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作 者:刘晶[1] 贾晓燕[1] 程美令[1] 任艳秋[1] 苏森[1] 刘琦[1,2] 尹桂[2]
机构地区:[1]常州大学石油化工学院,江苏省精细石油化工重点实验室,常州213164 [2]南京大学配位化学国家重点实验室,南京210093
出 处:《无机化学学报》2014年第9期2165-2173,共9页Chinese Journal of Inorganic Chemistry
基 金:国家自然科学基金(No.20971060,21101018);南京大学配位化学国家重点实验室开放课题资助项目;江苏精细石油化工重点实验室资助项目
摘 要:在4-甲基咪唑/三氮唑存在下,利用四氟对苯二甲酸为配体、与Pb(NO3)2作用,得到了2种配位聚合物{[Pb(tfbdc)(H2tfbdc)0.5]·(4-MI)·(H2O)}n(1)和{[Pb(tfbdc)(H2O)2]}n(2)(H2tfbdc=四氟对苯二甲酸,4-MI=4-甲基咪唑),并用红外光谱、元素分析和X-单晶衍射对其进行了表征。化合物1属于单斜晶系,空间群为P21/n,化合物2属于三斜晶系,空间群为P1。配合物1中,铅离子依靠正常的Pb-O键和次级键Pb…O,与7个氧原子配位;tfbdc2-阴离子和H2tfbdc分别采用不同的配位方式桥联铅离子,导致1个具有孔道的三维结构的形成。而4-甲基咪唑和游离水分子通过氢键作用嵌在这三维结构的孔道中。π-π堆积作用的存在增强了1的稳定性。配合物2中,铅离子是位于8个氧原子的配位环境中,tfbdc2-阴离子以螯合和桥联的方式与铅离子作用,导致1个二维层状结构的形成。此外还考察了1和2的热稳定性和固体荧光性质。In the present of 4-MI/triazole, Two lead(Ⅱ) coordination polymers, {[Pb(tfbdc)(H2tfbdc)0.5]·(4-MI)·(H2O)}n(1) and {[Pb(tfbdc)(H2O)2]}n(2)(tfbdc=tetrafluoroterephthalate, 4-MI=4-methylimidazole) have been synthesized and characterized by elemental analysis, IR spectra, thermogravimetric and X-ray single crystal structure analyses.Structure analyses reveal that 1 has monoclinic crystal system and space group of P21/n, and 2 has triclinic crystal system and space group of P1. In 1, each Pb(Ⅱ) ion is coordinated with seven oxygen atoms via the normal Pb-O bond and the sencondary bond Pb…O; tfbdc2-anion and H2 tfbdc ligands are bridged to Pb(Ⅱ) ions in different coordination fashion, resulting in the formation of a 3D structure with channels. 4-MI and free water molecules are clathrated in the channels via hydrogen bonds interactions.The existence of π-π stacking interactions further enhance the stabiltity of 1. In 2, each Pb(Ⅱ) ion is surrounded by eight oxygens, and tfbdc2-coordinates with Pb(Ⅱ) ion in chelating and bridging fashion, constructing a 2D layer structure. The thermal stability and solid-state luminescent properties of 1 and 2 have also been studied. CCDC: 977618, 1; 977147, 2.
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