Syntheses,Crystal Structures and Magnetic Properties of Ni(Ⅱ) and Mn(Ⅱ) Coordination Polymers Constructed from 5-(2'-Carboxylphenyl) Nicotate and 2,2'-Biimidazole

Two coordination polymers, namely {[Ni(cpna)(H2biim)(H2O)]·H2O}n(1) and {[Mn(cpna)(H2biim)]·H2O}n(2)(H2cpna = 5-(2'-carboxylphenyl) nicotic acid, H2biim = 2,2'-biimidazole),have been hydrothermally synthesized and characterized by elemental analysis, IR, TG, magnetic properties, and single-crystal X-ray diffraction. Compound 1 exhibits a one- dimensional(1D) step-like chain structure, which further builds a three-dimensional(3D) supramolecular architecture via O–H···O and N–H···O hydrogen-bonding and π-π stacking interactions. Compound 2 possesses a one-dimensional(1D) double chain structure, which is further assembled into a 3D supramolecular framework by N–H···O hydrogen bonding and π-π stacking interactions. Magnetic susceptibility measurement indicates that compound 1 shows a weak antiferromagnetic coupling between the nearest Ni(II) centers, with g = 2.11 and J = –1.87 cm–1.     

Syntheses,Crystal Structures,and Magnetic Properties of the Cobalt(Ⅱ) and Nickel(Ⅱ) Coordination Polymers Constructed from 5-Halonicotinate and 2,2ˊ-Biimidazole

Two coordination polymers, namely [Co(5-Clnic)2(H2biim)]n 1 and {[Ni(5-Clnic)(Hbiim)]·H2O}n 2(5-Clnic H = 5-halonicotinic acid, H2 biim = 2,2ˊ-biimidazole), were assembled. Single-crystal X-ray diffraction studies show that compound 1 possesses a 1D chain coordination network, which is further extended into a 3D supramolecular architecture via N–H···O hydrogen bonds and π-π packing interactions. Compound 2 features a 1D chain structure based on the hexanuclear macrocycles. The adjacent 1D chains are held together into a 3D supramolecular framework via N–H···O and O–H···O hydrogen bonding interactions. Thermal stability and magnetic properties of both compounds were studied and discussed.     

Syntheses,Crystal Structures and Luminescent Properties of Lead(Ⅱ) and Cadmium(Ⅱ) Coordination Polymers Constructed from Biphenyl-2,5,3′-tricarboxylate

Two coordination polymers, namely [Pb(Hbtc)(phen)]n(1) and {[Cd3(btc)2(H2O)4]·2H2O}n(2, H3btc = biphenyl-2,5,3'-tricarboxylic acid, phen = 1,10-phenanthroline), were assembled. Single-crystal X-ray diffraction studies show that compound 1 possesses a zigzag chain 1D coordination network, which is further extended into a 3D supramolecular architecture via O–H···O hydrogen bonds and π-π packing interactions. Compound 2 features a 3D open framework based on a tricadmium(II) subunit, generating a trinodal 4,4,6-connected net with the 4,4,6T24 topology defined by the point symbol of(44·62)3(46·69)2. Thermal stability and luminescent properties of both compounds were studied and discussed.     

Syntheses,Crystal Structures and Magnetic Properties of Cobalt(Ⅱ) and Manganese(Ⅱ) Coordination Polymers Constructed from 5-(Pyridin-4-yl)Isophthalate Ligands

Two coordination polymers, namely {[Co(L)(H2O)]·H2O}n(1) and [Mn(L)(phen)]n(2, H2L = 5-(pyridin-4-yl)isophthalic acid, phen = 1,10-phenanthroline), have been hydrothermally synthesized and characterized by elemental analysis, IR, TG, magnetic properties, and single-crystal X-ray diffraction. 1 belongs to the triclinic system, space group P1 with a = 7.2188(7), b = 10.0835(8), c = 10.2069(7) ?, α = 113.713(7), β = 99.490(7), γ = 104.516(8)o, V = 628.24(9) ?3, C13H11NCoO6, Mr = 336.16, Z = 2, Dc = 1.777 Mg/m3, μ(MoKα) = 1.395 mm–1, F(000) = 342, S = 1.041, the final R = 0.0381 and wR = 0.0819 for 3744 observed reflections(I 2σ(I)) and R = 0.0448 and wR = 0.0874 for all data. 2 belongs to the monoclinic system, space group P2/c with a = 12.9185(3), b = 10.4343(2), c = 31.7650(6)?, β = 101.282(2)o, V = 4199.08(13)?3, C50H30N6Mn2O8, Mr = 952.68, Z = 4, Dc = 1.507 Mg/m3, μ(MoKα) = 5.447 mm–1, F(000) = 1944, S = 1.128, the final R = 0.1003 and wR = 0.1052 for 8247 observed reflections(I 2σ(I)) and R = 0.2595 and wR = 0.2625 for all data. Single-crystal X-ray diffraction studies show that compound 1 features a 2D sheet structure based on a dicobalt(II) subunit, which is further extended into a 3D metal-organic supramolecular framework by O–H···O hydrogen bond. Compound 2 also possesses a 2D sheet, which is held together into a 3D supramolecular architecture via C–H···O hydrogen bond and π-π stacking interactions. Magnetic studies for compound 2 show antiferromagnetic coupling between the adjacent metal centers, with J = –11.8 cm–1 and g = 2.12 for 2.     

Syntheses,Structures and Catalytic Properties of Two Mn(Ⅱ) and Cd(Ⅱ) Coordination Polymers through in Situ Ligand Reaction

Two coordination polymers, namely [Mn(μ-Hcpia)(bipy)(H_2O)_2]_n(1) and [Cd_3(μ_3-Hcpia)_2(μ-Hbiim)_2(μ-H_2biim)(H_2O)_2]_n(2), have been constructed hydrothermally using H_2cbia(H_2cbia = 5-(4'-cyanobenzoxy)isophthalic acid), bipy(bipy = 4,4'-bipyridine), H_2biim(H_2biim = 2,2'-biimidazole), and manganese or cadmium chlorides at 160℃. Interestingly, the H_3cpia(H_3cpia = 5-(4'-carboxylphenoxy)isophthalic acid) ligand was generated by in situ hydrolysis of cyano group in H_2cbia. The products were isolated as stable crystalline solids and were characterized by IR spectra, elemental analyses, thermogravimetric analyses(TGA), and single-crystal X-ray diffraction analyses. Both compounds crystallize in the triclinic system, space group P1. Compound 1 discloses a 1D linear chain of the 2C1 topological type. Adjacent chains are assembled into a 2D supramolecular sheet through O–H···O/N hydrogen bonds. Compound 2 features a 3D framework with a 3,4,4 T25 topology. The luminescent and catalytic properties of two compounds were investigated. Compound 1 exhibits a superior catalytic activity in the cyanosilylation at room temperature.     

Syntheses,Crystal Structures and Luminescent and Magnetic Properties of Cerium(Ⅲ) and Zinc(Ⅱ) Coordination Compounds Constructed from 3,5-Dibromobenzoic Acid

Two coordination compounds, namely [Ce(3,5-Br2BC)3(3,5-HBr2BC)]n(1) and [Zn(3,5-Br2BC)2(phen)](2, 3,5-HBr2 BC = 3,5-dibromobenzoic acid, phen = 1,10-phenanthroline), were assembled. Single-crystal X-ray diffraction studies show that compound 1 possesses a 1D chain coordination network, which is further extended into a 3D supramolecular architecture via Br···Br and Br···O halogen bonding. Compound 2 consists of a mononuclear molecule, which is assembled to a 3D supramolecular framework through C–H···O hydrogen bond, π-π stacking interactions and Br···π halogen bonding. Luminescent and magnetic properties of both compounds have also been studied.     

Syntheses,Crystal Structures,Magnetic and Luminescent Properties of Ni(Ⅱ), Cd(Ⅱ) and Pb(Ⅱ) Coordination Compounds Constructed from 5-Fluoronicotinic Acid

Five coordination compounds, namely [Ni_2(5-Fnic)_2(H_2 O)_4](1), [Ni(5-Fnic)(μ-5-Fnic)(H_2 biim)]n(2), {[Cd((μ-5-Fnic)2(H2 O)2]×4,4'-bipy}n(3), [Pb_2(μ-5-Fnic)_2(μ3-5-Fnic)_2(H_2 O)_2]n(4), and [Pb(5-Fnic)_2(4,4'-bipy)(H_2 O)](5), have been constructed hydrothermally using 5-FnicH(5-FnicH = 5-fluoronicotinic acid), H_2 biim(H_2 biim = 2,2'-biimidazole), 4,4'-bipy(4,4'-bipy = 4,4'-bipyridine), NiCl_2×6 H_2 O, CdCl_2×H_2 O and PbCl_2. The products were isolated as stable crystalline solids and were characterized by IR spectra, elemental analyses, thermogravimetric analyses(TGA), and single-crystal X-ray diffraction analyses. Structures of 1～5 range from discrete 0 D monomers(1 and 5) to 1 D coordination polymers(2 and 4) and 2 D metal-organic network(3). A broad structural diversity of 1～5 is guided by the type of the metal(Ⅱ) node and the introduction of auxiliary ligands. The magnetic(for 2) and luminescent(for 3～5) properties were also investigated and discussed.     

Syntheses,Crystal Structures and Properties of Mn(Ⅱ) and Co(Ⅱ) Coordination Complexes Based on 1,10-Phenanthroline Derivative

Two new coordination complexes[Mn(L)₂(DNSA)](1) and[Co(L)(1,4-bdc)]_n (2) have been achieved under hydrothermal conditions (H₂DNSA=3,5-dinitro-salicylic acid,1,4-bdc=1,4-benzenedicarboxylic acid and L=2-(2-fluoro-6-fluorophenyl)-1H-imidazo[4,5-f][1,10]phenanthroline).1 crystallizes in monoclinic,space group P2_1/c with a=15.871(3),b=17.274(4),c=16.078(3)A,β=113.03(3)^o,V=4056.6(16)A³,Z=4,C₄₅H₂₂Cl₂F₂Mn N₁₀O₇,M_r=978.57,D_c=1.602 g/cm³,F(000)=1980,μ(Mo Ka)=0.536 mm^–1,R=0.0437 and w R=0.1065.2 belongs to the monoclinic system,space group C2/c with a=14.665(2),b=30.856(4),c=11.237(2)A,β=111.166(2)^o,V=4742.0(12)A³,Z=8,C₂₇H₁₄Cl Co FN₄O₄,M_r=517.80,D_c=1.602 g/cm³,F(000)=2312,μ(Mo Ka)=0.889 mm^–1,R=0.0364 and w R=0.0862.The central Mn(II) ion in 1 is six-coordinated by four nitrogen atoms from two L ligands and two oxygen atoms from one DNSA anion.In 2,the two kinds of 1,4-bdc ligands link neighboring Co(II) atoms to yield a two-dimensional layer structure.The luminescence of 1 has been studied in detail.Moreover,thermal behaviors of 1 and 2 are also investigated.     

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.     

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.     

A Manganese(Ⅱ) Coordination Polymer Constructed from Phosphonate Ligand:Synthesis,Crystal Structure and Magnetic Properties

A coordination polymer formulated as[Mn(5-pncH₂)₂H₂O](1,5-pncH₃=5-phosphono-1-naphthalenecarboxylic acid),was hydrothermally synthesized and magnetically characterized.Compound 1 features a three-dimensional structure in which the inorganic chains of[Mn(O-P-O)]_n are cross-linked by the organic groups of phosphonate ligands.Magnetic measurements of 1 indicate that dominant antiferromagnetic interactions are mediated between the Mn^Ⅱ centers.     

Three Co(Ⅱ) Coordination Polymers Incorporated with a Bent Connector: Crystal Structures and Magnetic Properties

Based on the bent ligand 1 H-3-(3-pyridyl)-5-(4-pyridyl)-1,2,4-triazole(3,4?-Hbpt) with Co(Ⅱ) ions as well as a series of polycarboxylate co-ligands, three new coordination polymers were yielded, namely, {[Co(op)(3,4?-Hbpt)(H_2O)_3]?2 H_2O}n(1), [Co(cyc)(3,4′-Hbpt)(H_2O)]n(2) and [Co(pro)(3,4′-Hbpt)(H_2O)]n(3)(here, op = o-phthalic anion, cyc = 1,1-cyclobutanedicarboxylic anion, pro = propanedioic anion). In cooperation with the auxiliary polycarboxylate co-ligands, a variety of Co(Ⅱ) coordination networks, such as 1-D chain 1 and 2-D layer 2 and 3 have been assembled. The magnetic behaviors of compounds 1～3 were studied. All of them indicated the existence of interesting spin-canting behavior.     

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.     

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,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 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）.     

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 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.