 2O ( 4), [Zn(titmb) 2](NO 3) 2 · 2MeOH ( 5) and [Cd 3(titmb) 2Br 6] ( 6), where tib = 1,3,5-tris(1-imidazolyl)benzene, dien = diethylenetriamine, ibimb = 1-(1-imidazolyl)-3,5-bis(imidazol-1-ylmethyl)benzene, titmb = 1,3,5-tris(imidazol-1-ylmethyl)-2,4,6-trimethylbenzene, were obtained by self-assembly of tripodal ligands with the corresponding metal salts, and their structures were determined by single crystal X-ray diffraction analyses. Complexes 1 and 2 have similar 2D network structure in which only two of three imidazole groups of each tib ligand coordinated to the metal atoms and the additional one did not participate in the coordination. Complex 3 has a 1D chain structure in which there are two kinds of tib ligands, one kind of tib serves as a two-connecting (bridging) ligand using its two arms. The other kind of tib acts as guest molecule filled in the void of cationic 1D chains. Complex 4 has an infinite 1D hinged chain structure and ligand ibimb serves as a two-connecting (bridging) ligand using its two flexible arms. Complex 5 has a 2D honeycomb network structure with (6,3) topology in which titmb acts as a three-connecting ligand. Complex 6 has an infinite 1D chain structure in which each titmb ligand connects three metal atoms. Ligand titmb has cis, trans, trans-conformation in 6, which is different from that in complex 5( cis, cis, cis). The anion-exchange properties of complex 5 were investigated.

Syntheses, Crystal Structures and Electrospray Mass Spectra of Coordination Polymers of an N,N′‐Bis(3‐pyridylmethyl)‐1,4‐benzenebis(methylamine) Ligand and Silver(I) Salts

AbstractFour new coordination frameworks {[Ag2(L1)](NO3)2·2H2O}n (1), {[Ag(L1)](CF3COO)·2.5H2O}n (2), {[Ag2(L1)2][1,4‐C6H4(COO)2]·7H2O}n (3) and {[Ag(L1)]ClO4}n (4) were obtained by the reaction of N,N′‐bis(3‐pyridylmethyl)‐1,4‐benzenebis(methylamine) (L1) with the corresponding silver(I) salts. X‐ray diffraction analyses reveal that complex 1 has an infinite 1D chain structure, in which L1 acts as a tetradentate ligand. Complexes 2, 3 and 4 have 2D network structures, and the L1 ligands in these complexes adopt two different coordination modes: one kind of ligand coordinates four silver(I) atoms using its four N atoms, and the other kind of ligand connects only two silver(I) atoms with the two N atoms of the benzenebis(methylamine) unit, while the pyridine units remain free of coordination. Complex {[Ag(L2)]ClO4}n (5) was synthesized by reaction of N,N′‐bis(3‐pyridylmethyl)‐1,4‐benzenebis(methyleneamine) (L2) with silver(I) perchlorate. It has a novel 1D chain structure, which is different from that of 4 due to the different flexibility of the ligands L1 and L2. All of these complexes form 2D or 3D structures stabilized by hydrogen bonding, C−H···π and π‐π interactions. The results revealed that the nature of the counteranions and the flexibility of the ligand have an impact on the structure of the supramolecular architectures. The complexes were also characterized by electrospray mass spectrometry. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)