八面体纳米笼构筑的金属-有机框架化合物

doi:10.6023/A12080546

化学学报 ›› 2012, Vol. 70 ›› Issue (19): 2012-2015.DOI: 10.6023/A12080546 上一篇下一篇

研究通讯

八面体纳米笼构筑的金属-有机框架化合物

林祖金, 林熙, 曹荣

中国科学院福建物质结构研究所结构化学国家重点实验室福州 350002

投稿日期:2012-08-12 发布日期:2012-09-24
通讯作者: 曹荣 E-mail:rcao@fjirsm.ac.cn
基金资助:
项目受国家重点基础研究发展计划(973计划, Nos. 2011CB932504, 2012CB821705);国家自然科学基金(Nos. 91022007, 21003128和20901078);福建省纳米材料重点实验室(No. 2006L2005)和中国科学院重要方向性课题的资助.

Construction of Two Octahedral Cage-based Metal-organic Frameworks

Lin Zujin, Lin Xi, Cao Rong

State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002

Received:2012-08-12 Published:2012-09-24
Supported by:
Project supported by the 973 Program (Nos. 2011CB932504, 2012CB821705), National Natural Science Foundation of China (Nos. 91022007, 21003128, and 20901078), Fujian Key Laboratory of Nanomaterials (No. 2006L2005), and Key Projects from CAS.

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摘要/Abstract

利用半刚性的三足羧酸配体1,3,5-tris[3-(carboxyphenyl)oxamethyl]-2,4,6-trimethylbenzene acid (H₃TBTC)与金属离子自组装成功合成了两例八面体纳米笼构建的金属-有机框架化合物: {[Zn₃TBTC₂(DMA)(H₂O)]·3DMA·3H₂O}_n (1), {[Cd₃TBTC₂(DMA)₂(H₂O)₂]·2DMA·2H₂O}_n (2). TBTC³^-配体在化合物中呈现出cis,cis,cis-和cis,trans,trans-两种构型. cis,cis,cis-构型的TBTC³^-配体与Zn₃(COO)₆次级结构基元(secondary building units, SBUs)构筑了畸变的八面体金属-有机纳米笼, 因而化合物的结构可以看成是八面体金属-有机纳米笼作为超分子构建单元(supramolecular building blocks, SBBs), 在空间上与cis,trans,trans-构型的配体相连, 最终形成具有(3,18)-连接的三维无限网络. 荧光测试结果表明, 化合物1～2的荧光都是基于配体的发射. 相对于配体的发射光谱, 化合物1～2的发射光谱展现出蓝移的现象. 气体吸附测试结果表明, 化合物1～2具有选择性吸附二氧化碳的能力.

关键词: 金属-有机框架, 配位聚合物, 纳米笼, 半刚性配体, 气体吸附, 荧光

Two isostructural octahedral metal-organic frameworks formulated as {[Zn₃TBTC₂(DMA)(H₂O)]·3DMA·3H₂O}_n (1), {[Cd₃TBTC₂(DMA)₂(H₂O)₂]·2DMA·2H₂O}_n (2) have been successfully prepared via solvothermal synthesis based on a predesigned semi-rigid ligand, 1,3,5-tris[3-(carboxyphenyl)oxamethyl]-2,4,6-trimethylbenzene acid (H₃TBTC). In the structure, the semi-rigid ligand adopts cis,cis,cis- and cis,trans,trans-conformations. Six cis,cis,cis- conformational TBTC³^- ligands connect six M₃(COO)₆ (M＝Zn(II) or Cd(II) secondary building units (SBUs) to form a pumpkin-shaped metal- organic nanocage. Viewing only the SBUs as vertexes, the pumpkin-shaped nanocage can be seen as a slightly distorted octahedral nanocage. Acting as supramolecular building blocks (SBBs), every octahedral nanocage connects 18 cis,trans,trans-conformational TBTC³^- ligands, while every cis,trans,trans-conformational TBTC³^- ligand connects three octahedral cages. Thus, the framework can be simplified as a (3,18)-connected network with point symbol of {4³³.6⁸⁴.8³⁶}{4³}₆. Moreover, upon removal of free guest solvent molecules, compounds 1～2 have metal clusters locating in the tunnel walls, which may have strong interaction with molecules with high quadrapole moment, and they show preferential adsorption of CO₂ over N₂/H₂. The resulting materials have potential for separation of CO₂ from other gas molecules such as N₂ and H₂. The solid state photoluminescent spectra of 1～2 as well as the free H₃TBTC ligand were examined at room temperature. When excited at 320 nm, the free ligand shows a maximum emission at 434 nm, which can be ascribed to the π-π* transition of the aromatic rings. The strongest emission peak for compounds 1～2 are observed at about 424 nm. By comparison of the emission energies and profiles of the free H₃TBTC ligand and compounds 1～2, the luminescent behavior of compounds 1～2 are considered to be originated from H₃TBTC ligands. The blue-shifted bands of their emissions may result from the fact that the ligands are not allowed to relax along the torsional mode upon photoexcitation.

Key words: metal-organic frameworks, coordination polymers, nanocage, semi-rigid ligand, gas adsorption, luminescence

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林祖金, 林熙, 曹荣. 八面体纳米笼构筑的金属-有机框架化合物[J]. 化学学报, 2012, 70(19): 2012-2015.

Lin Zujin, Lin Xi, Cao Rong. Construction of Two Octahedral Cage-based Metal-organic Frameworks[J]. Acta Chimica Sinica, 2012, 70(19): 2012-2015.

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八面体纳米笼构筑的金属-有机框架化合物

Construction of Two Octahedral Cage-based Metal-organic Frameworks

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