Citation: HE Tian, YUE Ke-Fen, CHEN San-Ping, ZHOU Chun-Sheng, YAN Ni. Synthesis, Structure and Thermodynamics/Kinetics Analysis of Three Different Interpenetrating Zinc(II) Coordination Architectures[J]. Acta Physico-Chimica Sinica, ;2016, 32(6): 1397-1403. doi: 10.3866/PKU.WHXB201603102 shu

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

1.
Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of the Ministry of Education, College of Chemistry and Materials Science, Northwest University, Xi'an 710069, P. R. China;
2.
Shaanxi Key Laboratory of Comprehensive Utilization of Tailings Resources, College of Chemical Engineering and Modern Materials, Shangluo University, Shangluo 726000, Shaanxi Province, P. R. China

Received Date: 25 January 2016
Revised Date: 9 March 2016

Fund Project: The project was supported by the National Natural Science Foundation of China (21543001, 21273137), Open Foundation of Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of the Ministry of Education, China (338080041), and Open Foundation of the Shaanxi Key Laboratory of Comprehensive Utilization of Tailings Resources, China (2014SKY-WK002).

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.
- Coordination polymer,
- Interpenetration,
- Thermodynamics,
- Kinetics
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沈阳化工大学材料科学与工程学院沈阳 110142