One pot synthesis,crystal structures and properties of two new MOFs with imidazole-containing tripodal ligand

Two new different Cu(Ⅱ) MOFs with the same 1,3,5-tris(1-imidazolyl) benzene(tib) ligand {[Cu(tib)2]·(H2O)2·Br2}n(1) and {[Cu2(tib)·Br·Cl]·2Br}n(2) were obtained by one pot synthesized of tib with CuBr in the presences of HCl and water. X-ray single crystal diffraction analyses indicate that both complexes 1 and 2 have two dimensional frameworks containing different building blocks. Each Cu(Ⅱ) atom in complex 1 is coordinated by four N atoms from different tib ligands. However, there are two different cryptographic Cu(Ⅱ) atoms in complex 2, one is four coordinated by two bromine atoms and two N atoms from different tib ligands, the other is six coordinated by two chloride atoms and four N atoms from different tib ligands. The thermal gravimetric analysis of complexes 1 and 2 are depicted in the paper.     

Synthesis and Structural Characterization of Three Novel Macrocyclic Coordination Complexes Formed by Self-assembly of Bridged Bi-or Tetrapyridine with Transition Metal Salts

Serf-assembly of a ferrocenyl-bridged bipyridine ligand bpef [bpef=1, 1＇-bis（trans-2-pyrid-4＇-ylethenyl）ferrocene] with silver triflate in CH2Cl2/MeOH or mercuric diiodide in MeCN/CH2Cl2 gave the corresponding macrocyclic coordination complexes [bpef]2[AgSO3CF3]2 （1） and [bpef]2[Hg3I6] （2） in 93% and 89% yields, respectively, whereas the pentaerythritolyl-bridged tetrapyridine ligand ptpc [ptpc=pentaerythritol tetrakis-（4-pyridinecarboxylate）] reacted with cobalt thiocyanate via self-assembly to afford the macrocyclic coordination polymer [Co（NCS）2（ptpc）], （3） in 90% yield. The X-ray diffraction analyses for 1-3 confirmed their novel macrocyclic structures and revealed that （i） the two silver atoms in complex 1 have an essentially linear geometry with N-Ag-N bond angle of 175.7° and 172.9°, （ii） the geometry of the middle mercury atom in complex 2 is square-planar, while the other two mercury atoms in the other two complexes are tetrahedral, and （iii） all the cobalt atoms in complex 3 adopt an octahedral geometry. In addition, the synthetic procedure for the known tetrapyridine ligand ptpc has been improved.     

Syntheses and Crystal Structures of Two New Mercury（Ⅱ） Complexes with Double Betaine Ligands

Reaction of HgCl2 and double betaine ligands in water at about 80 ℃ yielded two new Hg(Ⅱ) complexes,[Hg(L1)Cl2]·H2O 1 and [Hg2(L2)Cl4]·3HgCl2 2(L1 = 1,3-bis(pyridinio-4-carboxylato)-propane,L2 = 1,4-bis(pyridinio-4-carboxylato)-1,4-dimenthylbenzene).Their struc-tures have been characterized by single-crystal X-ray diffraction techniques.The structure of 1 contains 1-D chains,in which the adjacent Hg(Ⅱ) atoms are bridged by L1 ligands in a syn-syn bis-monodentate mode.The chains are further connected through face-to-face π-π stacking interactions between pyridine rings to generate an infinite double-chain network.In 2,two Hg(Ⅱ) atoms are joined by L2 ligands in the same coordination mode as 1 to form an isolated dinuclear structure.The thermal stabilities of both complexes have also been investigated.     

Cis- and Trans-Coordination Assembly of Nitrogen Heterocycle with Copper（Ⅱ） and Silver（Ⅰ）

After the preparation of 1,4-bis（4,5-dihydro-lH-imidazol-2-yl）benzene（bdib）, a nitrogen heterocycle with potential coordination manners of both cis- and trans-configuration forms, three complexes, including cis-[Cuz（bdib ）2（/L-OCH3）2]Cl2·2MeOH（1）, trans-[Cu（bdib）（AcO）2]n（2）, and cis-[Ag2（bdib）2]（NO3）2.2H20（3）, were successfully self-assembled. Complexes 1 and 2 crystallized in the monoclinic system with P21/n space group and complex 3 in the triclinic system with P1 space group.     

Synthesis and Crystal Structures of Two Di-Cu(Ⅱ) Complexes Based on an Asymmetric Dinucleating Ligand

Two new dicopper(II) complexes [Cu2L(OAc)2](ClO4)·H2O(1) and [Cu2L(BPP)2]-(ClO4)(2) using an asymmetric dinucleating ligand HL and auxiliary ligands such as acetate(OAc) and bisphenyl phosphate(BPP) have been synthesized and characterized by elemental analysis, IR and single-crystal X-ray diffraction. Complex 1 crystallizes as blue single crystals that belong to the triclinic crystal system and P1 space group, while complex 2 crystallizes in a monoclinic P21/c space group. Single-crystal X-ray diffraction analysis reveals that the two copper ions in complexes 1 and 2 reside within the adjacent ligand compartments and are bridged by the endogenous phenoxo-O from ligand L and the introduction of two desired exogenous carboxylates or phosphates in the bidentate μ-1,3-bridged mode. The coordination geometries of Cu(1) and Cu(2) are both distorted square pyramids.     

Crystal Structures and Theoretical Calculation of Zn（Ⅱ） and Cu（Ⅱ） Supramolecular Complexes Based on Macrocyclic Triamine Ligand 1,4,7-Triazacyclodecane （tacd）

Two supramolecular complexes [Zn（tacd）2]（C6H8O4）·6H2O（1） and [Cu（tacd）2]Cl2·4H2O（2） were synthesized and characterized by elemental analysis, IR spectra, TGA and single-crystal X-ray diffraction analysis. The crystal structure showed that the metal ions in complexes 1 and 2 had similar coordination circumstance. But for the complex 2, it formed a novel two-dimensional supramolecular network with 12-membered rings and four-membered rings via hydrogen bond interaction. The thermal gravimetric analyses indicated that the two complexes had similar steps of weight-loss. On the basis of experiment, the two complexes were calculated by DFT-B3LYP/6-31G（d） in Gaussian 03. The results of calculation are in good agreement with the experiment.     

Crystal Structure, Thermal Stability and Luminescence of Coordination Polymer [Cd（BBP）（p-PDOA）]n

Hydrothermal reaction of Cd（NO3）2·4H2O with bbp and p-PDOAH2 at 140 ℃ yielded a novel 1D cadmium（Ⅱ） coordination polymer, [Cd（bbp）（p-PDOA）]n （bbp=2,6-bis（benzimidazol-2-yl）pyridine, p-PDOA=p-phenylenedioxydiacetate dianion）, in which CdN3O4 pentagonal bipyramids were linked by p-PDOA ligands in a bis-bidentate mode to construct a zigzag chain with the adjacent Cd…Cd distance of 1.14（1） nm, There exists a 2D supramolecular network linked by π-π stacking with a face-to-face distance of 0.35（1） nm between the 2,6-bis（benzimidazol-2-yl） pyridine ligands and hydrogen-bonding interactions （0.27（4） nm）. A 3D supramolecular network was further constructed by these non-covalent interactions between the zippers. The TG/DTG showed that its chain skeleton was thermally stable up to 389 ℃ and the blue fluorescent emission of the complex was determined at 428 nm in a solid state with its long decay lifetime of 7.24 ns.     

Synthesis and Crystal Structure of a Coordination Polymer [Zn（p-pdoa）（bbp）]n with a One-dimensional Helical Chain

The coordination polymer [Zn（p-pdoa）4（bbp）]n 1 （p-pdoa = p-phenylenedioxydiacetate dianion and bbp = 2,6-bis（benzimidazol-2-yl）pyridine） has been synthesized by hydrothermal method and characterized by elemental analysis, IR and X-ray single-crystal diffraction. The title complex crystallizes in the triclinic system, space group P1^- with a = 7.8383（2）, b = 12.6610（4）, c = 13.1792（5）A, a = 84.433（2）,β = 74.2980（1）, γ = 87.4290（1）°, V = 1252.93（7）A^3, Z = 2, Dc = 1.593 g/cm^3,/z = 1.038 mm^-1, F（000） = 616, the final R = 0.0361 and wR = 0.1139. The Zn（Ⅱ） atom assumes a distorted trigonal bipyramidal geometry, involving two carboxyl O atoms from two different p-pdoa ligands and three N atoms from the bbp ligand. The Zn（Ⅱ） atom is alternately interlinked by p-pdoa ligands in a bismonodentate mode into a helical chain with a long pitch of 12.661 A and the adjacent Zn…Zn distance of 11.056 and 12.245 A. There exists a 2D supramolecular framework linked by π-π stacking （3.312 A） between adjacent benzimidazoles of bbp ligands and intermolecular hydrogen-bonding interactions between the uncoordinated carboxylate oxygen atoms （O（2）, 0（5）） and the uncoordinated imidazolyl N atoms （N…O distances 2.706 and 2.786 A）. There also exist two interlayer π-π stacking interactions of 3.299 A between adjacent central pyridines of bbp ligand and 3.176 A between the phenyl groups of p-pdoa ligand. Such π-π stacking interactions extend the two-dimensional layers into a 3D supramolecular network.     

Cis-and Trans-Coordination Assembly of Nitrogen Heterocycle with Copper(Ⅱ) and Silver(Ⅰ)

After the preparation of 1,4-bis(4,5-dihydro-1H-imidazol-2-yl)benzene(bdib), a nitrogen heterocycle with potential coordination manners of both cis- and trans-configuration forms, three complexes, including cis-[Cu2(bdib)2(μ-OCH3)2]Cl2·2MeOH(1), trans-[Cu(bdib)(AcO)2]n(2), and cis-[Ag2(bdib)2](NO3)2·2H2O(3), were successfully self-assembled. Complexes 1 and 2 crystallized in the monoclinic system with P21/n space group and complex 3 in the triclinic system with Pī space group.     

Synthesis,Crystal Structures and Properties of Two Novel Co（Ⅱ） and Cd（Ⅱ） Complexes of N-AcetyI-L-glutamic Acid and Imidazole Ligands

Two novel complexes {[Co（A-glu）（Im）2]·0.5H2O}n （1） and [Cd（A-glu）（Im）3]n （2） （H2A-glu=N-acetyl-L-glutamic acid, Im=imidazole） have been synthesized from the reaction of H2A-glu with Co（CH3COO）2·4H2O or Cd（CH3COO）2·2H2O in the presence of Im. Both of the complexes display different coordination environment and similar one-dimensional chain structure. The magnetic susceptibility measurements for 1 show a weak antiferromagnetic interaction between two cobalt（Ⅱ） ions bridged by A-glu ligand. The complex 2 exhibits an intense fluorescent emission in solid state at room temperature.     

Zinc(Ⅱ) coordination architectures based on 5-(1H-tetrazol-1-yl)-isophthalic acid:Synthesis,structures and luminescent properties

With different pyridine-analogs as auxiliary ligands,three novel Zn(Ⅱ) complexes(1-3) based on 5-(1Htetrazol-1-yl) isophthalic acid(H_2L) have been synthesized and structurally characterized.Single crystal X-ray diffraction analyses of complexes 1-3 show the presence of tetrazolyl group,as well as the coordination behavior of the auxiliary ligands as critical factors determining the structures of such Zn(Ⅱ)-carboxyIate coordination architectures.In addition,the resulting complexes all exhibit luminescence properties in the solid state at room temperature.     

Syntheses, Crystal Structures and Theoretical Calculation of Two Transition Metal Dinuclear Complexes

Two transition metal dinuclear complexes of [Mn2（OOCC6H4SSC6H4COO）- （Phen）2（H20）]n 1 and [CuE（OOCC6H4S）2（Phen）2] 2 were hydrothermally synthesized by the reaction of equivalent metal dichloride with 2,2＇-dithiobis（benzoic acid） （HE-DTBB）. Structure analysis indicates that each Mn2＋ ion in I is coordinated by one chelate phen ligand, one bridging water molecule and three DTBB ligands forming Mn2＋ dinuclear units which are further linked into one-dimensional chain by DTBB ligand. Under similar reaction conditions, the 2,2＇-dithio- his（benzoic acid） ligand undergoes thiol reduction to form 2-mercaptobenzoic （H-2-MBA） in 2 where two Cu2＋ ions are coordinated by phen and MBA ligands only constructing a dinuclear unit.     

Substituent groups from aromatic dicarboxylates modulated structural diversification in the assembly of Co(II) complexes based on the bis-pyridyl-bis-amide ligands

Four coordination polymers based on two bis-pyridyl-bis-amide ligands and three aromatic dicarboxylates with different substituent groups, namely, [Co(3-bpcb) 1.5 (NPH)(H2O)]·4H2O (1), [Co(3-bpcb)(NIPH)] (2), [Co(3-bpcb)0.5 (5-H2 AIP)]·2H2O (3), [Co(3-bpcd) 0.5 (5-H2 AIP)(H2O)]·2H2O (4) [3-bpcb = N,N′-bis(3-pyridinecarboxamide)-1,4-benzene, 3-bpcd = N,N′-bis(3- pyridine)cyclohexane-1,4-dicarboxamide, H2 NPH = 3-nitrophthalic acid, H2 NIPH = 5-nitroisophthalic acid, 5-H4 AIP = 5-aminoisophthalic acid] have been synthetized under hydrothermal conditions. Complex 1 displays a one dimensional (1D) chain based on the binuclear [Co2 (NPH)2 ] units and 3-bpcb ligands, which is extended into a three dimensional (3D) supramolecular framework through hydrogen bonding and - stacking interactions. In complex 2, the (3,5)-connected two dimensional (2D) layers are constructed from 1D Co-NIPH chains and bidentate-bridging 3-bpcb ligands. Complex 3 is a 2D double layer based on Co-5-H2 AIP 2D layers and 3-bpcb pillars. Complex 4 also displays a 2D network, which is constructed from the Co-5-H2AIP 1D double chains and 3-bpcd ligands. Finally, complexes 2-4 are extended into 3D supramolecular frameworks by hydrogen bonding or - stacking interactions. The substituent groups of dicarboxylates play an important role in the assembly and structures of the title complexes. In addition, the fluorescent properties of complexes 1-4 and the electrochemical behaviors of 3 and 4 at room temperature have been investigated.     

Crystal Structures and Photoluminescent Properties of Two Cd~(2+) Coordination Polymers Constructed from an 8-Hydroxyquinolinate Ligand

In order to perform a study on the structural modulation in the Cd(Ⅱ)-L architecture(HL =(E)-2-[2-(3-pyridyl)ethenyl]-8-hydroxyquinoline), two different dicarboxylic acids, namely, 2-aminoterephthalic acid(H_2ATA) and 4,4￠-biphenyldicarboxylic acid(H_2BPDC), are employed as the secondary auxiliary ligands. Two new complexes [Cd_2L_2(ATA)](1) and [Cd_2L_2(BPDC)·2MeO H· 4H_2O](2) with distinct 3D frameworks were obtained. In complex 1, ligands ATA bridge the 1D Cd(Ⅱ)-L infinite chains into a 3D polymeric coordination network. Complex 2 is a 3D porous framework, in which adjacent 2D Cd(Ⅱ)-L coordination layers were linked together by the coor- dinated BPDC ligands. The variant structures of two complexes indicate that the skeleton of dicarboxylate anions plays a great role in the assembly of such different frameworks. In addition, the photoluminescent properties(fluorescent emission, lifetime, and quantum yield) of polymers 1 and 2 were also investigated in the solid state.     

阴离子在构筑吡啶酰胺－铜(II)配位超分子体系中的作用

Three complexes Cu（ppca）2（H2O）2（NO3）2 （1）, Cu2（μ-OH）2（ppca）2（H2O）4）·（ClO4）2 （2） and Cu2（μ-CH3COO）4（ppca）2（3） have been synthesized by the reaction of copper（Ⅱ） salts with N-phenyl-4-pyridinecarboxamide （ppca） and characterized. For anions, in complex 1, NO3^- coordinated with copper（Ⅱ）, in complex 2 perchlorate anion did not take part in coordination, the copper（Ⅱ） cations were connected by μ-OH to form a dinuclear unit, and complex 3 had a dimeric copper（Ⅱ） carboxylate paddle-wheel core. Noncovalent interactions linked these complexes to form supramolecular networks. Different coordinating modes of anions controlled modes of intennolecular interactions, which resulted in different final structures.     

Synthesis and Crystal Structure of (CH_2)_3(3,5-Me_2Pz)_2. [PhBr_2Sn(CH_2)SnBr_2Ph].2HBr.H_2O (Pz=pyrazole)

1 INTRODUCTION The coordination chemistry of tin or organotin toward poly(pyrazol-1-yl)borate ligands has been extensively investigated in recent years owing to the antitumor activity of some related organotin derivatives containing N-donor ligands. A number of organotin(Ⅳ) complexes containing poly(pyrazol- 1-yl)borate ligands have been synthesized and characterized[1~3], some of which have also shown interesting structural characteristics and reactivities[4~6]. Recently, poly(pyrazol…     

Synthesis,Structure and Magnitic Properties of a Diphenoxobridged Binuclear Copper（Ⅲ） Complex

A mixed-ligand copper(Ⅱ） complex[Cu2(phen)2(HL^1)2]-(ClO4)2(1) was synthesized.X-ray analyses reveal that 1 has a bis(μ2-phenoxo)-bridged dicopper(Ⅱ） structure.2D hydrogen-bonded network is formed utilizing the N-H,O-H and C-H groups of the (HL^1) ligands (H2L^1=N-(2-hydroxybenzyl)ethanolamine),the C-H groups of the phenanthrolines and the perchlorate anions.Variable temperature magnetic properties of 1 have shown comparatively weak antiferromagnetic interactions with respect to the bridge angles, which have been ascribed to the unfavorable overlaps of the magnetic orbitals fo the highly distorted copper coordination polyhedra and the pyramidal distortions at the phenoxo oxygen atoms.     

Thermal Behavior and Decomposition Kinetics of the Complexes of CuX2 （X=NO3, Br, CI and CIO4） with 3,3＇-Dimethyl-1 -（1 H-1,2,4-triazol-1-yl）-2-butanone

The thermal behaviors of the complexes of Cu(DMTZB)4X2 (DMTZB=3,3‘-dimethyl-1-(1H-1,2,4-triazol-1-yl)-2-butanone, X=NO3 or ClO4) and Cu(DMTZB)2 X2 (X=Br or Cl) in a nitrogen atmosphere were studied under the non-isothermal conditions by simultaneous TG-DTG-DSC, EDS and elemental analysis techniques. The resuits showed that their decomposition proceeded in three different ways mainly depending on the anions in the molecules. The heat effect associated with the decomposition step of DMTZB molecules was also different. The decomposition mechanisms and the kinetic parameters of DMTZB were determined and calculated by jointly using four methods, which showed that its pyrolysis was controlled by D3 mechanism but with different activation energies and pre-exponential factors for different complexes.     

Synthesis,Crystal Structure and Photoluminescence of a Copper(Ⅰ)-iodide Coordination Polymer Based on Polyimidazolate Ligand

A copper(Ⅰ)-iodide coordination polymer, namely {[Cu3 I3(Tipa)2]·3(DMF)}n(1), was synthesized from tetrahedral Cu4 I4(py)4 precursor and tris(4-(~1H-imidazol-1-yl)phenyl) amine)(Tipa) ligand in N,N-dimethylformamide(DMF) and methanol, and characterized by single-crystal X-ray diffraction. Its crystal crystallizes in monoclinic system, space group P2/c with a = 12.849(4), b = 12.034(3), c = 24.619(7) ?, β = 104.681(4)°, Mr = 1604.52, V = 3682.4(18) ?3, Z = 2, Dc = 1.447 g/cm3, μ = 2.163 mm-1, S = 0.975, F(000) = 1580, the final R = 0.0835 and wR = 0.2354 for 6471 observed reflections(I 2σ(I)). In compound 1, the Cu4 I4(py)4 was in-situ changed into another neutral CuI unit. Interestingly, two CuI units and two imidazole rings of the tipa ligands form a macrocyclic loop, which are further linked by another CuI unit and the third imidazole ring of the tipa ligands to produce a 1 D loop-containing chain. Solvent molecules were filled in the pore of the loop, which prevents the interpenetration of each other. The packing of these 1 D chains generates a 1 D channel along the a-axis, which is filled by disordered DMF molecules. In addition, compound 1 exhibits high thermal stability and strong photoluminescence at room temperature.     

Synthesis, Spectroscopic and Electrochemical Investigations of Two vic-Dioximes and Their Mononuclear Ni（Ⅱ）, Cu（Ⅱ） and Co（Ⅱ） Metal Complexes Containing Morpholine Group

Two vic-dioxime ligands （LxH2） containing morpholine group have been synthesized from 4-[2-（dimethylaminoethyl）] morpholine with anti-phenylchloroglyoxime or anti-monochloroglyoxime in absolute THF at -15 ℃. Reaction of two vic-dioxime ligands with MCl2·nH2O （M： Ni, Cu or Co and n=2 or 6） salts in 1 ： 2 molar ratio afforded metal complexes of type [M（LxH）2] or [M（LxH）2·2H2O]. All of metal complexes are non-electrolytes as shown by their molar conductivities （Am） in DMF （dimethyl formamide） at 10^-3 mol·L^-1. Structures of the ligands and metal complexes have been solved by elemental analyses, FT-IR, UV-Vis, ^1H NMR and ^13C NMR, magnetic susceptibility measurements, molar conductivity measurements. Furthermore, redox properties of the metal complexes were investigated by cyclic voltammetry.