綠色化學原則之應用：含有2,4-吡啶二羧酸配位聚合物之合成， 結構分析與物性探討

Abstract

(1) Synthesis of mixed-metal coordination polymers under hydrothermal conditions. Treatment of Mg(NO3)2•6H2O 、 2,4-pyridinedicarboxylic acid with CuCl2•2H2O、Ni(NO3)2•6H2O or CoCl2•6H2O in aqueous solution under hydrothermal conditions led to the formation of compounds [MgCu(2,4-pydc)2(H2O)4]n (1), {[MgNi(2,4-pydc)2(H2O)6]•2H2O}n (2), [Mg(H2O)6][Co(2,4-pydc)2(H2O)2] (3), [Mg0.25Co0.75(2,4-pydc)(H2O)2]n (4), respectively. Compounds 1, 2 and 3 exhibit different architectures and morphologies. Compound 1 adopts a 2D structure, 2 exhibits a 1D chain. Compounds 3 and 4 were obtained by modulating the molar ratio of metal ion to ligand. Compound 3 is a discrete molecule, while 4 adopts a 2D structure. (2) Synthesis of coordination polymers tuned by structure directing agent under hydrothermal conditions. Treatment of metal ions and 2,4-pyridinedicarboxylic acid along with three types of nitrogen-rich-ligands afforded coordination polymers 5–7 under hydrothermal conditions. Mixing of Mg(NO3)2•6H2O, H2-2,4-pydc and 4,4'-dipyridylpiperazine (2N-DPyP) produced [Mg(2,4-pydc)(H2O)2]n (5). Compound {[Cu2I(2bpm)2CuII(2,4-pydc)2]•4H2O}n (6) was obtained from the reaction of Cu(NO3)2•3H2O, H2-2,4-pydc and 2,2'-bipyrimidine (2bpm); Treatment of CoCl2•6H2O, H2-2,4-pydc and 5,5'-bipyrimidine (5bpm) led to the formation of {[Co3(2,4-pydc)3(EtOH)(H2O)3]•EtOH}n (7). The structure directing agents, such as 2N-DPyD and 5bpm, play key roles in tuning the final topologies of compounds 5 and 7. Compound 5 adopts a 2D layer structure and 7 exhibits a 1D chain structure. The concept of green chemistry was applied on the synthesis of compounds 1–7 by using water and ethanol as solvents under hydrothermal reactions. To develop efficient, one-step synthetic strategies with environtally benign solvents for the preparation of functional materials is another goal of this study.