Construction of Two Octahedral Cage-based Metal-organic Frameworks

doi:10.6023/A12080546

Acta Chimica Sinica ›› 2012, Vol. 70 ›› Issue (19): 2012-2015.DOI: 10.6023/A12080546 Previous Articles Next Articles

Communications

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.

1. Construction of Two Octahedral Cage-based Metal-organic Frameworks.PDF(543KB)

Abstract

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

Cite this article

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

Export EndNote|Reference Manager|ProCite|BibTeX|RefWorks

share this article

References

[1] (a) Farrusseng, D.; Aguado, S.; Pinel, C. Angew. Chem., Int. Ed. 2009, 48, 7502; (b) Lin, J.-B.; Xue, W.; Zhang, J.-P.; Chen, X.-M. Chem. Commun. 2011, 47, 926; (c) Cui, Y.; Yue, Y.; Qian, G.; Chen, B. Chem. Rev. 2012, 112, 1126; (d) Zhong, D.; Lu, T. Sci. China Chem. 2011, 54, 1395.

[2] Mal, P.; Breiner, B.; Rissanen, K.; Nitschke, J. R. Science 2009, 324, 1697.

[3] Perry, J. J.; Perman, J. A.; Zaworotko, M. J. Chem. Soc. Rev. 2009, 38, 1400.

[4] (a) Seidel, S. R.; Stang, P. J. Acc. Chem. Res. 2002, 35, 972; (b) Tranchemontagne, D. J.; Ni, Z.; O'Keeffe, M.; Yaghi, O. M. Angew. Chem., Int. Ed. 2008, 47, 5136.

[5] (a) Wang, X.-S.; Ma, S.; Forster, P. M.; Yuan, D.; Eckert, J.; López, J. J.; Murphy, B. J.; Parise, J. B.; Zhou, H.-C. Angew. Chem., Int. Ed. 2008, 47, 7263; (b) Zhao, D.; Yuan, D.; Sun, D.; Zhou, H.-C. J. Am. Chem. Soc. 2009, 131, 9186; (c) Farha, O. K.; Özgür Yazayd?n, A.; Eryazici, I.; Malliakas, C. D.; Hauser, B. G.; Kanatzidis, M. G.; Nguyen, S. T.; Snurr, R. Q.; Hupp, J. T. Nat. Chem. 2010, 2, 944; (d) Yan, Y.; Telepeni, I.; Yang, S.; Lin, X.; Kockelmann, W.; Dailly, A.; Blake, A. J.; Lewis, W.; Walker, G. S.; Allan, D. R.; Barnett, S. A.; Champness, N. R.; Schroder, M. J. Am. Chem. Soc. 2010, 132, 4092; (e) Yuan, D.; Zhao, D.; Sun, D.; Zhou, H.-C. Angew. Chem., Int. Ed. 2010, 49, 5357.

[6] (a) Perry, J. J.; Kravtsov, V. C.; McManus, G. J.; Zaworotko, M. J. J. Am. Chem. Soc. 2007, 129, 10076; (b) Zou, Y.; Park, M.; Hong, S.; Lah, M. S. Chem. Commun. 2008, 2340; (c) Li, C.; Qiu, W.; Shi, W.; Song, H.; Bai, G.; He, H.; Li, J.; Zaworotko, M. J. CrystEngComm 2012, 14, 1929.

[7] (a) Liu, T.-F.; Lü, J.; Guo, Z.; Proserpio, D. M.; Cao, R. Cryst. Growth Des. 2010, 10, 1489; (b) Lin, Z.-J.; Liu, T.-F.; Xu, B.; Han, L.-W.; Huang, Y.-B.; Cao, R. CrystEngComm 2011, 13, 3321; (c) Lin, Z.-J.; Liu, T.-F.; Zhao, X.-L.; Lü, J.; Cao, R. Cryst. Growth Des. 2011, 11, 4284; (d) Liu, T.-F.; Lü, J.; Tian, C.; Cao, M.-N; Lin, Z.; Cao, R. Inorg. Chem. 2011, 50, 2264; (e) Lin, Z.-J.; Liu, T.-F.; Huang, Y.-B.; Lü, J.; Cao, R. Chem.-Eur. J. 2012, 18, 7896.

[8] Guo, Z.; Cao, R.; Wang, X.; Li, H.; Yuan, W.; Wang, G.; Wu, H.; Li, J. J. Am. Chem. Soc. 2009, 131, 6894.

[9] Liu, T.-F.; Lu, J.; Lin, X.; Cao, R. Chem. Commun. 2010, 46, 8439.

[10] (a) Qin, L.; Hu, J.-S.; Li, Y.-Z.; Zheng, H.-G. Cryst. Growth Des. 2011, 11, 3115; (b) Fang, Q. R.; Shi, X.; Wu, G.; Tian, G.; Zhu, G. S.; Li, Y. F.; Wang, L. F.; Wang, C. L.; Chen, Y.; Zhang, Z. D.; Guo, Z.; Shang, T. C.; Cai, X. H.; Qiu, S. L. Acta Chim. Sinica 2002, 60, 2087. (方千荣, 石鑫, 吴刚, 田歌, 朱广山, 李亚峰, 王立锋, 王春雷, 陈悦, 张震东, 郭卓, 商铁存, 蔡晓慧, 裘式纶, 化学学报, 2002, 60, 2087.)

[11] Liu, T.; Lu, J.; Shi, L.; Guo, Z.; Cao, R. CrystEngComm 2009, 11, 583.

[12] (a) Chen, Y. F.; Lee, J. Y.; Babarao, R.; Li, J. W. J. Phys. Chem. C 2010, 114, 6602; (b) Lin, Z.-J.; Yang, Z.; Liu, T.-F.; Huang, Y.-B.; Cao, R. Inorg. Chem. 2012, 51, 1813.

[13] (a) Lan, Y.-Q.; Jiang, H.-L.; Li, S.-L.; Xu, Q. Adv. Mater. 2011, 23, 5015; (b) Qin, J.-S.; Du, D.-Y.; Li, W.-L.; Zhang, J.-P.; Li, S.-L.; Su, Z.-M.; Wang, X.-L.; Xu, Q.; Shao, K.-Z.; Lan, Y.-Q. Chem. Sci. 2012, 3, 2114.

[14] (a) Wang, J.-J.; Cao, P.-X.; Gao, L.-J.; Fu, F.; Zhang, M.-L.; Ren, Y.-X.; Hou, X.-Y. Chin. J. Struct. Chem. 2011, 30, 1787; (b) Li, Y. J.; Song, H. H.; Wang, J. Y.; Han, Z. G. Acta Chim. Sinica 2007, 65, 2401. (李亚娟, 宋会花, 王继业, 韩占刚, 化学学报, 2007, 65, 2401.)

[15] (a) Allendorf, M. D.; Bauer, C. A.; Bhakta, R. K.; Houk, R. J. T. Chem. Soc. Rev. 2009, 38, 1330; (b) Kang, W.; Deng, Z. P.; Gao, S. Chinese J. Inorg. Chem. 2011, 27, 131. (康伟, 邓兆鹏, 高山, 无机化学学报, 2011, 27, 131.)

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

PDF

Supporting Info.

Knowledge

Cited

Abstract

Cite this article

share this article

References

Related Articles 15

Recommended Articles

Metrics

Comments

[1]	Peng Tao, Xiaokang Zheng, Guoliang Wang, Xinghao Sheng, He Jiang, Wentao Li, Jibiao Jin, Sui-Hung Wong, Yanqin Miao, Hua Wang, Wai-Yeung Wong. Novel Bipolar Orange Emissive Iridium(III) Complexes: Design, Synthesis, and Electroluminescence^★ [J]. Acta Chimica Sinica, 2023, 81(8): 891-897.
[2]	Jia Liu, Guanghai Chen, Yiqun Chen, Jietao Jiang, Xiao Xiao, Qiang Wu, Lijun Yang, Xizhang Wang, Zheng Hu. Boosting the Supercapacitance Performance of Mesostructured Carbon Nanocages by Enlarging Pore Sizes via Carbothermal Reduction^★ [J]. Acta Chimica Sinica, 2023, 81(7): 709-716.
[3]	Huimin Chen, Long Wang, Pan Zhang, Xilin Bai, Guojun Zhou. Investigation on Photoluminescence and Mechanoluminescence of Single Tb^3＋-doped Intense Green Phosphor [J]. Acta Chimica Sinica, 2023, 81(7): 771-776.
[4]	Bo Sun, Wenwen Ju, Tao Wang, Xiaojun Sun, Ting Zhao, Xiaomei Lu, Feng Lu, Quli Fan. Preparation of Highly-dispersed Conjugated Polymer-Metal Organic Framework Nanocubes for Antitumor Application [J]. Acta Chimica Sinica, 2023, 81(7): 757-762.
[5]	Yinfeng Wang, Meng Li, Chuanfeng Chen. Chiral Triptycene-Based Red Thermally Activated Delayed Fluorescence Polymers and Their Organic Light-Emitting Diodes^★ [J]. Acta Chimica Sinica, 2023, 81(6): 588-594.
[6]	Shaoqin Zhang, Meiqing Li, Zhongjun Zhou, Zexing Qu. Theoretical Study on the Multiple Resonance Thermally Activated Delayed Fluorescence Process [J]. Acta Chimica Sinica, 2023, 81(2): 124-130.
[7]	Junchang Chen, Mingxing Zhang, Shuao Wang. Research Progress of Synthesis Methods for Crystalline Porous Materials [J]. Acta Chimica Sinica, 2023, 81(2): 146-157.
[8]	Ge-Hua Wen, Wendurina, Xiumei Chen, Xiu-Fang Ma, Guo-Guo Weng, Yi-Fan Wei, Song-Song Bao, Xiaoji Xie, Shu-Xian Hu, Li-Min Zheng. Layered Uranyl Phosphonate as A Dual-response Luminescence Thermometer^★ [J]. Acta Chimica Sinica, 2023, 81(10): 1311-1317.
[9]	Xiaojuan Li, Ziyu Ye, Shuhan Xie, Yongjing Wang, Yonghao Wang, Yuancai Lv, Chunxiang Lin. Study on Performance and Mechanism of Phenol Degradation through Peroxymonosulfate Activation by Nitrogen/Chlorine Co-doped Porous Carbon Materials [J]. Acta Chimica Sinica, 2022, 80(9): 1238-1249.
[10]	Yanrong Jia, Guanlei Gao, Min Xia. Methods for Adjusting Mechanoluminescence Behaviors on Crystals of Purely Organic Small Molecules [J]. Acta Chimica Sinica, 2022, 80(9): 1309-1321.
[11]	Xu Yan, Hemi Qu, Ye Chang, Xuexin Duan. Application of Metal-Organic Frameworks in Gas Pre-concentration, Pre-separation and Detection [J]. Acta Chimica Sinica, 2022, 80(8): 1183-1202.
[12]	Zhihao Qi, Fujie Gao, Changkai Zhou, Yu Zeng, Qiang Wu, Lijun Yang, Xizhang Wang, Zheng Hu. Ruthenium Nanoparticles Anchored on Nitrogen-Doped Carbon Nanocages for Fischer-Tropsch Synthesis [J]. Acta Chimica Sinica, 2022, 80(8): 1100-1105.
[13]	Fang Liu, Tingting Pan, Xiurong Ren, Weiren Bao, Jiancheng Wang, Jiangliang Hu. Research on Preparation and Benzene Adsorption Performance of HCDs@MIL-100(Fe) Adsorbents [J]. Acta Chimica Sinica, 2022, 80(7): 879-887.
[14]	Linan Cao, Min Wei. Recent Progress of Electric Conductive Metal-Organic Frameworks Thin Film [J]. Acta Chimica Sinica, 2022, 80(7): 1042-1056.
[15]	Bin Liu, Pangkuan Chen. Synthesis and Properties of Novel Circularly Polarized Luminescence Materials Based on Binaphthol Skeleton [J]. Acta Chimica Sinica, 2022, 80(7): 929-935.