Two Metal-organic Coordination Polymers with Rigid Bis(triazole) Ligand: Assembly,Structures, and Fluorescence Properties

Two new coordination polymers containing rigid bis(triazole), namely, [Ni(btb)_(0.5)(nph)(H_2O)]_n(1) and [Zn(btb)(SO_4)]_n(2)(btb = 4,4?-bis(1,2,4-triazolyl-1-yl)-biphenyl, H_2nph = 3-nitrophthalic acid) have been synthesized and characterized by elemental analysis, IR spectra, and single-crystal X-ray diffraction. Complex 1 shows a 3D trinodal(3,4,4)-connected sqc69 topology. Complex 2 presents a 2D uninodal 4-connected sql network, which is further packed into a 3D supramolecular framework by C–H···O hydrogen bonds. Thermal stabilities and fluorescence properties of two complexes have been discussed in detail.     

A Novel 3D Twofold Zn(Ⅱ) Coordination Polymer Constructed by Mixed Flexible Ligands: Synthesis,Crystal Structure and Fluorescence Property

A new Zn(Ⅱ) coordination polymer, {[Zn(1,3-bip)(oba)]·0.5H_2O}n(1),1,3-bip =1,3-bis(imidazole)propane, H_2oba=4,4?-oxybis(benzoate)), have been synthesized and characterized by single-crystal X-ray diffraction, powder XRD, FTIR, TGA and elemental analysis techniques. The single-crystal X-ray diffraction reveals that complex 1 shows a 3D→3D twofold interpenetrating network that can be described as a 4-connected uninodal net with(65.8) topology. In addition, the photoluminescence property of complex 1 was also investigated at room temperature.     

Two Interpenetrated and Polycatenated Zn(Ⅱ) Coordination Polymers: Syntheses,Structures and Luminescent Properties

Two fascinating Zn(II)entangled coordination polymers,[Zn(eoba)(bbi)]_n·nH_2O(1)and[Zn(boba)(bbi)_(1/2)]_n(2),(bbi=1,1?-(1,4-butanediyl)-bis(imidazole),H_2eoba=4,4?-(ethane-1,2-diyldioxy)-dibenzoic acid,H_2boba=4,4?-(butane-1,4-diyldioxy)-dibenzoic acid),were obtained by hydrothermal technology and characterized by elemental analysis,infrared spectrum,thermogravimetric analysis and single-crystal X-ray diffraction.1 is a rare 2D→3D example with a 3-fold parallel interpenetration and polycatenaned architecture.2 features a scarce2D→2D example with a 3-fold parallel interpenetrating network which possesses polyrotaxane and polycatenane characters.Moreover,the luminescent properties of 1 and 2 have been discussed.     

DNA-binding Studies of Two Silver(I)-sulfonate Complexes Constructed by In Situ Reaction

Two silver(I)-sulfonate complexes,[Ag(NO_3)(4,4'-bipy)][Ag(HL)(4,4'-bipy)]·2H_2O(1) and[Ag(H_2O)(4,4'-bipy)][AgL(4,4'-bipy)]·2H_2O(2),have been synthesized by in situ reaction(H_2L = 2-formylbenzenesulfonic acid,4,4-bipy = 4,4-bipyridine).1 displays two parallel 1D chains expending to a 3D supramolecule by n—n interactions and O-H…O hydrogen bonds,in which the[Ag(NO_3)]or[Ag(HL)]units are joined by bridging 4,4'-bipy molecules,respectively.The interactions between the complexes and DNA were studied by means of fluorescence spectra and surface-enhanced Raman scattering(SERS) spectra.The special configuration and intercalation effects between 1 and DNA are stronger than that between 2 and DNA.     

Structures and Photoluminescent Properties of Two Complexes Based on Dipyrido[3,2-a:2?,3?-c]phenazine and 2,4?-Biphenyldicarboxylic Acid

ABSTRAC Two new complexes [Cd(2,4?-bpdc)(DPPZ)]_(2n)·n H_2O(1) and [Zn(2,4?-Hbpdc)_2(DPPZ)]· H_2O(DPPZ = dipyrido[3,2-a:2?,3?-c]phenazine, 2,4?-H_2bpdc = 2,4?-biphenyldicarboxylic acid) have been hydrothermally synthesized. The structure of complex 1 was determined by single-crystal X-ray diffraction diffraction and further characterized by elemental analysis, IR spectrum, powder X-ray diffraction(XRD) and single-crystal X-ray diffraction. Complex 1 has 1D chains, which are further connected by π-π stacking interactions of neighbouring chains, generating a steady 3D supramolecular structure. Complex 2 shows the isolated mononuclear units, which are further extended to a 2D supramolecular layered structure through π-π stacking interactions and hydrogen bonds. Furthermore, complexes 1 and 2 exhibit green photoluminescent properties at room temperature.     

Syntheses,Crystal Structures,and Magnetic Properties of Cobalt(Ⅱ) Complexes with 1,1-Cyclohexanediacetic Acid

Two new Co(Ⅱ) coordination polymers,{[Co_3(Hchda)_2(chda)_2(bpp)_2(H_2O)_2]}_n 1 and {[Co(chda)(bpe)(H_2O)]·3H_2O}_n 2(H_2chda = 1,1-cyclohexanediacetic acid,bpp = 1,3-bis(4-pyridinyl)propane and bpe = 1,2-bis(4-pyridinyl)ethylene),were hydrothermally synthesized and then characterized by elemental analysis,IR spectroscopy,thermogravimetric analysis(TGA),and single-crystal X-ray diffraction.Complex 1 possesses an infinite metal-organic layer based on triply bridged linear trinuclear subunits and complex 2 exhibits a square(4,4) grid layer with dangling lateral arms resulting from eight-membered rings above and below the layer.In addition,magnetic properties of complexes 1 and 2 are also given.     

Interpenetration of Three 2D In-MOFs with(6,3) Topology:Syntheses,Structures and Fluorescent Properties

Three indium metal-organic frameworks(In-MOFs), [In(BTB)(2,2?-bipy)]·NMP(1), [In(BTB)(2,2?-bipy)]·NMP·2H_2O(2), and [In(BTB)(NMP)]·0.5NMP(3), have been constructed by the solvothermal reaction of In(NO_3)3·5H_2O and 1,3,5-benzenetribenzoic acid(H3BTB) in similar reaction conditions, and characterized by single-crystal X-ray crystallography, power X-ray diffraction(PXRD), infrared spectroscopy(IR), elemental analysis(EA) and thermogravimetry analysis(TGA). Complex 1 bears a two-dimensional(2D) layered structure of 6,3-connected hcb net topology, and complexes 2 and 3 have 2-fold interpenetrating structures based on 6,3-connected layer, which display the same net topologies with the C_3-symmetric H_3B TB ligands as 3-connected linkers and the In(ⅡI) ions as 6-connected nodes. Moreover, the fluorescent properties of 1~3 have also been studied.     

Syntheses,Structures,and Properties of Two New Coordination Polymers Based on Tetracarboxylate and 2,2′-Bipyridine Mixed Ligands

Two new coordination polymers {[Zn2L1(2,2'-bpy)2(H2O)2]·4H2O}n(1) and [Zn2L2(2,2'-bpy)2(H2O)2]n(2)(H4L1 = terphenyl-2,2',4,4'-tetracarboxylic acid, H4L2 = quarterphenyl-2,2',4,4'-tetracarboxylic acid, and 2,2'-bpy = 2,2'-bipyridine) have been synthesized and characterized by elemental analysis, IR and X-ray single-crystal diffraction studies. Complex 1 displays 2D wavelike networks, which are further joined together through O–H···O hydrogen bonds to give a 3D supramolecular network. Complex 2 exhibits 1D ladder-like chains, and they are further joined together by π-π stacking and O–H···O hydrogen bonding interactions to form a 3D supramolecular network. The results indicate that the backbone of carboxylate ligands has significant effects on the formation and structure of the resulting functional coordination polymers. Additionally, thermal stability and photoluminescent properties of 1 and 2 are also investigated in detail.     

Syntheses,Structures and Properties of Three Novel La(Ⅲ)/Co(Ⅱ) Coordination Polymers Based on 5-(3-(Tetrazo-5-yl)phenyl)isophthalic Acid

Three novel complexes, namely {[La(tapipa)(4,4′-bibp)·(H_2O)_2]·H_2O}n(1), {[La-(tapipa)(H_2O)_4(OH)]·3 H_2O}n(2), [Co(tapipa)(1,4-bbib)]n(3)(tapipa = 5-(3-(tetrazo-5-yl)phenyl)isophthalic acid, 4,4′-bibp = 4,4′-bis(imidazolyl)biphenyl, and 1,4-bbib = 1,4-bis(benzimidazo-1-ly)benzene) have been synthesized under solvothermal conditions and characterized by PXRD, IR,TGA, and so on. Complex 1 presents a 2 D layer structure, which is finally packed into a 3 D supramolecular structure by means of hydrogen bonds; complexes 2 and 3 exhibit 1 D chains and 2 D wavy-type structures, respectively, which are expanded into 3 D supramolecular structures through hydrogen bonds and π-π interactions. Furthermore, the luminescence properties of complex 1 and the variable-temperature magnetic susceptibilities of 3 were investigated. Complex 1 has highly selective sensing for Fe~(3+) and Cr_2O_7~(2-) ions.     

Hydrothermal Syntheses and Crystal Structures of Six Complexes Constructed from 1,3,5-Benzenetricarboxylic Acid and 4?-(4-Pyridyl)-2,2?:6?,2??-terpyridine Mixed Ligands

Six new transition metal complexes, [Zn(HBTC)(PYTPY)]_n·n PYTPY(1), [Cu(HBTC)(PYTPY)]_n·n PYTPY(2), [Co(HBTC)(PYTPY)]_n·n DMF(3), [Mn(HBTC)(PYTPY)]_n·n DMF(4), [Cd(HBTC)(PYTPY)(H2O)]_n·2nH_2O(5), and [Co(HBTC)(PYTPY)(H_2O)_2](6),(H_3BTC = 1,3,5-benzenetricarboxylic acid, PYTPY = 4?-(4-pyridyl)-2,2?:6?,2??-terpyridine, DMF = N,N?-dimethylformamide), have been synthesized and characterized by elemental analysis, IR and X-ray single-crystal diffraction. Complexes 1~5 all feature one-dimensional chain structures, and complex 6 exhibits a zero-dimensional structure. Complexes 1~5 present three-dimensional(3D) supramolecular frameworks via π-π stacking interactions, whenas 6 has also a 3D supramolecular structure assembled by hydrogen bonding. Meanwhile, complexes 1 ~ 6 exhibit the thermal stabilities and photoluminescent properties.     

A New 3d-4f Heterobimetallic Complex Based on 4,4?-Dicarboxybiphenyl Sulfone: Synthesis,Crystal Structure and Antifungal Activity

A new 3 d-4 f heterobimetallic complex [PrCu(sba)_2(Hsba)(H_2 O)_3]·H_2 O(1) based on a versatile ligand H_2 sba(H_2 sba = 4,4?-dicarboxybiphenyl sulfone) was prepared and characterized by single-crystal X-ray diffraction, elemental analysis, IR spectroscopy and thermogravimetric analysis. Single-crystal X-ray diffraction indicates that complex 1 belongs to the monoclinic system, space group P2_1/n with a = 12.4642(11), b = 16.0586(16), c = 21.9678(19) ?, β = 92.888(1)o, V = 4391.4(7) ?~3, Z = 4, D_c = 1.800 g·cm~(-3), μ = 1.812 mm-1, M_r = 1190.31, F(000) = 2388, the final R = 0.0663 and wR = 0.1539 for 7737 observed reflections with I 2s(I). Complex 1 exhibits 2D network skeletons which are linked by hydrogen-bonding interactions to give a 3D supramolecular architecture. In addition, the antifungal effects of H_2 sba, metal salts and the title complex have also been studied by disc diffusion method against Colletotrichum gloeosporioides Penz. Complex 1 has better antifungal activity than H_2 sba and the corresponding metal salts. Complex 1 has potential applications in the antifungal activity.     

Hydrothermal Syntheses,Structure Characteristics and Magnetic Properties of a Series of New Molybdenum Arsenates Based on {(As_3O_3)_2(Mo_6O_(18)(MO_6)}(M=Ni,(1);Co,(2);Zn,(3))

Three new polyoxometalates K_2[H_2(As_3O_3)_2(Mo_6O_(18))(NiO_6)]×H_2O(1), K_2[H_2-(As_3O_3)_2(Mo_6O_(18))(Co O6)]×H_2O(2) and [Zn(H4,4?-bpy)2(H_2O)4][(As3O3)2(Mo_6O_(18))(ZnO_6)]×4H2O(3)(4,4?-bpy = 4,4?-bipyridine) have been synthesized under hydrothermal conditions and characterized by IR, elemental analyses, XPS and single-crystal X-ray diffraction analyses, respectively. Compound 1 represents a new 3D framework structure constructed from polyoxoanion [(As3O3)2(Mo_6O_(18))(Ni O6)]4-via covalent bond. Compound 2 has an identical structure with 1. Compound 3 represents a new 2D layer structure constructed from transition metal coordination cations [Zn(H4,4?-bipy)2(H_2O)4]4+, lattice water molecules and polyoxoanions [(As_3O_3)_2-(Mo_6O_(18))(Zn O6)]4-via multi-point N–H···O and O–H···O hydrogen bonding interactions. Crystal data: for 1, cubic, space group Pa-3, a = 15.0022(8) ?, V = 3376.5(3) ?3, Z = 24; for 2, cubic space group Pa-3, a = 15.1596(10), V = 3483.88 ?3, Z = 24; for 3, monoclinic, space group C2/m, a = 19.699(4), b = 14.223(3), c = 9.1455(18) ?, β = 106.80(3)o, V = 2453.0(9) ?3, Z = 8. In addition, the magnetic behaviors for compounds 1 and 2 have been investigated.     

Syntheses,Crystal Structures and Properties of Two New Compounds from a Flexible Bipodal Acid with Additional Amide Groups

Two novel compounds {[Cu(IBG)(4,4-bipy)(H_2O)_2]_2·11H_2O}_n(1) and {[Co(IBG)-(μ-H_2O)(H_2O)_2]·2H_2O}n(2) based on isophthaloylbisglycine(H_2IBG) have been synthesized and structurally characterized by thermogravimetric analysis, elemental analysis and single-crystal X-ray diffraction. Compound 1 shows a 1D chain sine/cosine chain structure, and compound 2 can be characterized as a 4-connected sql tetragonal planar network with the point symbol of {44·62}. Compound 2 has been characterized by magnetic measurements. In addition, 1 and 2 display an interesting reversible crystal-to-amorphous transformation.     

Solvothermal Syntheses,Crystal Structures,and Luminescent Properties of Three Coordination Polymers Derived from Semirigid 3-(Carboxymethyl)benzonic Acid and Dipyridyl Coligands

Three coordination polymers, namely, {[Zn(cmba)(bpp)]×H_2O}_n(1), {[Zn(cmba)(bpa)1.5]×2.25H_2O}_n(2) and {[Cd(cmba)(bpa)(H_2O)]×H_2O}_n(3)(H_2cmba = 3-(carboxymethyl)benzonic acid, bpp = 1,3-bis(4-pyridyl)propane and bpa = 1,2-bi(4-pyridyl)ethane), were synthesized under solvothermal conditions and characterized by elemental analysis, IR spectroscopy, thermogravimetric analysis(TGA), and single-crystal X-ray diffraction. Complex 1 features a 2D(4,4) grid layer with a side length of 9.827(10)/12.176(13) ?. Complex 2 shows a 2D → 2D 2-fold interpenetrating layer structure through the flexible bpa coligands. Compound 3 presents a 2D layer formed from the metal-carboxylate chains further extending through bpa pairs. Furthermore, the solid state luminescent properties of complexes 1~3 were investigated at room temperature.     

Hydrothermal Syntheses and Crystal Structures of Two Complexes of Cobalt and Manganese Assembled by 4,4'-Oxydibenzoic Acid

Two new coordination polymers [Co(oba)(mbix)]2n·n H2O(1) and [Mn(Hoba)2(H2O)2]n(2)(H2oba = 4,4'-oxydibenzoic acid, mbix = 1,3-bis(imidazol-1-ylmethyl)benzene) have been successfully synthesized under hydrothermal conditions. Their structures have been determined by elemental analyses, IR spectroscopy, UV and single-crystal X-ray diffraction analysis. The intermolecular hydrogen bonding and π-π stacking interactions extend the complexes into a 3D supramolecular structure.     

pH Dependent Supramolecules Based on Co-crystallization of Pyrazine-2,3,5,6-tetracarboxylic Acid with 4,4'-Bipyridine through Intermolecular Hydrogen Bonds

Co-crystallization of pztcH_4 with 4,4?-bipyridine(4,4?-bipy) in pH = 3~4 and 1~2 gave two new binary molecular adducts: [(4,4?-bipy H2)(pztc H_2)](1) and [(4,4?-bipy H_2)(pztcH_3)(Cl)]·4H_2O(2), respectively. Compounds 1 and 2 have been characterized by IR, elemental analysis, NMR and X-ray single-crystal diffraction. Compound 1 crystallizes in triclinic, space group P1 with a = 5.7752(12), b = 7.9126(16), c = 9.4492(19) ?, α = 97.49(3), β = 107.71(3), γ = 94.52(3)o, V = 404.62(14) ?3, Z = 1, μ = 0.137 mm-1, Dc = 1.692 Mg/m3, C_(18)H_(12)N_4O_8, Mr = 412.32, F(000) = 212, S = 1.025, R = 0.0360 and w R = 0.0973. Compound 2 crystallizes in monoclinic, space group C2/c with a = 17.093(3), b = 7.7665(16), c = 18.414(4) ?, β = 113.36(3)o, V = 2244.1(8) ?3, Z = 4, μ = 0.244 mm-1, Dc = 1.542 Mg/m~3, C_(18)H_(21)ClN_4O_(12), Mr = 520.84, F(000) = 1080, S = 1.021, R = 0.0343 and w R = 0.0978. In compound 1, pztc H22- anions self-formed 2-D sheets by strong Oacid-H···Oacidhydrogen bonds, which are further extended to form a 3-D supramolecular network bridged with 4,4?-bipy via N-H···Oacid interactions. In compound 2, besides the 1-D chain constructed by pztc H3-itself through strong H-bond Oacid-H···Oacid, the other chain is constructed with 4,4?-bipy H22+, Cl-anion and water molecules by moderate H-bonds and Ow-H···Cl and N-H···Ow. The two chains are linked with μ3-connected water molecules resulting from the combination of strong synthon-assisted H-bonding O_(acid)-H···O_w to afford an interlaced 3-D network.     

Syntheses and Crystal Structures of Three Novel Zn~Ⅱ-sulfonyldibenzoilate Coordination Polymers

Three coordination polymers based on the V-shaped 4,4＇-dicarboxybiphenyl sulfone （H2sdba） ligands, [Zn3（μ-OH）2（sdba）2]n·2nH2O 1, [Zn2（sdba）2（4,4＇-bipy）]n·2nH2O 2 and [Zn3（sdba）3（py）2]n·n（py）·nH2O 3 （4,4＇-bipy = 4,4＇-bipydine）, were hydrothermally synthesized and structurally characterized. Complex 1 features the 2D planes constructed by the sdba ligands linking infinite Zn-O-C SBUs. The 4,4＇-bipy ligands in 2 bridge the Zn^II-sdba chains into interpenetrated 2D planes. The 3D network of α-Po topology in 3 is built from tri-nuclear Zn3 units with a [Zn3（OOC）6] structure. The intense blue and yellow luminescence was observed in complexes 1～3 which may result from ligand-to-metal charge transfer （LMCT）.     

Hydrothermal Syntheses,Crystal Structures,and Characterization of Two Zinc(Ⅱ) Complexes Containing Flexible Bis(benzimidazole) Ligands

Two zinc(Ⅱ) complexes, namely, [Zn(L_1)Cl_2]_2(1) and {[Zn(L_2)(tbta)]·3H_2O}n(2)(L_1 = 1,3-bis(2-methylbenzimidazol-1-ylmethyl)benzene, H2 tbta = tetrabromoterephthalic acid, L2_ = 1,3-bis(2-methylbenzimidazol-1-yl)-2-propanol), have been successfully obtained under hydrothermal conditions. Complex 1 displays a binuclear structure which is further extended into a 1D supramolecular chain through π-π stacking. Complex 2 features a 2D(4,4) network based on a L2/tbta2- double linker. The thermal stability, fluorescence properties and catalytic activities of two complexes for the degradation of methyl orange in a Fenton-like process were discussed.     

Synthesis, crystal structures and fluorescence properties of four mixed-ligands Zn(Ⅱ) and Cd(Ⅱ) coordination compounds

Four new coordination compounds, [Zn(dba)(bpy)]n (1), {[Zn(dba)(phen)]·2H2O}n (2), [Cd(dba)(bpy)(H2O)2] (3) and [Cd2(dba)2(phen)2]n (4) (H2dba = 2,5-dihydroxy-p-benzenediacetic acid, bpy = 2,2′-bipyridine, phen = 1,10-phenanthroline) have been prepared via solvothermal method and characterized by sin-gle-crystal X-ray diffraction, infrared spectroscopy, elemental analysis and powder X-ray diffraction. 1 and 2 possess 1D infinite chain structures. Complex 3 exhibits a mononuclear structure. Complex 4 owns bi...     

Two New Mn(Ⅱ)/Co(Ⅱ) Complexes Assembled by 2,5-Dihydroxy-1,4-benzenedicarboxylic Acid and Phenanthroline or Derivative

Two new complexes [Mn(DHTA)(PLQ)]n(1) and{[Co2(DHTA)(phen)2(H2 O)6]· DHTA}n(2)(H2 DHTA = 2,5-dihydroxy-1,4-benzenedicarboxylic acid, PLQ = 1,10-phenanthroline-5,6-quinone, phen = 1,10-phenanthroline) have been hydrothermally synthesized and structurally characterized by elemental analysis, IR spectrum, fluorescence spectrum, single-crystal and power X-ray diffraction. Complex 1 exhibits a two-dimensional(2 D) network, which was stabilized through O–H···O hydrogen bonding interactions. Complex 2 shows a zero-dimensional structure, which was further extended into a three-dimensional supramolecular structure through O–H···O hydrogen bonds and π-π interactions.