Synthesis,Crystal Structure and Spectroscopic Properties of Cyanide-bridged Complex [Ru~Ⅱ(ttpy)(CN)_3Mn~Ⅲ(salen)]

Tricyanide building block K[Ru(ttpy)(CN)_3] and [Mn~Ⅲ(salen)](ClO_4) have been used to design and synthesize a heterobimetallic one-dimensional(1D) zigzag chain complex 1,[Ru~Ⅱ(ttpy)(CN)_3 Mn~Ⅲ(salen)](ttpy = 4?-(p-tolyl)-2,2?:6?,2??-terpyridine, salen = N,N?-ethylenebis-(salicylideneaminato)dianion). Single-crystal X-ray diffraction analysis shows complex 1 crystallizes in orthorhombic Pbca space group and the asymmetric unit of 1 contains one[-NC-Ru~Ⅱ(ttpy)(CN)(m-CN)-Mn ~Ⅲ-(salen)-] molecule. In the structure of 1, each [Ru ~Ⅱ(ttpy)(CN)_3]~-connects two [Mn~Ⅲ(salen)]~+ with two cyanide groups in a cis-conformation, and in turn each[Mn~Ⅲ(salen)]~+ unit links two [Ru~Ⅱ(ttpy)(CN)_3]~-building blocks in a trans-conformation, resulting in a 1D [-NC-Ru~Ⅱ-CN-Mn~Ⅲ-]_n chain. Furthermore, the electronic absorption spectra and luminescence spectroscopy of complex 1 have also been studied.     

Cyanide-bridged One-dimensional Heterobimetallic Complex cis-[Fe~Ⅱ(phen)_2(CN)_2Mn~Ⅲ(salen)](PF_6): Synthesis,Crystal Structure and Magnetic Properties

Dicyanide building block cis-Fe(phen)_2(CN)_2 and [Mn~Ⅲ(salen)](ClO_4) have been used to design and synthesize a cyanide-bridged complex, resulting in a heterobimetallic one-dimensional(1D) zigzag chain complex 1, [cis-Fe(phen)_2(CN)_2Mn(salen)](PF_6)(phen =1,10-phenanthroline, salen=N,N?-ethylenebis-(salicylideneaminato) dianion). Single-crystal X-ray diffraction analysis shows complex 1 crystallizes in the monoclinic P2_(1/c) space group and the asymmetric unit contains one [-NC-Fe(phen)_2(μ-CN)-Mn~Ⅲ-(salen)-]~+ cation and one PF_6~- anion. In the cationic structure of 1, each Fe~Ⅱ(phen)_2(CN)_2 connects two [Mn~Ⅲ(salen)]~+ with two cyanide groups in a cis-conformation, and in turn each [Mn~Ⅲ(salen)]~+ unit links two Fe~Ⅱ(phen)2(CN)_2 building blocks in a trans-conformation, resulting in a 1D [-NC-Fe~Ⅱ-CN-Mn~Ⅲ-]n chain. Furthermore, the electronic absorption spectra and electrochemical and magnetic properties of complex 1 have also been studied.     

Cyanide-bridged complexes based on dinuclear Cu(II)-M(II) [M = Pb and Cu] building blocks: Synthesis, crystal structures and magnetic properties

Four cyanide-bridged heterometallic complexes {[CuPb(L 1 )][Fe III (bpb)(CN) 2 ]} 2 ·(ClO 4 ) 2 ·2H 2 O·2CH 3 CN (1), {[CuPb(L 1 )] 2 [Fe II (CN) 6 ](H 2 O) 2 }·10H 2 O (2), {[Cu 2 (L 2 )][Fe III (bpb)(CN) 2 ] 2 }·2H 2 O·2CH 3 OH (3) and {[Cu 2 (L 2 )] 3 [Fe III (CN) 6 ] 2 (H 2 O) 2 }·10H 2 O (4) have been synthesized by treating K[Fe III (bpb)(CN) 2 ] [bpb 2-=1,2-bis(pyridine-2-carboxamido)benzenate] and K 3 [Fe III (CN)] 6 with dinuclear compartmental macrocyclic Schiff-base complexes [CuPb(L 1 )] (ClO 4 ) 2 or [Cu 2 (L 2 )]·(ClO 4 ) 2 , in which H 2 L 1 was derived from 2,6-diformyl-4-methyl-phenol, ethylenediamine, and diethylenetriamine in the molar ratio of 2:1:1 and H 2 L 2 from 2,6-diformyl-4-methyl-phenol and propylenediamine in the molar ratio of 1:1. Single crystal X-ray diffraction analysis reveals that compound 1 displays a cyclic hexanuclear heterotrimetallic molecular structure with alternating [FeⅢ (bpb)(CN) 2 ]- and [CuPb(L 1 )] 2+ units. Complex 2 is of a neutral dumb-bell-type pentanuclear molecular configuration consisting of one [Fe(CN)6] 4- anion sandwiched in two [CuPu(L 1 )] 2+ cations, and the pentanuclear moieties are further connected by the hydrogen bonding to give a 2D supramolecular framework. Heterobimetallic complex 3 is a tetranuclear molecule composed of a centrosymmetric [Cu 2 (L2)] 2+ segment and two terminal cyanide-containing blocks [FeⅢ (bpb)(CN)2 ]- . Octanuclear compound 4 is built from two [Fe(CN)6]3- anions sandwiched in the three [Cu 2 L 2 ] 2+ cations. Investigation of their magnetic properties reveals the overall antiferromagnetic behavior in the series of complexes except 2.     

Two Tetranuclear Zinc(Ⅱ) Coordination Polymers Based on 3,5-Bis(2-carboxylphenoxy)benzoic Acid with Highly Selective Sensing of Nitrobenzene

Two novel zinc(Ⅱ) coordination polymers, [Zn_2(BCB)(CH_3OH)(μ_3-OH)]n(1) and {[Zn_2(BCB)(μ_3-OH)(H_2O)_2]·CH_3OH}n (2), have been constructed from 3,5-bis(2-carboxylphenoxy)benzoic acid(H_3BCB) and characterized by elemental analysis(EA), IR, powder X-ray diffraction(PXRD), and thermogravimetric(TG) analyses. Structural analysis reveals that complexes 1 and 2 are both 1D polymeric chains with unprecedented tetranuclear {Zn_4(COO)_4(μ_3-OH)_2} clusters, which were further expanded into a 2D structure. Fluorescence measurements show that 1 and 2 have highly selective and sensitive detection of nitrobenzene.     

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.     

Synthesis and Structural Characterization of a Cyano-bridged 1-D Lanthanum(Ⅲ)-iron(Ⅲ)Complex [La(DMSO)5(H2O)](μ-CN)2[Fe(CN)4]·H2O

A new lanthanumⅢ-ironⅢ complex [La(DMSO)5(H2O)](μ-CN)2[Fe(CN)4]·H2O 1 (DMSO=dimethylsulfoxide) has been prepared by a facile approach, ball-milling method, and characterized by X-ray diffraction. The crystal belongs to monoclinic, space group P21/n with a=9.7125(3), b=21.5336(7), c=14.3804(5) (A), β=93.242(3)°, C16H34FeLaN6O7S5, Mr=777.55, V=3002.8(2)(A)3, Z=4, Dc=1.720 g/cm3, S=1.053, μ(MoKα)=2.278 mm-1, F(000)=1564, R=0.0490 and wR=0.1270. The crystal structure analysis of 1 reveals a slightly distorted squareantiprism eightfold-coordinated La(Ⅲ) ion and a 1-D zigzag chain structure extending through the Fe-CN-La-NC-Fe linkages. The [La(DMSO)5(H2O)](μ-CN)2[Fe(CN)4] species are held together via hydrogen bonds to form a three-dimensional framework.     

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.     

Metal-induced Coordination Networks Using a C_(2v)-based Hexacarboxylate Ligand:Syntheses,Structures and Properties

Metal-organic frameworks(MOFs), consisting of metal, anion and organic ligands, have attracted much attention. The structure of MOFs is affected by various factors. To explore the effects of metal ions, we synthesized six complexes, namely {[Me_2NH_2][Zn_4(H_2L)(L)]·2 H_2O·2 DMF}_n(1), {[Me_2NH_2]_2[Cd_2(L)]·2H_2O}_n(2), {[Me_2NH_2]_2[Ca_3(L)(μ-OH)_2(DMF)_2]·2H_2O}_n(3) and {[Me_2NH_2]_2[M_2(L)(μ-OH)]· H_2O·2DMF}_n(M = Co, 4; Ni, 5; Mn, 6), from a C_(2v)-based hexacarboxylate ligand([1,1';4',1']terphenyl-3,5,2',5',3',5'-hexacarboxylic acid(H_6L)) using metal-induced strategy. These MOFs were thoroughly characterized by single-crystal and X-ray diffraction, elemental analysis, Fourier-transform infrared spectra(FTIR) and photoluminescence.     

Temperature-dependent Syntheses of Two Manganese(Ⅱ) Coordination Compounds Based on an Ether-bridged Tetracarbolylic Acid

0D dinuclear manganese(Ⅱ) coordination compound and 1 D chain manganese(Ⅱ) coordination polymer, namely [Mn_2(μ-L)(phen)4]·4 H_2 O(1) and {[Mn_2(μ5-L)(phen)_2]·H_2O}n(2), have been constructed hydrothermally using H4 L(H4 L = 2,3,3',4'-diphenyl ether tetracarboxylic acid), phen(phen = 1,10-phenanthroline), and manganese chloride at 120 and 160℃, respectively. 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. Single-crystal X-ray diffraction analyses revealed that two compounds crystallize in the triclinic or monoclinic system, space group P1 or P2_1/c. Compound 1 discloses a discrete dimeric structure, which is assembled into a 3 D supramolecular framework through O–H···O hydrogen bond. Compound 2 has a chain structure. Structural differences between compounds 1 and 2 are attributed to the different reaction temperature. Magnetic studies for compound 2 demonstrate an antiferromagnetic coupling between the adjacent Mn(Ⅱ) centers.     

Trinuclear Cu(Ⅱ) and Zn(Ⅱ) complexes bridged by μ_3-carbonato anion

The trinuclear Cu(Ⅱ) and Zn(Ⅱ) complexes [(CuTPA)_3(μ3-CO_3)] (ClO_4)_4(1) and [(ZnTPA)_3(μ_3-CO_3)] (ClO_4)_4 (2) (TPA=tri(pyridylmethyl) amine) have been synthesized. X-ray structure analysis of the two complexes proves that CO_3~(2-) anion has an unusual triply bridging ligand, bridging three CuTPA and ZnTPA units respectively, and assembles new trinuclear complexes. The CO_3_(2-) comes from atmospheric CO_2. The structure of each trinuclear unit consists of three copper or zinc atoms in a five-coordinate triangular bipyramidal environment. The [(CuTPA)_3 (μ_3-CO_3)] (ClO_4)_4 compound shows a very weak antiferromagnetic coupling.     

Coexistence of metamagnetism and single chain magnet behavior in a Fe~Ⅲ_2Co~Ⅱ layer compound

A cyanide-bridged Fe~Ⅲ_2Co~Ⅱ double zigzag chain, {[Fe~Ⅲ(bipy)(CN)_4]_2Co～Ⅱ(btab)_2}n [bipy=2,2′-bipyridine, btab=4,4′-(1,3-phenylene)-bis-4H-1,2,4-triazole](1), was obtained with tetracyanometalate precursors and CoII ions. The chains were further linked by the ditopic btab ligands to a layer. Magnetic property studies demonstrate that 1 shows both metamagnetism with a critical field Hc=400 Oe and single-chain magnet behavior.     

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%.     

Heterometal–organic frameworks: Three novel copper(Ⅱ)–lanthanide(Ⅲ) 15-metallacrown-5 complexes based on pyrazinohydroxamic acid as new multiple-binding pentagonal platform

Reactions of copper(Ⅱ) sulfate or copper(Ⅱ) perchlorate,samarium(Ⅲ),erbium(Ⅲ) or neodymium(Ⅲ)nitrate(5/1 equiv.) with pyrazinohydroxamic acid(H_2Pyzha) in H_2O/Me0 H led to three new heterobimetallic 15-metallacrown-5 complexes.In a MeOH/H_2O solution,when adding inorganic salts,the ligands exist as protonated metallacrowns.In the solid state,their structures are more complicated as confirmed by X-ray analysis:metallacrown[Sm(H_2O)_3 {Cu(pyzha)}_5(H_2O)_2(MeOH)(HSO_4)_2]·(H_2O)_2(HSO_4)(1);[Nd(H_2O)_2(MeOH) {Cu(pyzha)}_5(ClO_4)_2(H_2O)_5(NO_3)](2);[Eu(H_2O)_2(MeOH) {Cu(pyzha)}_5(ClO_4)_2(H_2O)_5(NO_3)](3).The differentiation of atomic and ionic radii between the encapsulated lanthanide(Ⅲ) could be used to control the bowl-shape distortion of the metallacrowns from the planar geometry.The complex 1 clearly exhibits fluorescence behavior of samarium(Ⅲ),while 2and 3 show that of copper(Ⅱ) and ligand.     

Synthesis and Structural Characterization of a Cyano-bridged 1-D Lanthanum(Ⅲ)-iron(Ⅲ) Complex [La(DMSO)_5(H_2O)](μ-CN)_2[Fe(CN)_4]·H_2O

A new lanthanumⅢ-ironⅢ complex [La(DMSO)5(H2O)](μ-CN)2[Fe(CN)4]·H2O 1 (DMSO=dimethylsulfoxide) has been prepared by a facile approach,ball-milling method,and characterized by X-ray diffraction. The crystal belongs to monoclinic,space group P21/n with a= 9.7125(3),b=21.5336(7),c=14.3804(5),β=93.242(3)o,C16H34FeLaN6O7S5,Mr=777.55,V =3002.8(2)3,Z=4,Dc=1.720 g/cm3,S=1.053,μ(MoKα)=2.278 mm–1,F(000)=1564,R= 0.0490 and wR=0.1270. The crystal structure analysis of 1 reveals a slightly distorted square-antiprism eightfold-coordinated La(Ⅲ) ion and a 1-D zigzag chain structure extending through the Fe-CN-La-NC-Fe linkages. The [La(DMSO)5(H2O)](μ-CN)2[Fe(CN)4] species are held together via hydrogen bonds to form a three-dimensional framework.     

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.     

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...     

Syntheses and Anti-lung Cancer Activities of Zn(Ⅱ) and Cu(Ⅱ) Complexes Based on Triazole and Tetrazole,respectively

The reactions of 4H-1,2,4-triazole(Htrz) with ZnCl_2, 1H-tetrazole(Htez) and Cu(NO_3)2·6H_2O afford two novel coordination polymers respectively, {[Zn_2(trz)_2(ox)](H_2O)_3}n(1) and {[Cu_3(tez)_3(OH)_2(H_2O)_2](NO_3)(DMF)_4}_n(2)(H_2ox =(COOH_)2, DMF = N,N-dimethylformamide). 1 shows 1D channels along the a axis filled with water molecules and 2 features a 2D bi-layered framework based on trinuclear Cu(II) units bridged by two μ3-OH groups. In addition, in vitro antitumor activities of compounds 1 and 2 on four human lung cancer cells(16HBE, NCI-H1299, NCI-H460 and NCI-H292) were further determined.     

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.     

Construction of a Set of Cadmium（Ⅱ） Coordination Polymers with Atza and 2,2′-Bipy or 1,10-Phen Ligands （Atza=5-Aminotetrazole-1-acetato Anion）

Reactions of CdX2(X=NO3-, ClO4-) with Hatza (atza=5-aminotetrazole-1-acetato anion) and 2,2′-bipyridine (2,2′-bipy) or 1,10-phenanthroline (1,10-phen) in a methanol/aqueous solution produced a set of new Cd(Ⅱ) coordination polymers, {[Cd(atza)(H2O)(2,2′-bipy)]ClO4}n (1), {[Cd(atza)(H2O)(1,10-phen)]ClO4 }n (2), {[Cd(atza)(H2O)(2,2′-bipy)]NO3}n (3) and {[Cd(atza)2 (1,10-phen)]·0.5H2O}n (4). Single-crystal X-ray diffraction analysis reveals that each Cd(Ⅱ) ion has a distorted octahedral coordination geometry in 1-4, and the Cd(Ⅱ) ion centers are connected through the tridentate atza bridging ligands to form a 2D layer (1-3) or ID chain (4) structure. The fluorescent properties of 2 and 4 are also discussed.     

Two Metal Ion-controlled Zn(Ⅱ)/Cd(Ⅱ) Coordination Polymers Based on 1,3,5-Benzenetricarboxylic Acid

Two new coordination polymers {[Zn(Hbtc)(bpyb)]·H_2O}n(1) and {[Cd(Hbtc)-(bpyb)_(1.5)]·0.5 bpyb}_n(2)(H_3btc = 1,3,5-benzenetricarboxylic acid, bpyb = 1,4-bis(4-pyridyl)benzene) have been synthesized under hydrothermal conditions. The two compounds were characterized by elemental analysis, IR spectroscopy, and X-ray single-crystal diffraction. Compound 1 displays a 2-fold interpenetrating 3D supramolecular architecture through O–H···N/O hydrogen bonds and π-π stacking interactions. Compound 2 exhibits a 2D→3D polycatenated structure, which is further stabilized by O–H···N hydrogen bonds. The results indicate that the metal ion has significant effects on the formation and structure of the resulted coordination polymers. Furthermore, thermal stability and photoluminescent properties of 1 and 2 are also discussed in detail.