Citation: HU Yun-Xia, ZHANG Wen-Wei, WANG Li-Feng, BAI Jun-Feng. Synthesis and Gas Sorption Properties of Cupric Microporous Metal-Organic Framework Based on 1,1’-Ethynebenzene-3,3’,5,5’-tetracarboxylate[J]. Chinese Journal of Inorganic Chemistry, ;2013, 29(7): 1471-1479. doi: 10.3969/j.issn.1001-4861.2013.00.200 shu

Synthesis and Gas Sorption Properties of Cupric Microporous Metal-Organic Framework Based on 1,1’-Ethynebenzene-3,3’,5,5’-tetracarboxylate

1.
1 State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210093, China;

Received Date: 7 August 2012
Available Online: 17 March 2013
Fund Project: 国家自然科学基金(No.20771058) (No.20771058)国家自然科学基金创新研究群体(No.20721002) (No.20721002)教育部博士点基金(No.200802840011) (No.200802840011)新疆凝聚态相变与微结构实验室开放课题基金(No.XJDX0912-2011-01)资助项目。 (No.XJDX0912-2011-01)

The synthesis, crystal structure, and sorption properties of [Cu₂(EBTC)(H₂O)₂]·8H₂O·DMF·DMSO (abbreviated as 1, EBTC=1,1'-ethynebenzene-3,3',5,5'-tetracarboxylate; DMF=N,N-dimethyl formamide; DMSO=dimethyl sulfoxide) are reported. 1 features two kinds of cavities with a diameter of 0.85 nm and 0.85×2.15 nm, which are enclosed respectively by six and twelve tetracarboxylate-bridged [Cu₂(CO₂)₄] paddle-wheels and extended by the EBTC linkers into a three-dimensional (3D) supramolecular structure with 1D channels accommodating the solvent molecules. It adopts the (3,4)-c net of fof (sqc 1575) topology, possesses very large solvent accessible pore volume which reaches 72.8% of the unit cell volume. After removal of the solvent molecules, the desolvated 1a exhibits permanent porosity verified by an N₂ sorption isotherm with a Langmuir surface area of 2844 m²·g^-1 and Brunauer-Emmett-Teller (BET) surface area of 1 852 m²·g^-1. It displays significant uptake of gases (H₂, CO₂, CH₄, C₂H₂) and relatively high adsorption enthalpies. Especially, it is notable that 1a exhibits the highest acetylene storage of 252 cm³·g^-1 at 273 K under 1.0×105 Pa with higher adsorption enthalpy (34.5 kJ·mol^-1 at the coverage of 1 mmol·g^-1) among all porous metal-organic materials reported to date. CCDC: 744108.
- microporous MOFs;solvothermal synthesis;crystal structure;adsorption property
1. [1]
  [1] (a)Zaworotko M J. Nature Chemistry, 2009,1:267-268 (b)Zaworotko M. J. Nature, 2009,451:410-411 (c)Ma S, Sun D, Yuan D, et al. J. Am. Chem. Soc., 2009,131: 6445-6451 (d)Férey G, Mellot-Draznieks C, Serre C, et al. Science, 2005, 309:2040-2042 (e)Zhang J P, Chen X M. J. Am. Chem. Soc., 2009,131:5516-5521
2. [2]
  [2] (a)Kitagawa S, Kitaura R, Noro I S. Angew. Chem. Int. Ed., 2004,43:2334-2375 (b)Zhang J P, Chen X M. J. Am. Chem. Soc., 2008,130:6010-6017
3. [3]
  [3] (a)Férey G. Chem. Soc. Rev., 2008,37:191-214 (b)Kitagawa S, Matsuda R. Coord. Chem. Rev., 2007,251: 2490-2509 (c)Kepert C J. Chem. Commun., 2006,7:695-700 (d)Fletcher A J, Thomas K M, Rosseinsky M J. J. Solid State Chem., 2005,78:2491-2510
4. [4]
  [4] (a)Ghosh S K, Zhang J P, Kitagawa S. Angew. Chem. Int. Ed., 2007,46:7965-7968 (b)Serre C, Mellot-Draznieks C, Surble S, et al. Science, 2007,315:1828-1831 (c)Kubota Y, Takata M, Matsuda R, et al. Angew. Chem. Int. Ed., 2006,45:4932-4936
5. [5]
  [5] (a)Lee Y G, Moon H R, Cheon Y E et al. Angew. Chem. Int. Ed., 2008,47:7741-7745 (b)Zhang J P, Horike S, Kitagawa S. Angew. Chem. Int. Ed., 2007,46:889-892 (c)Chen B L, Ockwig N W, Millward A R, et al. Angew. Chem. Int. Ed., 2005,44:4745-4749
6. [6]
  [6] (a)Horike S, Bureekaew S, Kitagawa S. Chem. Commun., 2008,4:471-473 (b)Hasegawa S, Horike S, Matsuda R, et al. J. Am. Chem. Soc., 2007,129:2607-2614
7. [7]
  [7] Lin X, Jia J, Zhao X, et al. Angew. Chem. Int. Ed., 2006, 118:7358-7364
8. [8]
  [8] Chen B, Ockwig N W, Fronczek F R, et al. Inorg. Chem., 2005,44:181-183
9. [9]
  [9] Hausdorf S, Seichter W, Weber E, et al. Dalton Trans., 2009,7:1107-1113
10. [10]
  [10] Wang X S, Ma S Q, Rauch K, et al. Chem. Mater., 2008,20: 3145-3152
11. [11]
  [11] (a)Wang L F, Kang L C, Zhang W W, et al. Dalton Trans., 2011,40:9490-9497 (b)Hu Y X, Ma H B, Zheng B, et al. Inorg. Chem., 2012,51: 7066-7074
12. [12]
  [12] Kitagawa S, Noro S I, Nakamura T. Chem. Commun., 2006, 7:701-707
13. [13]
  [13] (a)Thorand S, Krause N. J. Org. Chem., 1998,63:8551-8553 (b)Sonogashira K. J. Organomet. Chem., 2002,653:46-49 (c)Bodwell G J, Miller D O, Vermeij R J. Org. Lett., 2001,3: 2093-2096
14. [14]
  [14] Hu Y X, Xiang S C, Zhang W W, et al. Chem. Commun., 2009,48:7551-7553
15. [15]
  [15] (a)Spek A L. J. Appl. Crystallogr., 2003,36:7-13 (b)Spek A L. PLATON, A Multipurpose Crystallographic Tool, Utrecht University, The Netherlands, 2006. available via http://www.cryst.chem.uu.nl/platon (for Unix) and http://www.chem.gla.ac.uk/Blouis/software/platon/ (for MS Windows)
16. [16]
  [16] (a)Lin X, Jia J, Zhao X, et al. Angew. Chem. Int. Ed., 2006, 45:7358-7364 (b)Lin X, Telepeni I, Blake A J, et al. J. Am. Chem. Soc., 2009,131:2159-2171 (c)Zhao D, Yuan D, Yakovenko A, et al. Chem. Commun., 2010,46:4196-4198
17. [17]
  [17] (a)Sun D, Ma S, Simmons J M, et al. Chem. Commun., 2010, 46:1329-1331 (b)O'Keeffe M, Yaghi O M. Chem. Rev., 2012,112:675-702 (c)Alexandrov E V, Blatov V A, Kochetkov A V, et al. CrystEngComm, 2011,13:3947-3958 (d)O'Keeffe M, Peskov M A, Ramsden, S J, et al. Acc. Chem. Res., 2008,41:1782-1789 (e)Ramsden S J, Robins V, Hyde S T, Acta Crystallogr. Sect. A: Found. Crystallogr., 2009,65:81-108 (f)Blatov V A, O'Keeffe M, Proserpio D M. CrystEngComm, 2010,12:44-48
18. [18]
  [18] (a)Walton K S, Snurr R Q. J. Am. Chem. Soc., 2007,129: 8552-8556 (b)Han S S, Goddard W A. J. Phys. Chem. C, 2008,112: 13431-13436
19. [19]
  [19] Rowsell J L C, Yaghi O M. J. Am. Chem. Soc., 2006,128: 1304-1315
20. [20]
  [20] (a)Ma S Q, Sun D F, Simmons J M, et al. J. Am. Chem. Soc., 2008,130:1012-1016 (b)Wu H, Zhou W, Yildirim T. J. Am. Chem. Soc., 2009, 131:4995-5000
21. [21]
  [21] Senkovska I, Kaskel S. Micropor. Mesopor. Mat., 2008,112: 108-115
22. [22]
  [22] Busker M, Hber T, Nispel M, et al. Angew. Chem. Int. Ed., 2008,47:10094-10097
23. [23]
  [23] Li J R, Kuppler R J, Zhou H C. Chem. Soc. Rev., 2009,38: 1477-1504
24. [24]
  [24] (a)Xiang S C, Zhou W, Gallegos J M, et al. J. Am. Chem. Soc., 2009,131:12415-12419 (b)Reisinger A, Trapp N, Krossing I, et al. Angew. Chem. Int. Ed., 2007,46:8295-8298 (c)Wang X S, Ma S, Forster P M, et al. Angew. Chem. Int. Ed., 2008,47:7263-7266
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沈阳化工大学材料科学与工程学院沈阳 110142