物理化学学报 >> 2016, Vol. 32 >> Issue (6): 1397-1403.doi: 10.3866/PKU.WHXB201603102

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三个不同穿插的锌配合物的合成、结构和热动力学分析

何甜1,岳可芬1,*(),陈三平1,周春生2,*(),晏妮1   

  1. 1 西北大学化学与材料科学学院,教育部合成与天然功能分子化学重点实验室,西安710069
    2 商洛学院化工与现代材料科学学院,陕西省尾矿资源利用重点实验室,陕西商洛726000
  • 收稿日期:2016-01-25 发布日期:2016-06-03
  • 通讯作者: 岳可芬,周春生 E-mail:ykflyy@nwu.edu.cn;slzhoucs@126.com.cn
  • 基金资助:
    国家自然科学基金(21543001, 21273137);教育部合成与天然功能分子化学重点实验室开放基金(338080041);陕西省尾矿资源综合利用实验室开放基金(2014SKY-WK002)

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

Tian HE1,Ke-Fen YUE1,*(),San-Ping CHEN1,Chun-Sheng ZHOU2,*(),Ni YAN1   

  1. 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:2016-01-25 Published:2016-06-03
  • Contact: Ke-Fen YUE,Chun-Sheng ZHOU E-mail:ykflyy@nwu.edu.cn;slzhoucs@126.com.cn
  • Supported by:
    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);Open Foundation of the Shaanxi Key Laboratory of Comprehensive Utilization of Tailings Resources, China(2014SKY-WK002)

摘要:

使用醋酸锌,柔性的1,4-二甲基咪唑丁烷(bib)和三个刚性直链型羧酸混合配体,在溶剂热条件下合成了三个具有不同穿插结构的配合物。并通过元素分析,红外,X射线单晶衍射进行了表征。配合物 1是一个具有三种Z字链的四重穿插结构,配合物2是一个特殊的[2+2]型四重穿插结构,配合物3是一个具有双核结构单元的三重穿插结构。通过使用热重分析/微分热重和差示扫描量热(TG/DTG-DSC)技术研究了它们的热分解过程,由热重分析得出特殊的[2+2]型四重穿插结构稳定性最好,四重穿插结构比三重穿插结构稳定。使用Kissinger和Ozawa-Doyle法对配合物骨架坍塌过程进行了计算,得出配合物1-3的表观活化能分别为276.887、318.515、149.310 kJ·mol-1,可以得出配合物1-3的反应速率关系为3 > 1 > 2。从热力学和动力学的角度来说明配合物的结构稳定性。其次,还对配合物1-3的荧光性质进行了表征。

关键词: 配合物, 穿插, 热力学, 动力学

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), {[Zn0.5(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: 312. 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