Two Cd(Ⅱ) Coordination Polymers Based on a Flexible Tricarboxylate Ligand: Syntheses,Structures, and Photoluminescence and Catalytic Properties

Studies on the synthesis and design of coordination polymers(CPs) with flexible ligands are of great interest owing to their dynamic structures and promising applications. The title coordination polymers, {[Cd·(HTTTA)·(phen)]·2H_2 O}n(1) and [Cd·(HTTTA)·(phen)]n(2)(H3 TTTA = 2,2',2'-[1,3,5-triazine-2,4,6-triyltris(thio)] tris-acetic acid, phen = 1,10-phenanthroline) have been synthesized and characterized by elemental analysis, IR, powder XRD and single-crystal X-ray diffraction. Complex 1 consists of one CdII ion, one HTTTA2-ligand and one phen co-ligand. The Cd(Ⅱ) metal clusters were bridged by the tridentate HTTTA2-ligands into infinite 1D chains, which are further connected into the 3D architecture by abundant hydrogen bonds. In 2, three carboxyl groups of HTTTA2-ligand show different coordination directions because of the C–S–C flexible bond angle, which leads to different 1D chains of 2. The strong π-π stacking interaction and four C–H···O hydrogen bonds connect the 1D chains into a 3D framework. The solid-state photoluminescence and catalytic properties were studied as well.     

Syntheses,Crystal Structures,and Magnetic Properties of Mn(Ⅱ) and Co(Ⅱ) Coordination Polymers Constructed from Pyridine-tricarboxylate Ligand

Two coordination polymers, namely {[Mn(HL_1)(phen)]·4H_2O}_n(1) and [Co_2(HL_2)_2(H_2O)_2]_n(2) have been constructed hydrothermally using H_3L_1 and H_3L_2(H_3L_1 = 2-(5-carboxypyridin-2-yl)terephthalic acid, H_3L_2 = 2-(4-carboxypyridin-3-yl)terephthalic acid), phen, MnCl_2×4H_2O and CoCl_2×6H_2O. The products were isolated as stable crystalline solids and were characterized by IR spectroscopy, elemental, thermogravimetric(TGA), powder(PXRD) and single-crystal X-ray diffraction analyses. Compound 1 features a 3D framework structure, which was topologically classified as a trinodal 4,6,6-connected net with the unique topology defined by the point symbol of(3~(10).5.6~4)4(3~(10).6.7~4)2(5.6~2.8~2.9). Compound 2 possesses a 2D metal-organic layer, which was topologically classified as a binodal 4,4-connected layer defined by the point symbol of(4~3.6~2.8). The layers are further extended into a 3D supramolecular framework via hydrogen bonds. The magnetic properties for both compounds were also investigated, indicating antiferromagnetic interactions between the adjacent metal ions.     

Syntheses,Structures,and Photoluminescent Properties of Two Zn(Ⅱ) Coordination Polymers with Helical Chains Structures

Two novel coordination polymers with helical chains, {[Zn(L)(H2O)]?H2O}n(1) and {[Zn(L)(p-bix)]?3.5H2O}n(2), where H2 L = 5-(4-hydroxypyridinium-1-ylmethyl) isophthalic acid and p-bix = 1,4-bis(imidazol-1-ylmethyl)benzene, have been hydrothermally synthesized, and charac-terized by elemental analysis, powder X-ray diffraction(PXRD), IR, thermal gravimetric analyses(TGA) and also by single-crystal X-ray diffraction. Both complexes 1 and 2 crystallize inmonoclinic, space group P21/c. Compound 1 displays a two-dimensional(2D) structure with two distinct types of helical chains; 2 shows a layered coordination polymer with two types of helical chains and features an interesting 2D→3D interdigitated architecture. Meanwhile, the luminescent properties of 1 and 2 have also been investigated in detail.     

Syntheses,Structures and Photocatalytic Degradation Properties of Two Copper(Ⅱ)Coordination Polymers with Flexible Bis(imidazole)Ligand

Two copper(Ⅱ)coordination polymers{[Cu(bib)(nip)]·1.5H2O}n(1)and[Cu2(bib)(glu)2]n(2)(bib= 1,4-bis(2-methyl-imidazol-1-yl)butane,H2nip = 5-nitroisophthalic acid,...     

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.     

Two Coordination Polymers Constructed by Cd(Ⅱ) and Zn(Ⅱ) with in situ Generated 5-(3-Pyridyl)tetrazolate Ligand:Syntheses,Crystal Structures and Luminescence Properties

Hydrothermal reactions of 3-cyanopyridine and Na N3 with Zn Cl_2 or Cd Cl_2·5/2H_2 O in the presence of 1,4-benzenedicarboxylic acid(H2bdc) yielded two new coordination polymers,{[Zn(3-ptz)(bdc)_(0.5)(H_2O)_2]n·2H_2O}_n(1) and [Cd_2(3-ptz)_2Cl_2]_n(2),based on in situ synthesized 5-(3-pyridyl)tetrazolate(3-ptz-) organic ligand.They have been structurally characterized by elemental analysis(EA),infrared spectroscopy(IR) and single-crystal/powder X-ray diffraction(PXRD).In 1,two Zn(Ⅱ) ions are linked together through two μ_2-(3-ptz-) ligands to form a dimeric unit of [Zn(μ_2-3-ptz)(H_2O)_2]_2~(2+),which is further connected with other equivalent units by μ_2-bdc~(2-)spacers,resulting in an infinite 1D polymeric chain of [Zn_2(3-ptz)_2(H_2O)_2(bdc)]_n,and then strong hydrogen bonding interactions extend these 1D chains into a 3D supramolecular structure.In 2,the Cd(Ⅱ) ions are connected through μ_4-(3-ptz-) ligands and Cl-anions,leading to infinite 2D layers of [Cd_2(3-ptz)Cl_2]_n~(n+),which are further linked by another μ_4-(3-ptz-) pillared ligand to form a 3D layered-pillared framework architecture of [Cd)2(3-ptz))2Cl)2])n.Furthermore,thermal stability of these compounds was measured by thermogravimetric analysis(TGA) and their photoluminescent properties were also investigated in the solid state at room temperature.     

Hydrothermal Syntheses,Crystal Structures and Characteristics of Two New Isostructural Ni(Ⅱ) Coordination Polymers

Two new isostructure nickel(Ⅱ) coordination polymers, [Ni_2(5-Me-ip)(1,2-Bie)(H_2O)_2]_n(1) and [Ni2(5-Br-ip)(1,2-Bie)(H_2O)_2]n(2)(5-Me-H2 ip = 5-methylisophthalic acid, 5-Br-H2 ip = 5-mromoisophthalic acid, 1,2-Bie = 1,2-bis(imidazole)ethane), have been synthesized and structurally characterized by single-crystal X-ray diffraction. The result shows that complexes 1 and 2 crystallize in orthorhombic system, space group Pna21 with a = 16.3602(13), b = 10.1465(8), c = 21.8803(17) ?, V = 3632.1(5) ?3, Z = 4, D3 c = 1.525 g/cm, F(000) = 1728, R = 0.0292 and wR = 0.0668 for 6646 observed reflections(I 2σ(I)) for complex 1 and a = 16.409(3), b = 10.1625(17), c = 21.918(4) ?, V = 3654.9(11) ?3, Z = 4, Dc = 1.752 g/cm~3, F(000) = 1936, R = 0.0309 and wR = 0.0600 for 6809 observed reflections(I 2σ(I)) for complex 2. They both feature zigzag 2D layer structures, which are further staked along the a-axis through π···π and hydrogen interactions to form 3D supramolecular structures.     

Syntheses,Structures and Properties of Two Mn(Ⅱ) Clusters Based on 1,10-Phenanthroline-2,9-dicarbaldehyde Dioxime Ligand

Two novel clusters [Mn~Ⅲ_3(μ_3-O)(phendox)3]X·13H_2O(X = Cl(1), Br(2]) have been obtained from the solvothermal reactions of 1,10-phenanthroline-2,9-dicarbaldehyde dioxime(H_2phendox) with MnCl_2·4H_2O or anhydrous MnBr_2, and their structures were characterized by elemental analysis, FT-IR, XRD, TGA, MS and single-crystal X-ray diffraction. It crystallizes in trigonal, space group P3_1/c. X-ray analysis reveals that the neighbouring [Mn_3(μ_3-O)(phendox)_3]+ cores are linked by C–H···Cl hydrogen bonds and form an infinite supramolecular chain along the c-axis. Neighbouring chains are packed with each other by off-set p-p interactions of the aromatic rings on phenox2-. A 3D supramolecular architecture in a honeycomb topology is formed with 1D hexagonal channel in the dimensions of 13? × 13? along the c-axis. The gas adsorption studies show that compound 1·13H_2O is stable upon the removal of guest molecules and the desolvated compound absorbed considerable amount of CO_2.     

Syntheses,Structures and Luminescent Properties of Cd(Ⅱ)/Zn(Ⅱ) Coordination Polymers Based on the Flexible 4-Substituted Bis(1,2,4-triazole) Ligand

Two new cadmium(Ⅱ) and zinc(Ⅱ) coordination polymers, {[Cd(btre)0.5-(mip)(H_2O)_2]·H_2O}n(1) and [Zn(btre)(mip)]n(2), were synthesized at room temperature condition and characterized by IR spectra, elemental analyses, single-crystal and powder X-ray diffractions(btre = 1,2-bis(1,2,4-triazol-4-yl)ethane, H2 mip = 5-methyl-1,3-benzenedicarboxylic acid). Complex 1 belongs to the triclinic system, P1 space group, with a = 8.9830(6), b = 10.0579(6), c = 10.2479(9) ?, α = 98.837(6), β = 115.975(8), γ = 106.370(6)°, V = 756.30(11) ?~3 and Z = 2; complex 2 crystallizes in monoclinic, space group P21/c, with a = 7.0332(3), b = 14.9947(7), c = 15.9689(7) ?, β = 97.1170(10)°, V = 1671.12(13) ?~3 and Z = 4. Compounds 1 and 2 based on the same N/O-donor ligands show different structures. The one-dimensional chains of 1 are further linked by hydrogen bonding and π-π interactions to yield a three-dimensional supramolecular structure. The two-dimensional(6,3) networks of 2 are further extended into a 3D framework via π-π interactions. Thermal stabilities and luminescence of 1 and 2 were investigated.     

Syntheses,Crystal Structures,and Magnetic Properties of Two Manganese(Ⅱ) Coordination Polymers Based on Bifunctional Pyridine-benzene Carboxylic Acids

Two manganese(II) coordination polymers, namely, {[Mn(PIP)(BIBP)]·(BIBP)0.5}n(1) and {[Mn(PTA)(BIMBP)(H_2O)]·H_2O_(0.69)}_n(2)(H_2PIP = 5-(4-pyridyl)-isophthalic acid, H_2 PTA =6-(4-pyridyl)-terephthalic acid, BIBP = 4,4?-bis(imidazol-1-yl)biphenyl, and BIMBP =4,4?-bis(imidazol-1-ylmethyl)biphenyl), have been synthesized by using the bifunctional pyrinde-benzene carboxylic acids and bis(imidazole) linkers as mixed ligands to react with Mn SO4,and further characterized by elemental analysis, IR, and PXRD. Compound 1 is in the triclicnic system, space group P1 with a = 10.1089(8), b = 13.1927(12), c = 14.0638(12) ?, α = 69.437(2), β= 73.2890(10), γ = 78.5320(10)o, V = 1671.9(2) ?~3, Z = 2, Dc = 1.449 g/cm3, F(000) = 705,μ(MoK α) = 0.453 mm-1, S = 1.053, R = 0.0491 and wR = 0.1367 for 5837 unique reflections(Rint =0.0208) with I 2σ(I). Compound 2 belongs to the monoclicnic system, space group C2/c with a =15.199(3), b = 19.731(3), c = 21.537(5) ?, β = 105.228(3)o, V = 6232(2) ?3, Z = 8, Dc = 1.363g/cm3, F(000) = 2648, μ(MoK α) = 0.475 mm-1, S = 1.048, R = 0.0489 and wR = 0.1151 for 7414 unique reflections(Rint = 0.0425) with I 2σ(I). Structural analyses reveal that complex 1 is a4-connected(44.62)-sql bilayer structure with binuclear [Mn_2(COO)_2] SBU, while complex 2 is a normally(3,5)-connected(42.67.8)(42.6)-3,5L2 monolayer. And the sheets interacted with the adjacent sheets through weak interactions, finally giving a stable three-dimensional(3D)supramolecule. Besides, the variable-temperature magnetic susceptibility measurement of complex1 was investigated.     

Organic Carboxylate Ligand Tuned Topological Variations in Three Zn(Ⅱ) Coordination Polymers: Syntheses,Crystal Structures and Photoluminescent Properties

Three new Zn(Ⅱ) coordination polymers, namely [Zn_2(suc)_2(bib)_2]_n·nH_2 O(1), [Zn(glu)(bib)]_n·4 nH_2 O(2), and [Zn(adp)(bib)]n(3)(bib = 1,4-bis(N-imidazolyl)butane, H_2 suc = succinic acid, H_2 glu = glutaric acid, H_2 adp = adipic acid) have been hydrothermally synthesized and structurally characterized. Compound 1 features a 3D framework with 4-connected hxg-d topological network, compound 2 is comprised of 2D 4~4-sql-type sheets, and the adjacent 2D sheets are further packed into a 3D supramolecular architecture via intermolecular hydrogenbonding interactions, and compound 3 is a 3D framework with 4-fold interpenetrating dia topology. The structural comparison of these three compounds demonstrates that the topological variations can be well controlled by employing aliphatic dicarboxylate ligands with different spacer lengths. Moreover, the thermal stabilities and photoluminescent properties of them were also studied in detail.     

Syntheses,Crystal Structures and Magnetic Properties of Two New Low-dimensional Manganese (Ⅱ) Coordination Compounds

Two new low-dimensional Mn(Ⅱ) coordination compounds of Mn(H_2pimdc)_2(phen)(compound 1) and [Mn(Hpimdc)(phen)]n·nH_2O(compound 2) were synthesized, where H_3pimdc is a 2-propyl-imidazole-4,5-dicarboxylic acid and phen is 1,10-phenanthroline. Both compounds were thoroughly analyzed by X-ray single-crystal diffraction, element analysis, IR spectra, PXRD and thermal analysis. X-ray single-crystal diffraction analyses indicate that the phen ligands terminate metal ions on two sides to prevent the linkage between the neighboring metal ions into a higher dimensional structure in compounds 1 and 2. Compound 1 is constructed from mononuclear molecules which form the 1D helical supramolecular chain by N–H···O hydrogen bonds. In compound 2, Hpimdc is a tetradentate bridging ligand, which binds Mn(Ⅱ) ions to generate a single-stranded right helical chain parallel to the b axis. These 1D chains are additionally coupled by H-bonds as well as π···π stacking interactions, which formed a 3D supramolecular structure. Additionally, compound 2 demonstrated temperature-dependent magnetic susceptibility and negative value of θ(equal to –9.09 K), which is indicative of weak antiferromagnetic interactions between Mn(Ⅱ) ions.     

Two New Coordination Polymers Assembled with a Functionalized Ligand：Syntheses and Crystal Structures

Two new transition-metal organic coordination polymers [M(mna)2](M = Cd(1),Zn(2);mna = 2-mercaptonicotinic anion) have been hydrothermally synthesized and structurally characterized by single-crystal X-ray diffraction along with IR and elemental analyses.Compound 1 is generally a one-dimensional linear structure bridged through the sulfur donor of mna ligand,while 2 is a one-dimensional zigzag chain ligated via the oxygen donor of mna ligand.These compounds further result in three-dimensional structures via intermolecular π...π stacking interactions and/or hydrogen bonding interactions.The two compounds were structurally determined by single-crystal X-ray diffraction.Complex 1 crystallizes in monoclinic space group P21/c with a = 3.730(3),b = 13.973(12),c = 12.380(11) ,β = 97.953(18)°,V = 639.0(10) 3,Z = 2,CdC12H8O4N2S2,Mr = 420.72,Dc = 2.187 g/cm3,F(000) = 412,Rint = 0.0252,T = 293(2) K,μ = 2.052 mm?1,the final R = 0.0269 and wR = 0.0586 for 1377 observed reflections with I > 2σ(I).Complex 2 belongs to monoclinic space group P21/c with a = 13.376(2),b = 12.8429(14),c = 7.4856(10) ,β = 96.190(10)°,V = 1278.5(3) 3,Z = 4,ZnC12H8O4N2S2,Mr = 373.69,Dc = 1.941 g/cm3,F(000) = 752,Rint = 0.0414,T = 293(2) K,μ = 2.264 mm?1,the final R = 0.0418 and wR = 0.0966 for 2396 observed reflections with I > 2σ(I).     

Two N-donor Auxiliary Ligands Mediated Zn(Ⅱ) Coordination Polymers Incorporating 5-Nitro-1,2,3-benzenetricarboxylate Ligand: Syntheses,Crystal Structures,and Luminescent Properties

Two N-donor auxiliary ligands mediated Zn(Ⅱ) coordination polymers, namely, {[Zn(Hnbta)-(bimm)](3H_2O)}_n(1) and {[Zn_(1.5)(nbta)(pyim)(H_2O)](2H_2O)}_n(2)(H_3nbta = 5-nitro-1,2,3-benzenetricarboxylic acid, bimm = bis(imidazol-1-yl)methane and pyim = N-(4-pyridylmethyl)imidazole), have been prepared by the hydrothermal reaction. Their structures were determined by single-crystal X-ray diffraction analysis, elemental analyses and infrared spectra. Compound 1 possesses a one-dimensional(1D) chain structure, while compound 2 features a two-dimensional(2D) network. In addition, they both exhibit high thermal stabilities and photoluminescent properties in the solid, and can be explored as potential luminescent materials.     

Syntheses, Structures and Photoluminescence of Two New Europium（III） Coordination Polymers

Two new europium (Ⅲ) coordination polymers formulated as Eu2(H2O)2(ox)4 ]· (C5H6N)2 ·2H 2 O(1) and Eu 2(ad)3(H2O)4 ]·0.25H2O (2) (H2ox = oxalic acid, H2ad = adipic acid) have been synthesized from the self-assembly of lanthanide ions Eu 3+ with flexible oxalic and adipic acid ligands, respectively. Structural analyses revealed that complex 1 exhibits three-dimensional metalorganic frameworks, and 2 has intricate two-dimensional interpenetrated metal-organic networks. In addition, the photoluminescent properties of complexes 1 and 2 were discussed in detail, which shows strong red emission, corresponding to 5 D0 → 7 F 2 transition of Eu3+ ions.     

Two Ni~Ⅱ/Cu~Ⅱ Coordination Polymers Based on Pyridyl-carboxylate Ligand: Synthesis,Crystal Structures and Magnetic Properties

Under hydrothermal conditions, the reactions of Ni~Ⅱ/Cu~Ⅱ ions with 3-(6-aminpyridinium-3-yl) benzoate(HL) afford two compounds [NiL 2]n(1) and [Cu L2(H2 O)]n(2). On the basis of X-ray diffraction analysis of the two compounds, the results show that compound 1 features one-dimensional(1 D) double-strand coordination arrays, while 2 presents the 63-hcb layers. Both compounds are further constructed into a 3 D supramolecular structure with the aid of weak secondary interactions. Thermal stabilities and magnetic properties of compounds 1 and 2 were also investigated.     

Syntheses,Crystal Structures and Luminescent Properties of Two New Zinc(Ⅱ) Complexes Based on Bifunctional Ligand

By using solvothermal method,two novel coordination polymers based on 4-(4-carboxyphen-yl)-1,2,4-triazole(Hcpt) and Zn(Ⅱ) cations,[Zn(cpt)(OH)]_n·n H_2O(FJU-32) and [Zn(cpt)(atrz)]n(FJU-33)(Hatrz = 3-amino-1,2,4-triazolate),were synthesized and characterized by single-crystal X-ray diffraction analyses,elemental analyses,FT-IR and powder X-ray diffraction. FJU-32 crystallizes in monoclinic,space group P21/c with a = 3.7441(3),b = 23.0384(19),c = 11.8562(10) ?,β = 99.069(8)o,V = 1009.91(15) ?3,Dc = 1.898 g/cm3,C_9H_9N_3O_4Zn,Mr = 288.57,F(000) = 916,μ(MoKα) = 2.439 mm~(-1),Z = 4,R = 0.0600 and wR = 0.1306 for 2412 observed reflections(I 2σ(I)),and R = 0.0704 and wR = 0.1349 for all data. FJU-33 crystallizes in monoclinic space group P21/c with a = 12.7483(5),b = 9.9922(3),c = 9.8403(3) ?,β = 100.756(4)°,V = 1231.47(7) ?~3,Dc = 1.816 g/cm~3,C_(11)H_9N_7O_2Zn,Mr = 336.62,F(000) = 680,μ(Cu Kα) = 2.957 mm~(-1),Z = 4,R = 0.0478 and w R = 0.1184 for 2466 observed reflections(I 2σ(I)),and R = 0.0687 and w R = 0.1309 for all data. In FJU-32,Zn(Ⅱ) is coordinated to three μ3-OH groups forming an unprecedented 1D zigzag-like double chain,and the 1D double chains are connected to four neighbouring double chains by the cpt ligands to form an extended 3D porous coordination polymer. In FJU-33,the adjacent [Zn(atrz)] 2D layers are further connected by the cpt ligands via Zn–O coordinated bonds and neighboring interlayer hydrogen-bonding interactions to give rise to an overall 3D pillared layer structure. The neutron triazole group of the cpt ligand has weaker coordination ability than the triazolate anion of atrz ligand. Furthermore,FJU-32 and FJU-33 display high thermal stability up to 300 ℃,and the solid state fluorescence reveals that two new complexes are potential optical materials.     

Auxiliary Ligand-tuned Structural Variation of Cd(Ⅱ) Coordination Polymers: Synthesis,Crystal Structures and Luminescent Properties

Two new Cd(Ⅱ) coordination polymers, [Cd(PT)(1,4-BDC)0.5]_n(1) and [Cd(PT)(1,3-BDC)0.5]_n(2)(HPT = 3-(pyridin-2-yl)-1,2,4-triazole, 1,4-H2 BDC = 1,4-benzenedicarboxylic acid, 1,3-H2 BDC = 1,3-benzenedicarboxylic acid), have been hydrothermally synthesized and structurally characterized by single-crystal X-ray diffraction as well as elemental analysis and IR. Complexes 1 and 2 are both three-dimensional coordination polymers with two-dimensional sheet structures bridged by the deprotonated carboxylate ligands. In 1, 1,4-BDC~(2-) bridges the layered network to generate a quadrangular framework, and 2 owns a sexangular framework, which was caused by the different steric hindrance between 1,4-BDC~(2-) and 1,3-BDC~(2-). Their thermal stabilities and photoluminescent properties have been also investigated.