C3对称性芳香三羧酸配体构筑的稀土-有机骨架化合物的合成、结构及荧光性质

doi:10.7503/cjcu20140555

高等学校化学学报 ›› 2014, Vol. 35 ›› Issue (10): 2055.doi: 10.7503/cjcu20140555

• 研究论文: 无机化学 • 上一篇下一篇

C₃对称性芳香三羧酸配体构筑的稀土-有机骨架化合物的合成、结构及荧光性质

汪淑华(), 胡汉珍, 陈超, 马润宁, 张宁()

南昌大学化学系, 南昌 330031

收稿日期:2014-06-20 出版日期:2014-10-10 发布日期:2014-09-30
作者简介:联系人简介: 汪淑华, 女, 博士, 副教授, 主要从事光谱分析研究. E-mail: shwang@ncu.edu.cn. 张宁, 男, 博士, 教授, 主要从事多相催化研究. E-mail: nzhang. ncu@163.com
基金资助:
国家自然科学基金(批准号: 21261017)、江西省自然科学基金(批准号: 20122BAB213003, 20132BAB203009, 20132BAB213004, 20133ACB20001)和江西省教育厅自然科学基金(批准号: GJJ13112)资助

Lanthanide Metal-organic Frameworks Constructed from Evolution of a C₃ Symmetry Ligand: Syntheses,Structures and Luminescent Properties^†

WANG Shuhua^*(), HU Hanzhen, CHEN Chao, MA Running, ZHANG Ning^*()

Department of Chemistry, Nanchang University, Nanchang 330031, China

Received:2014-06-20 Online:2014-10-10 Published:2014-09-30
Contact: WANG Shuhua,ZHANG Ning E-mail:shwang@ncu.edu.cn;nzhang. ncu@163.com
Supported by:
Supported by the National Natural Science Foundation of China(No.21261017), the Natural Science Foundation of Jiangxi Province, China(Nos.20122BAB213003, 20132BAB203009, 20132BAB213004, 20133ACB20001) and the Natural Science Foundation of Educational Department of Jiangxi Province, China(No.GJJ13112)

摘要/Abstract

摘要：

以稀土离子(La, Ce, Pr, Nd) 与具有C₃对称结构的芳香羧酸配体N,N',N″-三(4-苯甲酸基)-1,3,5-苯三甲酰胺(BTMC)为构筑单元, 合成了4个同构的三维非穿插金属-有机骨架化合物[Ln(BTMC)(DMF)]·3H₂O·2.5DMF[Ln=La(1), Ce(2), Pr(3), Nd(4)]. 采用单晶X射线衍射、粉末X射线衍射(PXRD)、红外光谱和热重分析对其结构及稳定性进行了表征, 并测试了它们捕获不同金属离子(La³⁺, Ce³⁺, Pr³⁺, Nd³⁺, Cd²⁺, Cr³⁺, Cu²⁺)及吸附染料甲基橙和曙红的固态荧光光谱变化. 结果表明, 化合物对金属离子及染料均有一定吸附作用, 捕获Cr³⁺后荧光强度变化最大, 说明对Cr³⁺具有较好的识别作用.

关键词: 稀土-有机骨架, 固态荧光, 金属离子识别

Abstract:

A series of 3D lanthanide metal-organic frameworks(MOFs) with similar structure, [Ln(BTMC)(DMF)]·2.5DMF·3H₂O[Ln=La(1), Ce(2), Pr(3), Nd(4), H₃BTMC=N,N',N″-tris(4-carboxyphenyl)-1,3,5-benzenetricarboxamide], has been synthesized under solvothermal conditions. The structures and thermal-stable properties of the four compounds were characterized by single-crystal X-ray diffraction, powder X-ray diffraction(PXRD), Fourier transform infrared(FTIR) spectra and thermal gravimetric(TG) analyses. The capacities of the compounds for capturing metal ions and dyes were investigated by solid state fluorescence spectra carefully, which indicated that after capturing different metal ions the emission peaks of the four compounds were blue-shift and exhibited a high Cr³⁺-specific luminescence enhancement.

Key words: Lanthanide metal-organic framework, Solid state fluorescence, Metal ion recognition

中图分类号:

O614.33

TrendMD:

汪淑华, 胡汉珍, 陈超, 马润宁, 张宁. C₃对称性芳香三羧酸配体构筑的稀土-有机骨架化合物的合成、结构及荧光性质. 高等学校化学学报, 2014, 35(10): 2055.

WANG Shuhua, HU Hanzhen, CHEN Chao, MA Running, ZHANG Ning. Lanthanide Metal-organic Frameworks Constructed from Evolution of a C₃ Symmetry Ligand: Syntheses,Structures and Luminescent Properties^†. Chem. J. Chinese Universities, 2014, 35(10): 2055.

图/表 7

Fig.1 Coordination environment of the Pr(Ⅲ) ions in compound 3 All the hydrogen atoms were omitted for clarity.

Fig.2 1D oval channels viewed along c axis in the framework of compound 3

Fig.3 Ball and stick schematic representations of 4-connected ligand(pink, A) and 8-connected Pr dimmer(green, B) and schematic representation of (4,8)-connected AlB2 topology(C) of compound 3

Fig.4 Simulated XRD pattern of compound 3(a) and experimental PXRD patterns of compounds 1—4(b—e, respectively)(A) and compound 3 after capturing/adsorbing Eosin(b), La3+(c), Cr3+(d) and methanol(e)(B)

Fig.5 FTIR spectra of compounds 1—4(a—d, respectively)(A) and compound 3 before(a) and after capturing/adsorbing methanol(b), Cr3+(c), La3+(d) and Cu2+(e)(B)

Fig.6 TG curves of compounds 1—4(A) and compound 3 before and after capturing/adsorbing methanol, Cr3+, La3+ and Eosin(B)

Fig.7 Fluorescence emission spectra of ligand BTMC(a) and compounds 1—4(b—e, respectively)(A) and fluorenscence spectra of compounds 1(B), 3(C) and 4(D) with different ions, methyl orange(MO) and Eosin, respectively The inset bar charts represent the intensity changes of the emission with different ions and dyes.

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C₃对称性芳香三羧酸配体构筑的稀土-有机骨架化合物的合成、结构及荧光性质

Lanthanide Metal-organic Frameworks Constructed from Evolution of a C₃ Symmetry Ligand: Syntheses,Structures and Luminescent Properties^†

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