| Coordination polymers（CPs）consist of organic ligands and metal ions/clusters and have been widely studied because of their potential applications in catalysis,drug delivery and gas storage and their rich structure.In recent years,the toxic pollutants had become a common concern around the world due to the harm to human body and environment.The luminescent CPs had been widely explored as chemosensors for detecting hazardous substances.In this paper,11 unusual CPs were synthesized based on two organic ligands with luminescent properties.Their structures were characterized by single X-ray diffraction,powder X-ray diffraction,infrared spectroscopy,thermogravimetric analyses,etc.Meanwhile,their emission properties were studied,and some CPs were detailed studied the application in the detection of TNP and Cu2+.The molecular formulae of the 11 CPs are as followed:（1）{Cd（pytpy）（INA）（OH）·2H2O}n（2）{Cd2（pytpy）（1,4-NDC）2（H2O）·3H2O}n（3）{Cd（pytpy）（HBTC）·H2O}n（4）{Cd（pytpy）（HBTC）·3H2O}n（5）{Zn2（2-bpt）（OBA）2·H2O}n（6）{Cd（2-bpt）（2,5-TDC）·7H2O·2-bpt}n（7）{Cd2（2-bpt）（HBTTC）（H2BTTC）0.5（H2O）}n（8）{Cd3（2-bpt）（BTTC）1.5·H2O}n（9）{Cd（2-bpt）Cl（μ2-Cl）}2（10）{Cd（2-bpt）Br（μ2-Br）}2（11）Cd2（2-bpt）2I3（μ2-I）In the above formula,pytpy=4′-（4-pyridyl）-2,2′:6′,2′′-terpyridine;INA=isonicotinic acid;1,4-NDC=1,4-naphthoic acid;H3BTC=1,3,5-Trimesic acid;H2OBA=4,4-diphenyl ether dicarboxylic acid;2,5-TDC=2,5-thiophenedicarboxylic acid;H4BTTC=1,2,4,5-benzene tetracarboxylic acid;2-bpt=4-amino-3,5-bis（2-pyridyl）-1,2,4-triazole.1.1 and 2 with different structures were successfully synthesized by polydentate ligand pytpy and two carboxylic acid ligands.Structure analysis showed that 1 adopts a 2D supermolecular network structure sustained throughπ-πinteraction,2 exhibit a 3D framework composed of{Cd2}dimer bridged by 1,4-NDC and pytpy.The emission studies indicated that both 1 and 2 showed a strong emission.Meanwhile,1 have detection properties for nitroaromatic explosives and heavy metal ions,expecially exhibit highly sensitivity for detecting TNP and Cu2+.2.3 and 4 with different structures were successfully synthesized by pytpy and H3BTC.Structure analysis showed that 3 and 4 have the same basic building blocks,but due to different synthesis condinations,different structures were formed.3 shows a 1D“zigzia”chain structure,and 4 presents a 1D linear structure.The emission studies indicated that both3 and 4 showed a strong emission.Meanwhile,3 have detection properties for nitroaromatic explosives and heavy metal ions,expecially exhibit highly sensitivity for detecting TNP and Cu2+.3.5-8 were successfully synthesized using polydentate ligand 2-bpt and three carboxylic acid ligands.Structure analysis showed 5 adopts a 2D network structure formed by{Zn2}dinuclear clusters and H2OBA bridges,6 shows a 1D double-chains structure in which Cd and 2,5-TDC are connected via 2-bpt.Both 7 and 8 are constructed from H4BTTC and Cd,but they have different structures due to the differences in synthesis conditions.7 exhibits a2D network structure formed by a doble-layered metal chain connected by H4BTTC and2-bpt and then bridged by H4BTTC.8 shows a 3D framework formed by H4BTTC bridged metal Cd chains.The emission studies indicated that both 5-8 showed a strong emission.Meanwhile,5 and 6 have detection properties for nitroaromatic explosives and heavy metal ions,expecially exhibit highly sensitivity for detecting TNP and Cu2+.4.Two-nuclear oligomer 9-11 were synthesized by introducing halogen with 2-bpt.In9-10,2-bpt is a dimer structure in which Cd is chelated unilaterally,and a halogen is bridged to form another Cd.The 2-bpt in 11 has both unilateral chelation and a bilateral chelation coordination mode and the metal is also bridged by halogen to form a binuclear cluster structure.The emission studies indicated that both 9-11 showed a strong emission.Meanwhile,9 and 10 have detection properties for nitroaromatic explosives and heavy metal ions,expecially exhibit highly sensitivity for detecting TNP and Cu2+. |
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