将吡啶-2,4,6-三羧酸(2,4,6-pytaH3),4-氨基-3,5-二(4-吡啶基)-1,2,4-三氮唑(4,4′-abpt)和CoCl2在不同的pH条件下发生水热反应,得到2个新的配位聚合物[Co(2,4,6-pytaH)(4,4′-abpt)(H2O)] (1)和[Co1.5(2,4,6-pyta)(4,4′-abpt)(H2O)3]· 3.5H2O (2).配合物1是在吡啶-2,4,6-三羧酸酸性环境下产生的,吡啶-2,4,6-三羧酸在水热条件下只脱去2个羧基上的质子变成2,4,6-pytaH2-,而配合物2是在NaOH碱性溶液下反应得到的,其中吡啶-2,4,6-三羧酸完全脱去3个羧基上的质子变成2,4,6-pyta3-.配合物1中包含一维Co-羧酸链,2中存在具有(4,4)拓扑网络的二维层.1和2中的一维链和二维层通过π-π堆积和丰富的氢键作用分别拓展成三维超分子网络.单晶结构分析表明,配合物1结晶于单斜晶系,P21空间群,a=0.961 30 (10) nm,b=0.632 09(6) nm,c =3.372 9(4) nm,β=95.104(2)°,V=2.041 3(4) nm3,Z=4.而配合物2结晶于单斜晶系,P21/c空间群,a=1.795 2(2)nm,b=0.729 62(8) nm,c=2.078 7(2) nm,β=112.323(2)°,V=2.518 6(5) nm3,Z=4.%Hydrothermal reaction of pyridine-2,4,6-tricarboxylic acid (2,4,6-pytaH3),4-amino-3,5-bis(4-pyridyl)-1,2,4-triazole (4,4′-abpt) and CoCl2 under different pH conditions generated two coordination polymers [Co(2,4,6-pytaH)(4,4′-abpt)(H2O)] (1) and [Co1.5(2,4,6-pyta)(4,4′-abpt)(H2O)3]·3.5H2O (2).Complex 1 was synthesized under 2,4,6-pytaH3 acid environment and 2,4,6-pytaH3 was partly deprotoned into 2,4,6-pytaH2-,while 2 was reacted under NaOH basic solution and 2,4,6-pytaH3 was completely deprotoned into 2,4,6-pyta3-.Complex 1 contains a one-dimensional (1D) Co-carboxylate chain,while 2 exhibits a two-dimensional (2D) grid-like coordination layer with (4,4) network topology.The three-dimensional (3D) supramolecular networks of 1 and 2 are further constructed through π-π stacking and fruitful hydrogen-bonding (H-bonding) of inter-layers and inter-chains,respectively.X-ray diffraction crystal structure analysis shows that 1 crystallizes in monoclinic system,space group P21,a=0.961 30(10) nm,b=0.632 09(6) nm,c=3.372 9(4) nm,β=95.104(2)°,V=2.041 3(4) nm3,Z=4; and 2 crystallizes in monoclinic system,space group P21/c,a=1.795 2(2) nm,b=0.729 62(8) nm,c=2.078 7(2) nm,β=112.323(2)°,V=2.518 6(5) nm3,Z=4.Thermal stability of 2 was measured in N2 atmosphere.CCDC:784916,1;784915,2.
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