The Synthesis of New Sulfur-containing Chiral Macrocyclic Ligands

Five new chiral sulfur-containing macrocyclic ligands which can be used in chiral recognition to guests have been synthesized and characterized

Intramolecular Hydrogen Bond Self-template Synthesis of Some New Robson-type Macrocyclic Ligands

The intramolecular hydrogen bond self-template effect was suggested in the process of directly synthesizing the first six chiral metal-free Robson-type macrocyclic ligands. These ligands were characterized by H-1 NMR, IR, FAB-MS.

The Synthesis of a New Macrocyclic Dinucleating Ligand,3,6,9,17,20,23-Hexaaza-29,30-Dihydroxy-13,27-Dimethyl-Tricyclo[23,3,1,1^(11,15)]Triaconta-1(28),11,13, 15(30),25,26-Hexaene

A new dinucleating 24-membered hexaazadiphenol macrocyclic ligand, 3,6,9,17,20, 23-hexaaza-29,30- dihydroxy-13,27-dimethyl-tricycl [23, 3, 1, 1 11,15] triaconta -1(28), 11,13,15(30),25, 26-hexaene, BDBPH, was synthesized by the NaBH4 reduction of the Schiff-base obtained from the [2+2] condensation between diethylenetriamine and diformyl -p-cresol. The structure was characterized by elemental analysis, 1HNMR and FAB-MS. The synthetic method was also discussed.

Hydrothermal in situ Ligand Synthesis from 1,10-Phenanthroline-5,6-dione and Characterization of 1D Coordination Polymers [Co(bpdc)(H_2O)_3]·H_2O and [Cu(bpy)V_2O_6]

Hydrothermal treatment of MCl2 （ M = Co or Cu ） , NH4 VO3, and 1,10-phenanthroline-5,6-dione （pdon） resulted in the formation of a duplex coordination polymer [ Co （ bpdc ） （ H2O ） 3 ] · H2O （ bpdc = 2,2＇-bipyridine-3,3＇-dicarboxylate） and a chain-like coordination polymer [ Cu （bpy） V2O6 ] （ bpy = 2,2＇-bipyridine ）. X-ray single-crystal structural analysis shows that under hydrothermal conditions and in the presence of different transition metals, the organic reagent pdon was transformed in situ into bpdc and bpy, respectively. Mechanism of the in situ ligand synthesis reaction has been discussed.

Heterometallic Trinuclear Ni_2Zn and Ni_2Mn Complexes of Macrocyclic Oxamide: Synthesis and Crystal Structures

Two novel heterometallic trinuclear complexes of macrocyclic oxamide [Mn（NiL）2（HBTC）H2O] （1） and [Zn（NiL）2（HBTC）H2O] （2） （NiL, H2L = 2,3-dioxo-5,6,14,15-dibenzo-1,4,8,12-tetraazacyclo-pentadeca-7,13-dien, H3BTC = 1,3,5-benzenetricarboxylic acid） have been solvothermally synthesized and structurally characterized by elemental analysis, IR spectroscopy and single-crystal X-ray diffraction. For 1, the crystals crystallize in the monoclinic system, space group P21/c with a = 11.3595（5）, b = 23.1498（11）, c = 17.2558（8） and =101.2530（10）°. For 2, the crystals crystallize in the monoclinic system, space group P21/c with a = 11.5214（8）, b = 20.6566（14）, c = 18.4126（13） and = 92.6770（10）°. The structures of 1 and 2 have oxamido-bridged trinuclear [NiⅡ2MⅡ] units and consist of two-dimensional supramolecular architectures formed by strong O–H…O intermolecular hydrogen bonds.

ASYMMETRIC SYNTHESIS WITH ORGANO-TITANATE REAGENTS COORDINATED BY TARTARATE-LIKE LIGAND

A series of substituted chiral benzhydrols were synthesized by the reaction of aromatic aldehydes with chiral intermediates formed from chiral titanates and arylmagnesium halides.

THE STUDY OF ENZYMATIC SYNTHESIS OF MACROCYCLIC LACTONES

The effects of the chain length and stereo-factor of substrates and solvents on the lipase catalysed lactonization of ω-hydroxy-ester were studied, And also the catalytic effects of various enzymes were compared.

Complexation Properties and Synthesis of 1,2-Bis(2 ,2' -bipyridinyl)ethylene and 1,2-Bis(2,2' -bipyridinyl)ethane Ligands with Cu(I)

l,2-Bis(2,2'-bipyridinyl)ethylene(1) ligand was synthesized by Wittig-Horner reaction and 1, 2-Bis(2, 2'-bipyridinyl)ethane(2) ligand(which can be obtained via another route ) was prepared by hydrogenation of (1). The formation of complexes of (1) and (2) with copper (I) has been studied. The influence of the different bridge chains (CH =CH, CH2CH2) on complexation is discussed on the basis of 1H NMR spectra. Keywords Dipyridine aldehyde, Dipyridine derivative, Copper complex

The Crystal and Molecular Structure of a New Macrocyclic Ligand, (H_6BDBPH)Br_6·4H_2O

The hexahydro\|bromide salt of a new 24\|membered hexaaza diphenol macrocyclic ligand, （H6BDBPH）Br6·4H2O （C 26H 56N6O6Br6, Mr= 1028.23）, crystallizes in the monoclinic system, space group P21/c, with cell parameters: a=14.441（5）, b=11.482（4）, c=12.090（6）, β=96.92°, V= 1990 （1）3, Z=2, Dc=1.716 g/cm3; F（000） =1024. MoKα radiation, λ= 0.71013), R = 0.0643 and wR = 0.1356 for 3507 independent reflections with I>2σ（I）. The macrocyclic ligand adapts chair form, and the crystallographic inversion center is located in the macrocyclic cavity, and the six bromide ions and four water molecules are situated symmetrically outside the macrocyclic cavity.

The Synthesis of Podophyllotoxin Derivatives with Macrocyclic Dilactone

Starting from podophyllotoxin, five new derivatives with macrocyclic dilactone 5 similar to 9 have been synthesized,and their structures were confirmed by IR, MS,H-1 NMR as well as HRMS. The key step is cyclization by high dilution method.

Crystal Structure of C19H22N2O3 and Synthesis of Two Potential Schiff-base Ligands

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Studies on Selena-Macrocyclic Amides Synthesis and Structural Characterization of 7-Phenyl-5, 9-dioxo-1-selena-4, 7, 10-triazacyclododecane and 6-(4-Nitrobenzyl )-5, 9-dioxo-1, 4, 7, 10-selenatriazacyclododecane

7-Phenyl-5, 9-dioxo-1-selena-4, 7, 10-triazacyclododecane (1) and 6-(4-Nitrobenzyl)-5, 9-dioxo-1, 4, 7, 10-selenatriazacycloedecane (2) were synthesizedby condensation of bis (2-aminoethyl) selenide and corresponding diethyl esters. Theircrystal structures were determined. Crystal data: C14H19N3O2Se (1), Mr= 340. 28,space group P212121, a=5. 328(5), b= 14. 043(5), c= 18. 569(5) A, V= 1403(1)A3, Z= 4, Dc = 1. 610 g/cm3, μ= 3. 676 mm-1, F(000) = 696, T= 296K, R=0. 0269 for 1577 observed data. C15 H20 N4O4Se (2), Mr = 399. 31, space groupP212121, a=13. 849(5), b=4. 936(5), c=24. 942(5) A, V= 1705(1) A s, Z=4,Dc= 1. 566g/cm3, μ= 3. 230 mm-1 F(000) =816, T= 296K, R=0. 0856 for 3442observed data.

The First Example of Inorganic-organic Compound Involving the Largest Vanadium Cluster of [V_(34)O_(82)]^(10-): Hydrothermal Synthesis and Characterization of a One-dimensional Chain of {[NiC_(16)H_(36)N_4]_5[V_(34)O_(82)]}_n

The title compound, [NiL]5[V34O82·8H2O （1, L=5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane）, has been synthesized under hydrothermal conditions and structurally characterized by EA, IR, XPS, TG and single-crystal X-ray diffraction. It crystallizes in the monoclinic system, space group C2/c with a=33.061（4）, b=15.3457（17）, c=33.902（4）, β=101.930（2）°, Mr=4904.08, V=16828（3）3 , Z=4, Dc=1.936 g/cm3 , F（000）=9832, μ=2.425 mm-1 , the final R=0.0402 and wR=0.0969. The mixed valence vanadium clusters of [V34O82]10- bridges [NiL]2＋ to form a one-dimensional chain in 1. To the best of our knowledge, the title complex is the first example of organic-inorganic hybrid material involving the largest vanadium cluster of [V34O82]10-.

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.

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.

THE SYNTHESIS AND CHARACTERIZATION OF ASYMMETRIC TRIPYRRANE-CONTAINING MACROCYCLES

An improved procedure was used to prepare the asymmetric tripyrrane-containing macrocycles, The yield was over 85% These maerocycles could be oxidized to the methine bridled 23 (?)-electron aromatic cadmium(Ⅱ)complexes by reating with cadmium chloride in the presence of air and their atructures were characterized.

Proton-Template Synthesis of a П─Conjugated Macrocycle and Structure of its Ni_2(Ⅱ)—Complex

metol-free Robson -type macrocycle was synthesized for first time by proton-templation and from that the metal complexes were prepared.By X-ray study the structure of Ni(Ⅱ)-complex was characterized.

Facile synthesis of flake-like dihydrate zinc oxalate particles

Monodispersed dihydrated zinc oxalate(ZnC_2O_4·2H_2O) particles with characteristic morphology were synthesized by aging a mixed solution of zinc nitrate(Zn(NO_3)_2) and sodium oxalate(Na_2C_2O_4) in the presence of a citrate ligand, with an average flat size of approximately 10–15 μm. The important parameters, including the solution pH values and the concentration of the zinc ions and citrate ligand, were investigated using a series of experiments. It is verified that the citrate ligand significantly affects the morphology of zinc oxalate particles, probably via its multiple roles of chelating, dispersing, and selective absorption. Thermodynamic equilibrium of the distribution of zinc species in an aqueous solution of Zn(Ⅱ)-citrate-oxalate-H_2O was estimated to explain the experimental results and to clarify the size and morphological evolution mechanism of the precipitated particles.

One-pot synthesis of Ag-rich AgPd alloy nanoactiniae and their enhanced electrocatalytic activity toward oxygen reduction

The electro-catalytic properties can be effectively optimized by designing bimetallic alloy nanoparticles with high-content less-active metal to enhance the competence of more-active noble metal. Herein, a one-pot hydrothermal approach is demonstrated for the controllable synthesis of Ag-rich Ag_9Pd_1 alloy nanoactiniae with obviously enhanced electro-catalytic activity(2.23 mA cm^(-2) at 0.85 V) and stability for oxygen reduction reaction. In alkaline solution, the ORR onset potential and half-wave potential of the Ag_9Pd_1 alloy nanoactiniae can reach a value of 1.02 V and 0.89 V, respectively, which origin from strong ligand and ensemble effects between Pd element and Ag element. The nanocrystals are uniformly alloyed, displaying a Ag_9Pd_1 combination, as displayed by an assembly of X-ray diffraction(XRD) spectrum,energy dispersive X-ray(EDX) analysis, and cyclic voltammetry(CV). This concept of tuning bimetallic alloy nanocrystals with low concentrations of more precious metal may be a promising approach to be applicable to a wide range of alloy nanocrystals.

A NOVEL THIOPHENE-DERIVED N_2O_2 MACROCYCLE AND ITS Ag(I) COMPLEX: SYNTHESIS AND CHARACTERIZATION

A novel macrocycle containing thiophene （L） was prepared first by the interaction of 2,5-bis-（chloromethyl）-thiophene （A） and salicylaldehyde to give 2, 5-bis-（2-formylphenoxymethyl）-thiophene （B）, and then by the nontemplate cyclocondensation of 1,3-diaminopropane with （B） followed by a "onepot" reduction without isolation of the diimine intermediate. The corresponding silver complex, AgLClO;, was also prepared. The macrocycle was characterized by IR, elemental analysis, MS and;HNMR.