ii) Paddlewheel Structures">
Australian Journal of Chemistry Australian Journal of Chemistry Society
An international journal for chemical science

Triazolium-Containing Metal–Organic Frameworks: Control of Catenation in 2D Copper(ii) Paddlewheel Structures

Alexandre Burgun A , Christian J. Doonan A and Christopher J. Sumby A B

A School of Chemistry and Physics, University of Adelaide, Adelaide, SA 5005, Australia.

B Corresponding author. Email: christopher.sumby@adelaide.edu.au

Australian Journal of Chemistry 66(4) 409-418 http://dx.doi.org/10.1071/CH12462
Submitted: 8 October 2012  Accepted: 6 November 2012   Published: 14 December 2012


One approach to exploit metal–organic frameworks (MOFs) as heterogeneous catalyst platforms requires the development of materials containing groups that can be utilised to anchor a catalytic moiety into the links within the structure. Here we report the synthesis of the first integrated triazolium-containing MOF linker and the first MOFs containing linkers of this type. 1,4-Bis(4-benzoic acid)-1-methyl-1H-1,2,3-triazolium chloride, H2L1Me, was synthesised in three steps by a ‘click’ reaction of methyl 4-ethynylbenzoate with methyl 4-azidobenzoate, methylation using methyl triflate, followed by ester hydrolysis in overall 74 % yield. The equivalent neutral triazole precursor, 1,4-bis(4-benzoic acid)-1H-1,2,3-triazole hydrochloride, H2L1(HCl), was also prepared and a comparison of the chemistry with Zn(NO3)2·6H2O and Cu(NO3)2·3H2O is presented. The results support the use of reaction conditions to control interpenetration and provide additional evidence that the charge on structurally similar ligands can drastically alter the types of structures that are accessible due to the requirements for charge balance in the final product.

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[1]  (a) S. Kitagawa, R. Kitaura, S.-I. Noro, Angew. Chem. Int. Ed. 2004, 43, 2334.
         | CrossRef | 1:CAS:528:DC%2BD2cXktFShtLk%3D&md5=4d6e8ebba2bca77ae2961e8f2e309d72CAS | open url image1
      (b) G. Ferey, Chem. Soc. Rev. 2008, 37, 191.
         | CrossRef | open url image1
      (c) R. Robson, Dalton Trans. 2008, 5113.
         | CrossRef | open url image1
         (d) S. R. Batten, S. M. Neville, D. R. Turner, Coordination Polymers: Design, Analysis and Application 2009, p. 471 (Royal Society of Chemistry: Cambridge).

[2]  (a) M. Eddaoudi, J. Kim, N. L. Rosi, D. T. Vodak, J. Wachter, M. O’Keeffe, O. M. Yaghi, Science 2002, 295, 469.
         | CrossRef | 1:CAS:528:DC%2BD1cXhtlyrtLjP&md5=8852d22faa86f042cbd8e4ac532b0148CAS | open url image1
      (b) H. Deng, C. J. Doonan, H. Furukawa, R. B. Ferreira, J. Towne, C. B. Knobler, B. Wang, O. M. Yaghi, Science 2010, 327, 846.
         | CrossRef | open url image1
      (c) N. Stock, S. Biswas, Chem. Rev. 2012, 112, 933.
         | CrossRef | open url image1

[3]  (a) A. Corma, H. Garcia, F. X. Llabres, I. Xamena, Chem. Rev. 2010, 110, 4606.
         | CrossRef | 1:CAS:528:DC%2BC3cXktFers7Y%3D&md5=33d24fa3642016d6ad7e54379258e2eaCAS | open url image1
      (b) L. Ma, C. Abney, W. Lin, Chem. Soc. Rev. 2009, 38, 1248.
         | CrossRef | open url image1
      (c) A. U. Czaja, N. Trukhan, U. Müller, Chem. Soc. Rev. 2009, 38, 1284.
         | CrossRef | open url image1
      (d) J. Lee, O. K. Farha, J. Roberts, K. A. Scheidt, S. T. Nguyen, J. T. Hupp, Chem. Soc. Rev. 2009, 38, 1450.
         | CrossRef | open url image1

[4]  (a) E. D. Bloch, D. Britt, C. Lee, C. J. Doonan, F. J. Uribe-Romo, H. Furukawa, J. R. Long, O. M. Yaghi, J. Am. Chem. Soc. 2010, 132, 14382.
         | CrossRef | 1:CAS:528:DC%2BC3cXhtFygt7bP&md5=9a8747cebded6828c9415314e241016dCAS | open url image1
      (b) C. J. Doonan, W. Morris, H. Furukawa, O. M. Yaghi, J. Am. Chem. Soc. 2009, 131, 9492.
         | CrossRef | open url image1
      (c) T. Jacobs, R. Clowes, A. I. Cooper, M. J. Hardie, Angew. Chem. Int. Ed. 2012, 51, 5192.
         | CrossRef | open url image1

[5]  (a) C. Wang, Z. Xie, K. E. deKrafft, W. Lin, J. Am. Chem. Soc. 2011, 133, 13445.
         | CrossRef | 1:CAS:528:DC%2BC3MXpvVWltrk%3D&md5=eabf477686501536997373c34f09ea38CAS | open url image1
      (b) P. V. Dau, M. Kim, S. J. Garibay, F. H. L. Muench, C. E. Moore, S. M. Cohen, Inorg. Chem. 2012, 51, 5671.
         | CrossRef | open url image1
      (c) P. V. Dau, M. Kim, S. M. Cohen, Chem. Sci. 2013, Advance Article.
         | CrossRef | open url image1

[6]  A. J. Nuñez, L. N. Shear, N. Dahal, I. A. Ibarra, J. Yoon, Y. K. Hwang, J.-S. Chang, S. M. Humphrey, Chem. Commun. 2011, 47, 11855.
         | CrossRef | open url image1

[7]  (a) J. S. Seo, D. Whang, H. Lee, S. I. Jun, J. Oh, Y. J. Jeon, K. Kim, Nature 2000, 404, 982.
         | CrossRef | 1:CAS:528:DC%2BD3cXjtFyns7k%3D&md5=49fa83281737c37b6b6f426dff7545bcCAS | open url image1
      (b) B. Chen, L. Wang, Y. Xiao, F. R. Fronczek, M. Xue, Y. Cui, G. Qian, Angew. Chem. Int. Ed. 2009, 48, 500.
         | CrossRef | open url image1
      (c) X.-P. Zhou, Z. Xu, M. Zeller, A. D. Hunter, Chem. Commun. 2009, 5439.
         | CrossRef | open url image1

[8]  (a) C.-D. Wu, A. Hu, L. Zhang, W. Lin, J. Am. Chem. Soc. 2005, 127, 8940.
         | CrossRef | 1:CAS:528:DC%2BD2MXkslGju7k%3D&md5=2449dccdbd58f006dbd1154063fd5725CAS | open url image1
      (b) K. L. Mulfort, O. K. Farha, C. L. Stern, A. A. Sarjent, J. T. Hupp, J. Am. Chem. Soc. 2009, 131, 3866.
         | CrossRef | open url image1
      (c) T. Devic, P. Horcajada, C. Serre, F. Salles, G. Maurin, B. Moulin, D. Heurtaux, G. Clet, A. Vimont, J.-M. Greneche, B. Le Ouay, F. Moreau, E. Magnier, Y. Filinchuk, J. Marrot, J.-C. Lavalley, M. Daturi, G. Ferey, J. Am. Chem. Soc. 2010, 132, 1127.
         | CrossRef | open url image1
      (d) K. S. Jeong, Y. B. Go, S. M. Shin, S. J. Lee, J. Kim, O. M. Yaghi, N. Jeong, Chem. Sci. 2011, 2, 877.
         | CrossRef | open url image1
      (e) D. Rankine, A. Avellaneda, M. R. Hill, C. J. Doonan, C. J. Sumby, Chem. Commun. 2012, 48, 10328.
         | CrossRef | open url image1

[9]  (a) Z. Fei, T. D. Geldbach, D. Zhao, R. Scopelliti, P. J. Dyson, Inorg. Chem. 2005, 44, 5200.
         | CrossRef | 1:CAS:528:DC%2BD2MXltlGnsL0%3D&md5=924783db3a99a4fa605648e21d7758f3CAS | open url image1
      (b) Z. Fei, T. D. Geldbach, D. Zhao, R. Scopelliti, P. J. Dyson, Inorg. Chem. 2006, 45, 6331.
         | CrossRef | open url image1
      (c) L. Han, S. Zhang, Y. Wang, X. Yan, X. Lu, Inorg. Chem. 2009, 48, 786.
         | CrossRef | open url image1
      (d) R. S. Crees, M. L. Cole, L. R. Hanton, C. J. Sumby, Inorg. Chem. 2010, 49, 1712.
         | CrossRef | open url image1
      (e) J. Chun, I. G. Jung, H. J. Kim, M. Park, M. S. Lah, S. U. Son, Inorg. Chem. 2009, 48, 6353.
         | CrossRef | open url image1
      (f) J. Chun, H. S. Lee, I. G. Jung, S. W. Lee, H. J. Kim, S. U. Son, Organometallics 2010, 29, 1518.
         | CrossRef | open url image1
      (g) J. Y. Lee, J. Roberts, O. K. Farha, J. T. Hupp, K. A. Scheidt, Inorg. Chem. 2009, 48, 9971.
         | CrossRef | open url image1
      (h) G.-Q. Kong, X. Xu, C. Zou, C.-D. Wu, Chem. Commun. 2011, 47, 11005.
         | CrossRef | open url image1

[10]  J. M. Roberts, O. K. Farha, A. A. Sarjeant, J. T. Hupp, K. A. Scheidt, Cryst. Growth Des. 2011, 11, 4747.
         | CrossRef | 1:CAS:528:DC%2BC3MXht1Kktr%2FI&md5=5cd083480cd94af30f8f9a728892dd69CAS | open url image1

[11]  K. Oisaki, Q. Li, H. Furukawa, A. U. Czaja, O. M. Yaghi, J. Am. Chem. Soc. 2010, 132, 9262.
         | CrossRef | 1:CAS:528:DC%2BC3cXnsFyhtL0%3D&md5=22d8a9f4d252b4ff9a4df1933ddb9b3eCAS | open url image1

[12]  (a) J. R. Struble, J. W. Bode, Tetrahedron 2008, 64, 6961.
         | CrossRef | 1:CAS:528:DC%2BD1cXnt1OltLg%3D&md5=eecead829c18b06759c296e767fd99beCAS | open url image1
      (b) J. R. Struble, J. Kaeobamrung, J. W. Bode, Org. Lett. 2008, 10, 957.
         | CrossRef | open url image1

[13]  (a) H. C. Kolb, M. G. Finn, K. B. Sharpless, Angew. Chem. Int. Ed. 2001, 40, 2004.
         | CrossRef | 1:CAS:528:DC%2BD3MXksVOis78%3D&md5=af962a1dfdc14748785758477eb28f57CAS | open url image1
      (b) J. E. Moses, A. D. Moorhouse, Chem. Soc. Rev. 2007, 36, 1249.
         | CrossRef | open url image1
      (c) M. G. Finn, V. V. Fokin, Chem. Soc. Rev. 2010, 39, 1231.
         | CrossRef | open url image1

[14]  (a) J. D. Crowley, A.-L. Lee, K. J. Kilpin, Aust. J. Chem. 2011, 64, 1118.
         | CrossRef | 1:CAS:528:DC%2BC3MXhtVegt7nK&md5=eab09d7d53c0ac75f4b651b96b2a17f4CAS | open url image1
         (b) J. D. Crowley, D. A. McMorran, in Click Triazoles: Topics in Heterocyclic Chemistry (Ed. J. Košmrlj) 2012, Vol. 28, pp. 31–84 (Springer: Berlin).
      (c) D. Schweinfurth, N. Deibel, F. Weisser, B. Sarkar, Nachr. Chem. 2011, 59, 937.
         | CrossRef | open url image1
      (d) H. Struthers, T. L. Mindt, R. Schibli, Dalton Trans. 2010, 39, 675.
         | CrossRef | open url image1
      (e) S. O. Scott, E. L. Gavey, S. J. Lind, K. C. Gordon, J. D. Crowley, Dalton Trans. 2011, 40, 12117.
         | CrossRef | open url image1
      (f) K. J. Kilpin, U. S. D. Paul, A.-L. Lee, J. D. Crowley, Chem. Commun. 2011, 47, 328.
         | CrossRef | open url image1
      (g) K. J. Kilpin, E. L. Gavey, C. J. McAdam, C. B. Anderson, S. J. Lind, C. C. Keep, K. C. Gordon, J. D. Crowley, Inorg. Chem. 2011, 50, 6334.
         | CrossRef | open url image1

[15]  V. V. Rostovtsev, L. G. Green, V. V. Fokin, K. B. Sharpless, Angew. Chem. Int. Ed. 2002, 41, 2596.
         | CrossRef | 1:CAS:528:DC%2BD38Xls1Ohsr4%3D&md5=82dc97e2fc246725b65dca4afe587274CAS | open url image1

[16]  A. R. Katritzky, Y. Zhang, S. K. Singh, Heterocycles 2003, 60, 1225.
         | CrossRef | 1:CAS:528:DC%2BD3sXjtlyrt74%3D&md5=28d30e79a4db1a5cf3f3161353b58ae9CAS | open url image1

[17]  G. Guisado-Barrios, J. Bouffard, B. Donnadieu, G. Bertrand, Organometallics 2011, 30, 6017.
         | CrossRef | 1:CAS:528:DC%2BC3MXht1ylurnJ&md5=6a159e2b98ffba7bd53192c8bcaca630CAS | open url image1

[18]  (a) Y. Hua, A. H. Flood, Chem. Soc. Rev. 2010, 39, 1262.
         | CrossRef | 1:CAS:528:DC%2BC3cXjs1Ggtbw%3D&md5=fe0a1acab219a962e73aa8ceb8c13b39CAS | open url image1
      (b) A. D. Pehere, C. J. Sumby, A. D. Abell, Org. Biomol. Chem. 2012, Advance Article.
         | CrossRef | open url image1

[19]  (a) J. Zhang, L. Wojtas, R. W. Larsen, M. Eddaoudi, M. J. Zaworotko, J. Am. Chem. Soc. 2009, 131, 17040.
         | CrossRef | 1:CAS:528:DC%2BD1MXhtlKrsb%2FF&md5=0f0f0e8a9e7422cf76e38c835867fdcaCAS | open url image1
      (b) J. I. Feldblyum, A. G. Wong-Foy, A. J. Matzger, Chem. Commun. 2012, 48, 9828.
         | CrossRef | open url image1

[20]  (a) M. Eddaoudi, D. B. Moler, H. Li, B. Chen, T. M. Reineke, M. O’Keeffe, O. M. Yaghi, Acc. Chem. Res. 2001, 34, 319.
         | CrossRef | 1:CAS:528:DC%2BD3MXhtFymsL0%3D&md5=279d664ee05a8886ccc5e61150f7d504CAS | open url image1
      (b) D. J. Tranchemontagne, J. L. Mendoza-Cortés, M. O’Keeffe, O. M. Yaghi, Chem. Soc. Rev. 2009, 38, 1257.
         | CrossRef | open url image1

[21]  A. L. Spek, Acta Crystallogr. 1990, A46, C34. open url image1

[22]  W. B. Austin, N. Bilow, W. J. Kelleghan, K. S. Y. Lau, J. Org. Chem. 1981, 46, 2280.
         | CrossRef | 1:CAS:528:DyaL3MXktVKlt7o%3D&md5=ba6fabafa9e2d0e97a0d427a12125d58CAS | open url image1

[23]  M. Tanno, S. Sueyoshi, S. Kamiya, Chem. Pharm. Bull. (Tokyo) 1982, 30, 3125.
         | CrossRef | 1:CAS:528:DyaL3sXht1GmtL8%3D&md5=d4d262025997ef8a3e24ab5b17fd6590CAS | open url image1

[24]  T. M. McPhillips, S. E. McPhillips, H. J. Chiu, A. E. Cohen, A. M. Deacon, P. J. Ellis, E. Garman, A. Gonzalez, N. K. Sauter, R. P. Phizackerley, S. M. Soltis, P. Kuhn, J. Synchrotron Radiat. 2002, 9, 401.
         | CrossRef | 1:CAS:528:DC%2BD38Xotleluro%3D&md5=380f70c3cee5e196922dc18c1fbabce4CAS | open url image1

[25]  G. M. Sheldrick, Acta Crystallogr. 1990, A46, 467.
         | 1:CAS:528:DyaK3cXksFSgsrc%3D&md5=09b52b130bb806d940d5e8080af07d30CAS | open url image1

[26]  G. M. Sheldrick, SHELXL-97 1997 (University of Göttingen: Göttingen).

[27]  L. J. Barbour, J. Supramol. Chem. 2001, 1, 189.
         | CrossRef | 1:CAS:528:DC%2BD3sXitlOlsb8%3D&md5=b8ca8c15e12e7249c9068cf6390b143aCAS | open url image1

[28]  Persistence of Vision Raytracer Pty Ltd, POV-Ray, Williamstown, Australia, 20032008.

[29]  G. M. Sheldrick, CIFTAB 1997 (University of Göttingen: Göttingen).

[30]  P. Gilli, L. Pretto, V. Bertolasi, G. Gilli, Acc. Chem. Res. 2009, 42, 33.
         | CrossRef | 1:CAS:528:DC%2BD1cXht1GjtrzO&md5=af993bb897a4e04ac4480654e43b7830CAS | open url image1

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