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, {[Zn0.5(H2L)(tp)0.5(H2O)]H2O}n(1) and {[Zn2(HL)(btc)(H2O)]H2O}n(2)(H2L = 3-(1 Hpyrazol-4-yl)-5-(pyridin-3-yl)-1,2,4-triazole, H2tp = terephthalic acid;H3 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.

Metal-free synthesis of 3-trifluoromethyl-1,2,4-triazoles via oxidative cyclization of trifluoroacetimidohydrazides with N,N-dimethylformamide as carbon synthons

A metal-free approach for the synthesis of 3-trifluoromethyl-1,2,4-triazoles via I2-mediated oxidative cyclization of readily accessible trifluoroacetimidohydrazides with N,N-dimethylformamide(DMF)has been disclosed.In this transformation,the commonly used organic solvent DMF is applied as a C1 synthon and the methine unit of the 1,2,4-triazole products is independently from N-methyl and N-acyl of DMF.The application potential of the developed method has been demonstrated by the synthesis of the key skeleton of factor IXa inhibitors.

Theoretical Study on the Nitrogen-rich Derivatives Based on 1,2,4-Triazole and 1,2,3-Triazole Rings:an Extended Family of Power Performance Energetic Materials

The geometric and electronic structures of the derivatives of 4-nitro-5-(5-nitroimino-1,2,4-triazol-3-yl)-2H-1,2,3-triazolate(named A~J)are explored employing density functional theory(DFT)calculations at the B3LYP/6-311G^(**)level of theory.Based on the optimized molecular structures,the heats of formation(HOF)are obtained,and the electronic properties,density and molecular sensitivity by characteristic heights(H_(50))are discussed.Besides,the detonation performances(detonation velocity,detonation pressure)are estimated via Kamlet-Jacobs(K-J)formula.Compounds B(H50=29.4 cm,ρ=1.91 g/cm^(3),Q=1563.04 cal/g,P=36.05 GPa,D=8.95 km/s)and H(H_(50)=31.9 cm,ρ=1.80 g/cm^(3),Q=1610.09 cal/g,P=37.31 GPa,D=9.12 km/s)have positive HOFs and remarkable insensitivity and good detonation performance,strongly suggesting them as the acceptable new-type explosive.The initiating power surpasses conventional primary explosives,such as HMX.The outstanding detonation power of compounds B and H contributes to its future prospects as a promising green primary explosive.

Molecular Design and Property Prediction of High Density 4-Nitro-5-(5-nitro-1,2,4-triazol-3-yl)-2H-1,2,3-triazolate Derivatives as the Potential High Energy Explosives

To search for potential energetic materials with large energy density and acceptable thermodynamics and kinetics stability,twelve derivatives of 4-nitro-5-(5-nitro-1,2,4-triazol-3-yl)-2H-1,2,3-triazolate(named A~L)are designed and analyzed by using density functional theory(DFT)calculations at the B3LYP/6-311G**level of theory.The molecular heats of formation(HOF),electronic structures,impact sensitivity(H_(50)),oxygen balance(OB)and density(ρ)are investigated by isodesmic reaction method and physicochemical formulas.Furthermore,the detonation velocity(D)and detonation pressure(P)are calculated to study the detonation performance by Kamlet-Jacobs(K-J)equation.These results show that new molecule J(H_(50)=36.9 cm,ρ=1.90g/cm^(3),Q=1912.46 cal/g,P=37.82 GPa,D=9.22 km/s,OB=0.00),compound A(H_(50)=27.9 cm,ρ=1.93 g/cm^(3),Q=1612.93 cal/g,P=38.90 GPa,D=9.19 km/s)and compound H(H_(50)=37.3 cm,ρ=1.97 g/cm^(3),Q=1505.06cal/g,P=37.20 GPa,D=9.01 km/s)present promising effects that are far better RDX and HMX as the high energy density materials.Our calculations can provide useful information for the molecular synthesis of novel high energy density materials.

Synergistic Modification of PVC with Nitrogen-Containing Heterocycle and Tung-Oil Based Derivative for Enhanced Heat Stabilization and Plasticization Behavior

The additives present in polyvinyl chloride(PVC)materials are the major source of organic by-products during PVC degradation.The thermal stabilizer and plasticizer are the main additives that endow PVC with the required properties during its processing.However,these two additives easily migrate when samples are obtained by physical mixing of the additives with PVC.This causes the reduction of PVC sample efficacy and the increase in the formation of organic by-products in the radiolysis process.In this work,two kinds of grafted PVC samples(tungoil derivative grafted PVC and Atz grafted PVC,abbreviated as P-GT4 and P-AZ3)were synthesized by chemical grafting of 3-amino-1,2,4-triazole(Atz)and tung-oil derivative on PVC,respectively.These two PVC samples were then blended at different mass ratios to obtain hybrid PVC materials with excellent plasticization,thermal stability and migration resistance ability.Differential scanning calorimetry(DSC),discoloration,Congo red test and thermogravimetric analysis(TGA)showed that when the mass ratio of P-GT4 to P-AZ3 in the mixed PVC resin was 1:3,the resulting P1:3-GT4-AZ3(P4)presented the best plasticization and thermal stability.The kinetics of thermal decomposition showed that the activation energy of P4 was much higher than that of the reference material[PVC/DOTP/CaSt2/ZnSt2,PVC/CZ41 for short]at mass lossα=20%and 80%.In addition,the leaching test showed that P4 material possessed excellent migration resistance ability.

Auxiliary Ligand-tuned Structural Variation of Cd(Ⅱ)Coordination Polymers:Synthesis,Crystal Structures and Luminescent Properties

Two new Cd（Ⅱ） coordination polymers, [Cd（PT）（1,4-BDC）0.5]n （1） and [Cd（PT） （1,3-BDC）0.5]n （2） （HPT = 3-（pyridin-2-yl）-1,2,4-triazole, 1,4-H2BDC = 1,4-benzenedicarboxylic acid, 1,3-H2BDC = 1,3-benzenedicarboxylic acid）, have been hydrothermally synthesized and structurally characterized by single-crystal X-ray diffraction as well as elemental analysis and IR. Complexes 1 and 2 are both three-dimensional coordination polymers with two-dimensional sheet structures bridged by the deprotonated carboxylate ligands. In 1, 1,4-BDC2- bridges the layered network to generate a quadrangular framework, and 2 owns a sexangular framework, which was caused by the different steric hindrance between 1,4-BDC^2- and 1,3-BDC^2-. Their thermal stabilities and photoluminescent properties have been also investigated.