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.     

Three Complexes Based on Synthetic-condition Strategy Involving a Universal Mixed-ligand System

Three coordination polymers([Zn(H_2biim)_2(H_2O)_2]_2·2(HO-BDC)·x(H_2O)(1)[Cd(H_2biim)_2(H_2O)_2]_2·2(HO-BDC)·x(H_2O)(2) and [Co(HO-BDC)(bbi)]n(3)) are obtained by using synthetic-condition strategy in the mixed-ligand system 5-hydroxyisophthalic acid(OH-BDC)together with bisimidazole ligands(2,2?-biimidazole(H2 biim) and 1,1?-(1,4-butanediyl)bis(imidazole)(bbi)). The structure determination reveals that complexes 1 and 2 are zero-dimensional(0 D) structures, and complex 3 is a dinuclear two-dimensional(2D) layer structure. They are all 3D supramolecular networks. The comparisons of the synthetic-condition effects and structure differences among 1 ～3 and our previous work complexes 4([Co_2(HO-BDC)_2(bbi)_2]·H_2O) and 5([Zn(HO-BDC)(bbi)]) have been discussed in detail. Furthermore, the luminescent properties and thermal stabilities of compounds 1～3 in the solid state have been studied.     

Hydrothermal Syntheses,Crystal Structures and Luminescence Properties of Cu(Ⅱ) and Cd(Ⅱ) Complexes Assembled by 6-Hydroxypicolinic Acid and 1,10-Phenanthroline

Two new complexes based on 6-hydroxypicolinic acid(H_2picO) and 1,10-phenanthroline(phen), such as [Cu_4(picO)_4(phen)_4]·12 H_2O(1) and {[Cd_4(picO)_4(phen)_4(H_2O)_2]·5H_2O}_n(2), have been synthesized and characterized by IR, elemental analyses, thermogravimetric analyses and X-ray diffraction technique. Single-crystal X-ray diffraction analyses revealed that the two complexes both crystallize in the triclinic system, space group P(16)-. For complex 1, the picO ligands adopt a tridentate coordination mode to link copper(Ⅱ) ions into dimmers. PicO ligands also adopt a tridentate mode in complex 2, which connects the cadmium(Ⅱ) to form a one-dimensional chain. Moreover, luminescent properties of 1 and 2 were also investigated.     

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 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.     

Two Co(Ⅱ)-based Coordination Polymers Constructed from π-electron-rich Polycarboxylate Aryl Ether Ligand: Structural Insights and Photocatalytic Dye Degradation

In the present study, two new Co(Ⅱ)-based coordination polymers(CPs) with chemical formulas of {[Co_3(μ_3-OH)(L)(H_2O)_3]·2H_2O}_n(1) and {[Co_3(μ_3-OH)(L)(H_2O)]·_2DMF·3H_2O}_n(2) have been successfully prepared by the reaction of Co(NO_3)_2·6H_2O with π-electron-rich polycarboxylate aryl ether ligand 5,5'-((5-carboxy-1,3-phenylene)bis(oxy))diisophthalic acid(H_5L) under different solvothermal reaction conditions. Both CPs have been studied via single-crystal X-day diffraction, powder X-ray diffraction(PXRD) and thermogravimetric analysis(TGA). The photophysical studies indicated that complex 2 with good water stability is a potential semiconductive material, which could be applied for the degradation of methylene blue(MB) under UV light irradiation and exhibit good stability and recyclability.     

Aromatic Multicarboxylate Ligands Tuned One-and Three-dimensional Zn(Ⅱ) Coordination Polymers Based on 3-(1H-pyrazol-4-yl)-5-(pyridin-3-yl)-1,2,4-triazole

Two aromatic multicarboxylate ligands tuned Zn(Ⅱ) coordination polymers, namely, {[Zn_(0.5)(H_2L)(tp)_(0.5)(H_2O)]H_2O}_n(1) and {[Zn_2(HL)(btc)(H_2O)]H_2O}_n(2)(H_2L = 3-(1 Hpyrazol-4-yl)-5-(pyridin-3-yl)-1,2,4-triazole, H_2tp = terephthalic acid; H_3 btc = 1,3,5-benzenetricarboxylic) have been synthesized. Their structures were characterized by single-crystal X-ray diffraction analysis, elemental analyses and infrared spectra. Compound 1 possesses a one-dimensional chain structure and is finally extended into a three-dimensional supramolecular architecture though hydrogen bonding interactions. Compound 2 shows a three-dimensional framework. Meanwhile, compounds 1 and 2 exhibit luminescent emission in the solid, and can be investigated as potential luminescent materials.     

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.     

Structures and Photoluminescent Properties of 3D Ho(Ⅲ) and Y(Ⅲ) Complexes with 2,4,6-Pyridinetricarboxylate

Two 3D rare earth coordination polymers {[Ho(ptc)(H_2O)_(2.5)]·0.5 H_2O}n(1) and {[Y2(ptc)2(H_2O)_5]·H_2O}n(2)(H_3ptc = 2,4,6-pyridinetricarboxylic acid) have been synthesized with Ho(Ⅲ) or Y(Ⅲ) chloride and H_3ptc by hydrothermal method. The X-ray structure analyses display the two complexes are isomorphic and crystallize in monoclinic crystal system with P21/n space group for 1 and P21/c space group for 2. Ho(Ⅲ) and Y(Ⅲ) both show two different coordination modes. One is nine-coordinated and forms a distorted tricapped trigonal prism and the other is eight-coordinated to get a distorted bicapped trigonal prism. The ptc3-also shows two different coordination modes by connecting four or three rare earth ions. The photoluminescent properties of 2 show that it can emit blue fluorescence at 440 nm with excitation at 335 nm. The fluorescence lifetime of 2 is 1.64 μs and the absolute fluorescence quantum yield is 10.2%.     

Preparations and characterizations of two MOFs constructed with hydroxylphenyl imidazole dicarboxylate

Using the hydrothermal reactions of Mn(Ⅱ) and Ba(Ⅱ) salts with 2-(3-hydroxylphenyl)-1H-imidazole-4,5-dicarboxylic acid(m-OHPhH_3IDC),two novel metal-organic frameworks,namely,{[Mn(mOHPhHIDC)(H_2O)]2H_2O}_n(1) and {[Ba(m-OHPhH_2IDC)_2(H_2O)_3]-2H_2O)_n,(2) have been synthesized and structurally characterized by single-crystal X-ray crystallography,elemental analyses,and IR spectroscopy.Complex 1 features a novel non-interpenetrated three-dimensional(3,4)-connected network with one-dimensional open channels.Complex 2 exhibits a two-dimensional layered structure with rhombic grids.The role of the central metals in the formation of final architectures has been discussed.Furthermore,luminescent and thermal properties of the two complexes have been studied.     

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.     

Syntheses,Crystal Structures and Antibacterial Activities of Schiff Base of Nickel(Ⅱ) and Copper(Ⅱ) Complexes

A new kind of Schiff base HL(HL= 1-phenyl-3-methyl-4-(p-methylbenzoyl)-5-pyrazolone with L-Leucine methyl ester) and complexes Ni L′_2·0.75C_2H_5OH·0.25H_2O,Cu L′′2(L′ = 1-phenyl-3-methyl-4-(p-methylbenzoyl)-5-pyrazolone with L-leucine ethyl,L′′ = 1-phenyl-3-methyl-4-(p-methylbenzoyl)-5-pyrazolone with L-leucine) have been synthesized and structurally determined by X-ray diffraction. For HL: crystal structure determination indicates that there are two independent HLs with different conformations in one asymmetric unit. For complex 1: the Ni(Ⅱ) ion is six-coordinated by two carbonyl oxygen atoms from pyrazolone ring,two nitrogen atoms from different HL′ and two oxygen atoms from L-Leucine ethyl ester to form a distorted octahedral geometry. For complex 2: the Cu(Ⅱ) ion is four-coordinated by one carbonyl oxygen atom from the pyrazolone ring,one nitrogen atom from HL′′,and two different carboxylic oxygen atoms from L-leucine with the same conformation to form a distorted quadrilateral geometry.     

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.     

Effect of pH/Auxiliary Ligand on the Structures of Coordination Compounds Based on a Novel Ligand 2,6-Bis(pyrazin-2-yl)pyridine-4-carboxylate

Four new coordination compounds, [Zn(bppc)_2(H_2O)_2]·3 H_2O(1), [Zn2(bppc)2(mbdc)(H_2O)4]·7 H_2O(2), [Zn(bppc)2(H_2O)2]n·n(m-Hbdc)·n(H_2O)(3), [Zn2(bppc)(btc)(H_2O)3]n·5 n H_2O(4)(Hbppc = 2,6-bis(pyrazin-2-yl)pyridine-4-carboxylate, H2(m-bdc) = 1,3-benzenedicarboxylic acid, H3 btc = 1,3,5-benzene-tricarboxylic acid), have been hydrothermally synthesized and structurally characterized. Compound 1 shows a mononuclear structure and 2 shows a dinuclear structure. Compound 3 is a one-dimensional chain structure, which is extended into a 3D supramolecular network by intermolecular hydrogen interactions. In 4, a 1D loop-like chain is connected by(btc)3-anions to generate a 2D layer structure. The structure differences of 1~4 show that the p H and aromatic acid as auxiliary ligand have important influence on the final structures.iAdditionally, the luminescent properties of 1~4 have been investigated with fluorescent spectra in the solid state, and 1~4 display a strong fluorescent emission at room temperature and have potential applications as fluorescent-emitting materials.     

Crystal Engineering of Co(Ⅱ) Metal-organic Frameworks Based on the Hydrolysis Product of Letrozole and Coligands

The cyanide groups of letrozole(1-[bis(4-cyanophenyl)methyl]-1,2,4-triazole) were hydrolyzed into the carboxylic groups under alkaline conditions. Then the hydrolysis product(1-[bis(4-carboxylphenyl)methyl]-1,2,4-triazole, H_2ltzda) reacted with Co(NO_3)_2·6H_2O in the presence of different bipyridl-typed ligands under hydrothermal conditions. As a result, two new Co(Ⅱ) MOFs were obtained, formulated as [Co_2(ltzda)_2(bpp)_2]_n(1) and {[Co_2(ltzda)_2(bpy)]·4H_2O}_n(2)(bpp = 1,3-di(4-pyridyl)propane, bpy = 4,4'-bipyridine). Two MOFs have been characterized by single-crystal X-ray diffraction, thermogravimetric analysis and magnetic measure. 1 displays a 2D metal-organic framework containing wave layers and 2 shows a pillared-layer structure existing in a 2-fold interpenetrated mode.     

Two Zn(Ⅱ)/Cd(Ⅱ) Metal-organic Frameworks Constructed from 1,3,5-Benzenetricarboxylic Acid and1,4-Bis(1-imidazolyl)benzene:Syntheses,Structures and Photoluminescent Properties

Two new d~(10 )metal-based metal-organic frameworks,{[Zn_3(btc)_2(bib)_2(H_2O)_2]·2H_2O}_n(1)and{[Cd_3(btc)_2(bib)_(1.5)(H_2O)_6]·6H_2O}_n(2)(btc=1,3,5-benzenetricarboxylate anion,bib=1,4-bis(1-imidazolyl)benzene)have been prepared under hydrothermal conditions by the reactions of d~(10 )metal oxides of ZnO and CdO with the aromatic polycarboxylic H_3btc and the N-heterocyclic bib.The two products were characterized by single-crystal X-ray diffraction analysis,elemental analysis,thermogravimetric analysis(TGA),and IR spectroscopy.Complexes 1 and 2 crystallize in monoclinic C2/c and triclinic P 1 space groups,respectively.1 shows a 3D framework,and the potential large voids of the 3D network lead to a 3-fold interpenetrating architecture.2 displays a 2D framework,and the adjacent 2D layers expand into a 3D supramulecular network via rich hydrogen bonds.Moreover,the luminescent properties of the two complexes are investigated in solid state.     

Two Co(Ⅱ) Complexes Constructed from 1-(3,5-Dicarboxybenzyl)-3,5-pyrazole Dicarboxylic Acid:Syntheses,Structures and Magnetic Properties

Two new complexes[Co_2(L)(4,4′-bip)(H_2O)_3]_n (1) and{[Co(L′)_2(phen)]·2H_2O)}_n (2)(H_4L=1-(3,5-dicarboxybenzyl)-3,5-pyrazole dicarboxylic acid,H_3L′=1-(3,5-dicarboxybenzyl)-3-pyrazole carboxylic acid,4,4′-bip=4,4′-bis(1-imidazolyl)biphenyl,phen=1,10-phenanthroline) were synthesized.Complexes 1 and 2have been characterized by IR spectrography,X-ray single-crystal diffraction,elemental analysis and thermogravimetry.1 crystallizes in monoclinic system,space group P2_1/c.Complex 2 crystallizes in monoclinic system,space group I2/a.It is remarkable that in situ hydrothermal decarboxylation was observed during preparing complex 2.In addition,magnetic analysis indicates that antiferromagnetic interaction exists among Co(Ⅱ) ions in complexes 1 and 2.     

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.     

Syntheses,Crystal Structures and Magnetic Studies of Two Mn(Ⅱ) Complexes Based on 2-Pyrimidineamidoxime

Two novel manganese(Ⅱ) complexes, [Mn(pmadH_2)_2(3-Sb)]n(1) and {[Mn(pmadH2)(Hssal)(H_2O)]·2 H_2O}n(2)(pmadH_2= 2-pyrimidineamidoxime, 3-Sb = 3-sulfobenzoate dianion, H_3ssal = 5-sulfosalicylic acid), have been successfully obtained. The two complexes were characterized by single-crystal X-ray diffraction, powder X-ray diffraction, thermal gravimetric analysis, infrared spectra and elemental analysis. They are one-dimensional manganese polymer(1) and two-dimensional manganese complex(2), respectively. The values of χmT at 300 K of 1 and 2 are lower than the spin-only value for the non-interacting Mn(Ⅱ) ion(S = 5/2).     

Structural Diversity and Luminescent Properties of Metal-organic Frameworks Based on a Rare Sulfonate and Imidazole Co-Ligand System

Four types of luminescent properties of metal-organic frameworks(MOFs) with formulas [Cd(1,2-BIYB)2(H_2O)_2]_n·n(AQ-1,5-DAD)(1), [Cd(AQ-1,5-DAD)(1,3-BIYB)_2]_n(2), [Cd(1,3-BIYB)]n·n(AQ-1,5-DAD)·n H_2O(3), and [Zn(1,4-BIYB)_2]_n·n(AQ-1,5-DAD)2·6H_2O(4),(Na_2AQ-1,5-DAD = anthraquinone-1,5-disulfonic acid disodium, 1,2-BIYB = 1,2-bis(imidazol-1-ylmethyl)benzene, 1,3-BIYB = 1,3-bis(imidazol-1-ylmethyl)benzene, 1,4-BIYB = 1,4-bis(imidazol-1-ylmethyl)benzene) have been synthesized based on a rare sulfonate and imidazole Co-ligand system under different conditions. The structural features of four types of MOFs 1~4 are as follows: MOFs 1 show a 3D supramolecular compound in which the double one-dimensional chains are further cross-linked by hydrogen bonds. 2 exhibits a 2D network constructed by two different 1D chains. 3 features a 2D supramolecular network, in which the 1D chains and AQ-1,5-DAD are arranged alternately through hydrogen bonds. 4 posseses a 3D supramolecular structure constructed by a 2D network and one-dimensional hydrogen bonding chains. All compounds 1~4 are characterized by elemental analysis, infrared spectroscopy, and thermogravimetric analysis. The luminescence properties of 1~4 have been investigated.