发光学报, 2009, 30 (1): 108, 网络出版: 2009-12-30
苯甲酸含氮杂环镝配合物的合成、表征及发光性质
Synthesis, Characterization and Fluorescence Property of Dy3+ with Halobenzoic Acid and Nitrogen-heterocyclic Complexes
摘要
合成了以稀土镝为中心离子,以苯甲酸、卤代苯甲酸及邻菲啰啉和2,2′-联吡啶为配体的五种固态配合物。对配合物进行了稀土络合滴定,C、H和N的元素分析、紫外光谱、红外光谱和荧光光谱测定,推测其组成分别为Dy (BA)3(bpy)、Dy (BA)3(phen)、Dy(ClBA)3(phen)(EtOH)、Dy(BrBA)3(phen)(EtOH)和Dy(IBA)3(phen)(EtOH)(BA=苯甲酸根,bpy=2,2′-联吡啶,phen=邻菲啰啉,ClBA=对氯苯甲酸,BrBA=对溴苯甲酸,IBA=对碘苯甲酸);苯甲酸羧基氧、邻菲啰啉和2,2′-联吡啶的氮原子与镝离子配位。配合物都具有较强的荧光,卤代苯甲酸配合物呈现规律发光,对氯苯甲酸-邻菲啰啉-镝配合物的发光效果较其它两种配合物强,对溴苯甲酸配合物又强于对碘苯甲酸配合物;苯甲酸-邻菲啰啉-镝配合物荧光强于苯甲酸-2,2′-联吡啶-镝配合物。
Abstract
Five complexes of dysprosium were synthesized, in which benzoic acid or halobenzoic acids were as the first ligand, and nitrogen-heterocyclic (phenanthroline or 2,2′-dipyridine) as the second ligand. By elemental analysis, rare earth coordination titration, the compositions of the complexes were confirmed to be Dy(BA)3(bpy), Dy(BA)3(phen), Dy(ClBA)3(phen)(EtOH), Dy(BrBA)3(phen)(EtOH) and Dy(IBA)3(phen)(EtOH),(BA=benzoic acid, ClBA=p-Cl-benzoic acid, BrBA=p-Br-benzoic acid, IBA=p-I-benzoic acid, bpy=2,2′-dipyridine, phen=1,10-phenanthroline), respectively. The ligands and coordination compounds were studied by means of IR spectra, UV-spectra, fluorescence excitation and emission spectra. The results showed that benzoic acid or halobenzoic acid is bonded with Dy(Ⅲ) through oxygen atoms in the carboxyl group, and phen or bpy ligands is bonded to Dy(Ⅲ) through nitrogen atoms. Fluore-scence emission spectra indicated that the fluorescence emission intensity of Dy(ClBA)3(phen)(EtOH) is the strongest, Dy(BrBA)3(phen)(EtOH) is second, and Dy(IBA)3(phen)(EtOH) is the weakest among the Dy(Ⅲ) with halobenzoic acid and phen complexes. The intensity of Dy(BA)3(bpy) is little stronger than Dy(BA)3(phen) at about 481 nm, but at about 573 nm, Dy(BA)3(phen) is more stronger.The 4F9/2 energy of Dy3+ ion is 20 509 cm-1, the triplet energy of phen is higher than the excitation energy of Dy3+ ion, thus the absorbing energy of phen can effectively transferred to Dy3+ ion, and producing a characteristic spectrum. The fluorescence intensity of Dy(ClBA)3(phen)(EtOH) is the strongest among the three halobenzoic acid complexes, it shows that the triplet state energy of p-Cl-benzoic acid matches well with the lowest excitation energy of Dy3+ ion.
魏晓燕, 赵永亮, 薛珍, 赵凤英, 于彦珠. 苯甲酸含氮杂环镝配合物的合成、表征及发光性质[J]. 发光学报, 2009, 30(1): 108. WEI Xiao-yan, ZHAO Yong-liang, XUE Zhen, ZHAO Feng-ying, YU Yan-zhu. Synthesis, Characterization and Fluorescence Property of Dy3+ with Halobenzoic Acid and Nitrogen-heterocyclic Complexes[J]. Chinese Journal of Luminescence, 2009, 30(1): 108.