Synthesis and Characterization of a Water-stable Metal-organic Framework Based on Mixed Ligands

A new water-stable metal-organic framework,[Cu_2（bdc）_2（tpt）_3]·2H_2O（1,H_2 bdc = terephthalic acid,tpt = 2,4,6-tri（4-pyridinyl）-1,3,5-triazine）,has been synthesized and characterized by elemental analysis,infrared（IR） spectrum,thermogravimetric analysis（TGA）,powder X-ray diffraction（PXRD） and single-crystal X-ray diffraction. Compund 1 crystalizes in monoclinic,space group C2/c with a = 30.147（5）,b = 11.0548（17）,c = 20.867（4） ？,β = 115.035（2）o,C_（70）H_（48）Cu_2N_（18）O_（10）,Mr = 1428.34,V = 6301.0（18） ？~3,Z = 8,D_c = 1.506 g/cm^3,μ = 0.754 mm^（–1）,F（000） = 2928,GOOF = 1.058,λ（MoK α） = 0.71073 ？,the final R = 0.0387 and wR = 0.1091 for 6230 observed reflections with I 〉 2σ（I）. In compound 1,the half metallacycles [Cu_2（tpt）_3] are linked by the bdc2-ligands to form a 1D bent ladder-like chain featured with a nano-sized channel,and these chains link each other via intermolecular hydrogen bonds and π-π stacking interactions to form a 3D supramolecular architecture with the voids filled with free water molecules. In addition,the water stability of 1 was investigated by PXRD patterns,which indicate that compound 1 keeps its structural integrity in boiling water for at least three days.

Metal-organic frameworks with mixed-ligands strategy as heterogeneous nucleation center to assist crystallization for efficient and stable perovskite solar cells

Deep-level defects and random oriented configuration in perovskite crystallization process would cause the nonradiative recombination and further affect the performance of perovskite solar cells(PSCs).Herein,two metal-organic frameworks(MOFs)with tunable Lewis-base passivation sites have been constructed(Cd-Httb and Cd-Httb-BDC,Httb=5-(4-(1H-1,2,4-triazole-1-yl)benzyl)-1h-tetrazole,BDC=1,4-dicarboxybenzene)to eliminate deep-level defects and simultaneously as nanostructured heterogeneous nucleation seed to assist the growth of large-grained perovskite films.Compared with the control and Cd-Httb,Cd-Httb-BDC designed with mix-ligands strategy exhibited the enhanced inducted effect on the crystallization and nucleation of high-quality perovskite films during annealing process.Consequently,the resultant Cd-Httb-BDC-modified device achieved higher power conversion efficiency(PCE)(22.18%)than the control(20.89%)and Cd-Httb(21.56%).Meanwhile,the unencapsulated Cd-Httb-BDC-modified device still maintained 90%of initial PCE after 1500 h in ambient conditions and exhibited enhanced thermal stability(85℃ in N_(2) atmosphere).This work presented a successful example of mixligands strategy on construction of high-quality MOF-assisted perovskite films for high-efficient and stable PSCs.

Assembling of a novel 3D Ag(Ⅰ)-MOFs with mixed ligands tactics：Syntheses, crystal structure and catalytic degradation of nitrophenol

A silver-based metal-organic framework（Ag-MOFs）, [Ag2（H3 ddcba）（dpp）2]（1）（H5 ddcba = 3,5-（di（2’,5’-dicarboxylphenyl）benozoic acid, dpp = 1,3-di（4-pyridyl）propane）, was successfully constructed via hydrothermal assembly of a pentacaboxylate ligand, a N-donor ligand and Ag（I） ions, which possesses a pcu topology and exhibits excellent catalytic properties in aqueous solution for the degradation of onitrophenol（2-NP）, m-nitrophenol（3-NP） and p-nitrophenol（4-NP）. Related kinetics of such catalytic reactions, photoluminescent and thermal stability of compound 1 were also investigated.

Synthesis,Structure and Fluorescent Property of a New Isolated Zn6Co9 Heteronuclear Cluster Constructed by Four Kinds of Ligands

A novel zero-dimensional heteronuclear cluster based on N-（phosphonomethyl）imi- no-diacetic acid （H4PMIDA） and Phen （1,10-phenanthroline）, [Zn6Co9（PMIDA）6（Phen）6（NO3）4（H2O）6]·2NO3·16H2O, has been synthesized under hydrothermal conditions and characterized by elemental analysis, IR spectrum, thermal analysis, and single-crystal X-ray diffraction. The isolated 15- nuclearity cluster [Zn6Co9（PMIDA）6（Phen）6（NO3）4（H2O）6]^2＋ was constructed by four kinds of ligands, and its charges are balanced by NO3^–. Each isolated cluster is further extended into a 3D supramolecular network through π？？？π interaction and C–H…O hydrogen bonds. Moreover, the solid-state fluorescent property of this complex has also been investigated at room temperature.

Synthesis of Coordination Polymers Using Different Maleic Acid Ligands under Hydrothermal Conditions

A novel coordination polymer, [ Ni （mal） （1,10＇-phen） （ H2O） ] n （ 1 ） （ mal = malate, 1,10＇-phen = 1,10- phenanthroline） was synthesized using malic acid which was generated from maleic acid via hydrothermal reaction. Complex 1, which displays a two-dimensional supramolecular network, was formed by the addition reaction of Ni and maleic acid with water molecules. To our knowledge, several coordination polymers have been directly synthesized from malic acid, but these types of complexes have seldom been synthesized from maleic acid via hydrothermal reactions. When Ni（ Ⅱ ） ion was changed to Zn（ Ⅱ） ion under the same condition, two-dimensional covalent complex 2 [ Zn2 （fma） 2 （1,10＇-phen） 2 ] n （fma = fumatic acid） was formed. Furthermore, complex 2 exhibits intense photolumi- nescent property at room temperature.

Syntheses and Crystal Structures of Mono-and Binuclear Copper(Ⅱ) Mixed-ligand Complexes Involving Schiff Base

The mononuclear copper（Ⅱ） complex [Cu（L）（2-AP）] 1 and binuclear copper（Ⅱ） complex [Cu（L）（py）]2 2 （L = C10H11O5NS, taurine o-vanillin, py = prydine, 2-AP = 2-aminopyridine） with mixed ligand have been synthesized and characterized by X-ray diffraction method. Crystal data for 1： orthorhombic, space group Pbca with a = 11.921（4）, b = 15.816（6）, c = 17.076（6） A, V= 3219.7（19） A^3, C15H17CuN3O5S, Z = 8, Mr = 414.92, De = 1.712 g/cm^3,μ（MoKα） = 1.520 mm^-1, F（000） = 1704, the final R = 0.0300 and wR = 0.0705 for 2840 observed reflections with I 〉 2σ（I）; and crystal data for 2： monoclinic, space group P21/c with a = 7.929（3）, b = 17.038（5）, c = 11.734（4） A, β = 98.162（6）°, V = 1569.1（9） A^3, C15H16CuN2O5S, Z = 4, Mr = 399.90, Dc = 1.693 g/cm^3, F（000） = 820,μ（MoKα） = 1.554 mm^-1, the final R = 0.0351 and wR = 0.0848 for 2767 observed reflections （I 〉 2σ（I））. The molecular structure of complex 1 consists of one tetra-coordinated Cu（Ⅱ） atom generating a slightly distorted square plane, and a one-dimensional chain structure is formed by intermolecular hydrogen bonds. Complex 2 consists of a diphenolic hydroxyl O-bridged binuclear copper（Ⅱ） structure. The crystal structures of complexes 1 and 2 reveal that the coordinate copper centers are bound to both nitrogen and oxygen atom donors. The usual N,O-trans arrangement of ligands is observed in both cases.

Synthesis and Crystal Structure of a Three-dimensional Mn(Ⅱ) Coordination Polymer with 3-(Pyrazin-2-yloxy)-pyridine and Azide Anion as Mixed Bridge Ligand

A three-dimensional coordination polymer [Mn2（μ1.3-N3）4（μ-PP）2]n （PP = 3-（pyrazin-2-yloxy）-pyridine） has been synthesized with 3-（pyrazin-2-yloxy）-pyridine and azide anion as mixed bridge ligand, and its crystal structure was determined by X-ray crystallography. The crystal data： triclinic system, space group P1, with a = 6.794（4）, b = 9.885（6）, c = 9.947（6） A, α = 64.170（6）, β= 84.190（8）, γ= 85.319（8）°, V = 597.7（6）A^3, Z = 1, C18H14Mn2N18O2, Mr = 624.35, Dc = 1.735 g/cm^3, F（000） = 314 and μ = 1.117 mm^-1. In the crystal, the azide anion acts as a bridge ligand and makes adjacent Mn（Ⅱ） ions connect into a two-dimensional sheet on the ab plane, then 3-（pyrazin-2-yloxy）-pyridine serves as a bidentate bridge ligand to connect neighboring sheets along

THE INTRAMOLECULAR AROMATIC-RING STACKING INTERACTION OF MIXED LIGAND PALLADIUM(Ⅱ)COMPLEXES Ⅲ.STUDIES ON THE Pd^(2+)-A-UTP^(4-)SYSTEMS BY HNMR

The intramolecular aromatic-ring stacking interaction of mixed- ligand complex Pd(A)(UTP)^(2-)in the system pd^(2+)-A-UTP^(4-)has been determined by ~1HNMR,where A=1,10-phenanthroline(phen),2,2'-bipyridyl(bpy)and DL- tryptophan(trp^-);UTP^(4-)=uridine 5-triphosphate.The result indicates that it is the partial stacking between the uracil ring of UTP^(4-)and the heterocyclic ring of A that makes H(5),H(6)and H(1')in the UTP^(4-)shift upfield signifi- cantly.Accordingly,the order of aromatic-ring interaction in the mixed- ligand complex has been obtained as follows:Pd(phen)(UTP)^(2-)(?)Pd(bpy)(UTP)^(2-) Pd(trp)(UTP)^(3-).

Syntheses of Coordination Compounds of 2-Amino-3-Methylbutanoic Acid Their Mixed Ligand Complexes and Antibacterial Activities

Coordination compounds of 2-amino-3-methylbutanoic acid were synthesized with chromium(III) and oxovanadium(IV) ions. M:L;1:2. Adducts of these complexes using 1,10-phenantroline and ethylenediamine were further synthesized, M:L, (1:2). These compounds were characterized using electronic, infra-red spectrophotometry, magnetic susceptibility measurement and percentage metal analyses. The zones of inhibition and minimum inhibitory concentrations of the compounds against eight microbes were studied. The results obtained indicated an octahedral geometry for the Cr(III) complexes, indicative of additional coordination of two water molecules. On the other hand a square pyramid geometry was obtained for the binary oxovanadium complex and its 1,10-phenantroline adduct. However, for the oxovanadium ethylenediamine adduct a distorted octahedral geometry was proposed. The result for the antibacterial studies indicated that both mixed ligand complexes of 1,10-phenantroline exhibited good antibacterial activity, and in some cases better activity than the standard, streptomycin.

Syntheses, Characterization and Biological Activity of Coordination Compounds of 3-Hydroxy-2-methyl-4<i>H</i>-pyran-4-one and Its Mixed Ligand Complexes with 1,2-Diaminocyclohexane

Coordination compounds of 3-hydroxy-2-methyl-4H-pyran-4-one with iron(III), cobat(III) and chromium(III) were synthesized with M:L (1:2). Mixed ligand coordination compounds of 3-hydroxy-2-methyl-4H-pyran-4-one and 1,2-diaminocyclohexane using the same metal ions were also synthesized M:L1:L2 (1:1:1) where L1 is 3-hydroxy-2-methyl-4H-pyran-4-one and L2 is 1,2-diaminocyclohexane. The coordination compounds obtained were characterized using electronic and infrared spectral analyses, magnetic susceptibility and percentage metal analysis. They were also evaluated for their cytotoxic and antioxidant activities. The result obtained suggested that octahedral geometry was obtained for all the compounds, as a result of additional two molecules of the solvent coordinated to the metal ions. Both the primary and secondary ligands coordinated in a bidentate fashion. The synthesized compounds exhibited moderate cytotoxicity, although none was as active as the standard. The cobalt(III) mixed ligand complex elicited the highest activity. The synthesized compounds all exhibited good to moderate antioxidant activity.

A New Coordination Polymer Built of 4-(5H-tetrazol)-benzoic Acid and 3,5-Dimethyl-1H,1,2,4-Triazole Showing a Rarely Observed(3,5)-Connected lhh Topology: Synthesis, Structure, CO_2 Adsorption and Luminescent Property

A three-dimensional coordination polymer,namely {[Zn2（tzba）（dmtrz）（OH）]·3H2O}n（1,H2tzba = 4-（5H-tetrazol）benzoic acid,Hdmtrz = 3,5-dimethyl-lH,l,2,4-triazole）,was hydrothermally synthesized and characterized by single-crystal X-ray diffraction.It crystallizes in monoclinic system,P21/c space group with a = 8.018（11）,b = 21.04（3）,c = 11.069（14） A,β=91.26（3）°,V= 1867（4） A^3,Z = 4,Dc = 1.729 g/cm^3,F（000） = 984,μ= 2.614 mm^（-1）,R（F^2 〉 2σ（F^2）） =0.0612 and wR（F^2） = 0.1533.Topological analysis reveals that compound 1 is a（3,5）-connected structure with a Schlafli symbol of（4~2.6）（4~2.6~5.8~3）,which is a rarely observed lhh topology.In addition,the CO2 adsorption performance and luminescent property of 1 have also been studied.

Synthesis, Characterization and Crystal Structure of Quaternary Complex of Gadolinium (Ⅲ)

A new quaternary mixed anion complex of gadolinium(Ⅲ), [Gd(CH 3CH 2COO) 2(N O 3)(phen)] 2, was synthesized and structurally characterized. The ESR spectr um of the complex with effective g values of 5.314, 2 473 and 1.880 in poly crys talline powder at room temperature is quite different from the U spectrum. The c oordination number of Gd 3+ is nine with a monocapped square antiprism geom etry. And the stacking effect was observed in the complex. The crystal of the co mplex belongs to triclinic with space group P 1, a=0.9626(4) n m, b=0.9732(4) nm, c=1.1758(5) nm, α=102.45(1)°, β=108.16(1) °, γ=96.68(2)°, V=1.0018(7) nm3, Z=2, D c=1.80 g·cm -3 , μ(MoKα)=33.63 mm -1, F(000)=530, GOF=1.80, R=0.023 and R w=0.027.

Hydrothermal Synthesis and Crystal Structure of a New Dimeric Lanthanum (Ⅲ) Complex

A new dimeric lanthanum (Ⅲ) complex [La_2(phen)_2(C_7H_3N_2O_6)_6] (phen=1, 10-phenanthroline) was synthesized by the hydrothermal method and determined by single crystal X-ray diffraction analysis. The La(Ⅲ) ion is coordinated to seven oxygen atoms from five carboxylate groups and two nitrogen atoms from a phen ligand, forming a monocapped square antiprismatic geometry. Six carboxylate groups coordinate to two La(Ⅲ) ions in three modes which are chelating bidentate, bridging bidentate and bridging tridentate. The crystal is triclinic with space group P-1, a=1.2030(4) nm, b=1.2962(5) nm, c=1.3330(5) nm, α=104.410(5)°, β=114.048(4)°, γ=100.054 (4)°, V=1.7467 (10) nm^3, M_r=952.46, Z=2, D_c=1.811 g·cm^(-3), F(000)=944, S=1.017, μ=1.320 mm^(-1), with R1=0.0298 and wR2=0.0625.

Two Zinc Architectures:A Mononuclear Complex and a 2D Wave-like Organic-inorganic Hybrid Layer

Self-assembly of Zn（NO3）2·6H2O and 2,3,5,6-tetrabromoterephthalic acid（H2TBTA） gave rise to two new zinc metal-organic frameworks,Zn（HTBTA）2（phen）2·H2O（1） and Zn（TBTA）1/2（μ2-OH）（H2O）·0.25EtOH（2）.Complex 1 is a mononuclear molecule.The hydrogen bonding interactions further connect the mononuclear molecules to generate a 2D supramolecular architecture.Complex 2 is a 2D organic-inorganic hybrid layer framework constructed from 1D rod-shaped secondary building units.

Hydrothermal Synthesis and Crystal Structure of Manganese(Ⅱ) Coordination Polymer Assembled by 4-Sulfophthalate and 4,4′-Bipyridine

The rational design and synthesis of metal-directed supramolecular framework compounds have received much attention in coordination chemistry because of their potential applications in catalysis, molecular selection, nonlinear optics, ion exchange, and microelectronics. Many high-dimensional coordination complexes have been designed and prepared through molecular self-assembly processes. The open metal organic framework can be produced via two kinds of interactions, i. e. , coordinate covalent bonds and weaker intermolecular forces. For this reason, the most efficient means to synthesize these compounds is to establish possible connections among different units.

Polynuclear Lanthanoid Complexes Containing Aluminium—The Structure of[HoAl(CF_3COO)_2(CF_3CHOO)(C_2H_5)_2(C_4H_8O)_2]_2 at 233K

[HoAl(CF_3COO)_2(CF_3CHOO)(C_2H_5)_2(C_4H_8O)_2]_2,Mr=1468.7,monoclinic,P 2_1/n,a=1.0084(4), b=1.8453(6),c=1.4501(6)nm,β=102.40(3)°,V=2.6355(1)nm^3,Z=2,D_c=1.81gcm^(-3),F(000)=1511, T=233K,Mo Kα radiation(λ=0.071069nm).R=0.052 for 6176 unique reflections[Ⅰ≥36(Ⅰ)].The structural units consist of dimeric molecules with the mixed ligand and central bimetallic atoms,which are polynuclear lanthanoid complexes containing aluminium.Ho-Ho'distance is 0.3619(1)nm.The coordination polyhedron of Ho can be described in terms of a distored bicap-prism.

Synthesis and Crystal Structure of 10-Phenyl-1,7-dithia-4-oxa-10-aza-12-crown-4

ＩｎｔｒｏｄｕｃｔｉｏｎＡｃｏｎｓｉｄｅｒａｂｌｅｉｎｔｅｒｅｓｔｈａｓｂｅｅｎｓｈｏｗｎｉｎｔｈｅｉｎｖｅｓｔｉｇａｔｉｏｎｏｆｍｉｘｅｄ－ｄｏｎｏｒｍａｃｒｏｍｏｌｅｃ－ｕｌａｒｌｉｇａｎｄｓｃｏｍｐｌｅｘｉｎｇｔｒａｎｓｉｔｉｏｎｉｏｎｓ［１］...

Steric hindrance effect of Schiff-base ligands on magnetic relaxation dynamics and emissive behavior of two dinuclear dysprosium complexes

The self-assembly reactions between mixed-ligand and tetrahydrate dysprosium acetate in the presence of mixed organic solvents lead to two structural similar dinuclear dysprosium complexes with composition formulas of Dy_(2)(L_1)_(2)(L_(2))_(2)(CH_(3)OH)_(2)·CH_(2)Cl_(2)·CH_(3)OH(1) and Dy_(2)(L_1)_(2)(L_(3))_(2)(CH_(3)OH)_(2)·CH_(3)CN(2),where L_1,L_(2) and L_(3) represent the deprotonated form of 4-tert-butyl-2-(7-methoxybenzo[d]oxazol-2-yl)phenol,(E)-1-(((3,5-di-tert-butyI-2-hydroxyphenyI)imino)methyl)naphthalen-2-ol and(E)-2,4-di-tertbutyl-6-((2-hydroxybenzylidene)amino)phenol.The tiny difference of the core structure of 1 and 2 is derived from the steric hindrance of Schiff base ligands L_(2) and L_(3).Dynamic magnetic measurements reveal that 1 and 2 show frequency-dependent out-of-phase alternating-current susceptibility signal peaks at different temperatures under zero dc field,diagnostic of single-molecule magnet behavior.The experimental derived energy barrier to magnetization reversal for 1 and 2 is 108(1),47(2) and 33(3) K.Ab initio CASSCF calculations performed on 1 and 2 suggest that the origin of the difference in magnetic properties originates from the variation in the single-ion anisotropy that arises due to minor structural variation.Further,the equation to calculate the effective energy barrier for Dy_(2) proposed earlier is found to yield an excellent agreement with the experimental results.Solid state fluorescence measurements performed on 1 and 2 demonstrate that both exhibit two ligands centered components of fluorescent emissive,in addition,with different emitting colors and chromaticity coordinates.The discrepancy of fluorescence and single molecule magnet behavior showed by 1 and 2 can be attributed to the steric hindrance effect of Schiff base ligands.

Synthesis,Structure and Theoretical Calculation of Metal Coordination Polymers with Pyrazine-2,3-dicarboxylic Acid and 3-(2-Pyridyl)pyrazole as Co-ligands

A new 2D metal coordination polymer(MCP),[Mn(pzdc)0.5(L)]n(1,pzdc=pyrazine-2,3-dicar-boxylic acid,HL=3-(2-pyridyl)pyrazole),was synthesized under hydrothermal conditions and characterized by single-crystal X-ray diffraction,powder XRD,FT-IR,TG,fluorescence and elemental analysis techniques.Pale yellow crystals crystallize in orthorhombic system,space group Fdd2 with a=11.2368(6),b=38.280(2),c=10.5682(6)Å,V=4545.9(4)Å3,C11H7MnN4O2,Mr=282.15,Dc=1.649 g/cm3,μ(MoKα)=1.159 mm^(-1),F(000)=2272,Z=16,the final R=0.0613 and wR=0.1773 for 2856 observed reflections(I>2σ(I)).It shows a two-dimensional network structure and is further assembled into a three-dimensional supramolecular framework via hydrogen bonds and abundantπ-πinteractions.In addition,we analyzed natural bond orbital(NBO)of 1 in using the PBE0/LANL2DZ method established in Gaussian 03 Program.There is obvious covalent interaction between the coordinated atoms and Mn(Ⅱ)ions.

The synthesis and structural studies of mixed ligand complex,tris(1-phenyl-3-methyl-4-trifluoroacetylpyrazol-5-one)mono(1-phenyl-3-methyl-pyrazol5-one)neodymium(Ⅲ)monohydrate

A mixed ligand neodymium complex containing 1-phenyl-3-methyl-4-trifluoroacetyl- pyrazol-5-one(HPMTFP)and 1-phenyl-3-methyl-pyrazol-5-one(PMP),with molecular formula Nd(PMTFP)_3·PMP·H_2O was synthesized.Its crystal and molecular structure has been determined by single crystal X-ray diffraction method.The complex crystallizes in monoclinic system with space group C_2~5h-P2_(1/n).There are four formula units in a cell of dimensions a=12.837(3),b=23.763(5),c=16.810(4) ,β=109.58(2)°.The structure has been refined by full-matrix least-squares techniques to a final R value of 0.0487 and Rw value of 0.432.The neodymium atom is coordinated to eight oxygen atoms with the average Nd-O bond length 2.439,Its thermostability,and mass spectrum have been discussed.