三个不同穿插的锌配合物的合成、结构和热动力学分析

doi:10.3866/PKU.WHXB201603102

Abstract

Abstract:

Based on flexible 1,4-bis(2-methyl-imidazol-1-yl)butane (bib) and three rigid line-shaped carboxylate mix-ligands, three Zn(Ⅱ) coordination polymers, {[Zn₂(bib)₂(1,4-ndc)₂]·H₂O}_n (1), {[Zn_0.5(bib)_0.5(bdc-Br₂)_0.5]·0.5H₂O}_n (2), {[Zn₂(bib) (4,4'- bpdc)₂]·H₂O}_n (3) (1,4-H₂ndc=1,4-naphthalenedicarboxylic acid, H₂bdc-Br₂=2,5-dibromoterephthalic acid, 4,4'-H₂bpdc=4,4'- biphenyldicarboxylic acid) have been synthesized under solvothermal conditions and characterized by elemental analysis, infrared (IR) spectrometry, and single crystal X-ray diffraction. 1 presents a 4-fold interpenetrating framework including three kinds of zigzag chains. 2 exhibits an unusual [2+2] interpenetrating framework. 3 features a 3-fold interpenetrating network. Their thermal decomposition behaviors were investigated by simultaneous thermogravimetry/differential thermal gravity and differential scanning calorimetry (TG/DTG-DSC) techniques. The TG curves indicate that the unusual [2+2] interpenetrating framework exhibits the highest thermal stability of the three frameworks, and the 4- fold interpenetrating framework exhibits higher thermal stability than the 3-fold interpenetrating framework. The thermodynamics and kinetics of skeleton collapse for the complexes were calculated by the integral Kissinger's method and Ozawa-Doyle's method. The activation energies (E) of 276.887, 318.515, and 149.310 kJ·mol^-1 illustrate the relationship of the reaction rates of complexes 1-3: 3 ＞ 1 ＞ 2. The structural characteristics could be elucidated from the thermodynamics and kinetics. Moreover, the fluorescent properties of complexes 1-3 were also studied.

Key words: Coordination polymer, Interpenetration, Thermodynamics, Kinetics

MSC2000:

O641

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Tian HE,Ke-Fen YUE,San-Ping CHEN,Chun-Sheng ZHOU,Ni YAN. Synthesis, Structure and Thermodynamics/Kinetics Analysis of Three Different Interpenetrating Zinc(Ⅱ) Coordination Architectures[J].Acta Phys. -Chim. Sin., 2016, 32(6): 1397-1403.

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Synthesis, Structure and Thermodynamics/Kinetics Analysis of Three Different Interpenetrating Zinc(Ⅱ) Coordination Architectures

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