pubs.acs.org/IC Published on Web 10/01/2010 r 2010 American Chemical Society Inorg. Chem. 2010, 49, 10191–10198 10191 DOI: 10.1021/ic101501p Coordination Networks from Cu Cations and Tetrakis(methylthio)benzenedicarboxylic Acid: Tunable Bonding Patterns and Selective Sensing for NH 3 Gas Xiao-Ping Zhou, † Zhengtao Xu,* ,† Jun He, † Matthias Zeller, ‡ Allen D. Hunter, ‡ Rodolphe Cl  erac, §,|| Corine Mathoni  ere, ^ Stephen Sin-Yin Chui, X and Chi-Ming Che X † Department of Biology and Chemistry, City University of Hong Kong, 83 Tat Chee Avenue, Kowloon, Hong Kong, P.R. China, ‡ Department of Chemistry, Youngstown State University, One University Plaza, Youngstown, Ohio 44555, United States, § CNRS, UPR 8641, Centre de Recherche Paul Pascal (CRPP), Equipe “Mat eriaux Mol eculaires Magn etiques”, 115 avenue du Dr. Albert Schweitzer, 33600 Pessac, France, || Universit e de Bordeaux, UPR 8641, Pessac F-33600, France, ^ CNRS UPR9048, Universit e Bordeaux, Institut de Chimie de la Mati ere Condens ee de Bordeaux (ICMCB), 87 avenue du Dr. Albert Schweitzer, Pessac Cedex, F-33608, France, and X Department of Chemistry and HKU-CAS Joint Laboratory on New Materials, The University of Hong Kong, Pokfulam Road, Hong Kong, China Received July 27, 2010 This paper aims to illustrate the rich potential of the thioether-carboxyl combination in generating coordination networks with tunable and interesting structural features. By simply varying the ratio between Cu(NO 3 ) 2 and the bifunctional ligand tetrakis(methylthio)benzenedicarboxylic acid (TMBD) as the reactants, three coordination networks can be hydrothermally synthesized in substantial yields, which present a distinct evolution with regard to metal -ligand interactions. Specifically, Cu(TMBD) 0.5 (H 2 TMBD) 0.5 3 H 2 TMBD (1) was obtained with a relatively small (1:1) Cu(NO 3 ) 2 /TMBD ratio, and crystallizes as an one-dimensional (1D) coordination assembly based on Cu(I)-thioether interactions, which is integrated by hydrogen- bonding to additional H 2 TMBD molecules to form a three-dimensional (3D) composite network with all the carboxylic acid and carboxylate groups remaining uncoordinated to the metal ions. A medium (1.25:1) Cu(NO 3 ) 2 /TMBD ratio leads to compound Cu 2 TMBD, in which Cu(I) ions simultaneously bond to the carboxylate and thioether groups, while an even higher (2.4:1) Cu(NO 3 ) 2 /TMBD ratio produced a mixed-cation compound Cu II 2 OHCu I (TMBD) 2 3 2H 2 O (2), in which the carboxylic groups are bonded to (cupric) Cu II ions, and the thioether groups to Cu I . Despite the lack of open channels in 2, crystallites of this compound exhibit a distinct and selective absorption of NH 3 , with a concomitant color change from green to blue, indicating substantial network flexibility and dynamics with regards to gas transport. Introduction Crystal engineering of extended networks 1 has entered a stage where it is ever more crucial to design and synthesize organic building blocks 2 with novel functional and struc- tural features. We have extensively explored the advan- tages of aromatic thioethers for building complex, advanced *To whom correspondence should be addressed. E-mail: zhengtao@ cityu.edu.hk. (1) (a) Batten, S. R.; Robson, R. Angew. Chem., Int. Ed. 1998, 37, 1461. (b) Carlucci, L.; Ciani, G.; Proserpio, D. M. Coord. Chem. Rev. 2003, 246, 247. (c) Kitagawa, S.; Kitaura, R.; Noro, S.-i. Angew. Chem., Int. Ed. 2004, 43, 2334. (d) Lee, S.; Mallik, A. B.; Xu, Z.; Lobkovsky, E. B.; Tran, L. Acc. Chem. Res. 2005, 38, 251. (e) Bradshaw, D.; Claridge, J. B.; Cussen, E. J.; Prior, T. J.; Rosseinsky, M. J. Acc. Chem. Res. 2005, 38, 273. (f) Suslick, K. S.; Bhyrappa, P.; Chou, J. H.; Kosal, M. E.; Nakagaki, S.; Smithenry, D. W.; Wilson, S. R. Acc. Chem. Res. 2005, 38, 283. (g) Mak, T. C. W.; Zhao, L. Chem. Asian J. 2007, 2, 456. (h) Ockwig, N. W.; Delgado-Friedrichs, O.; O'Keeffe, M.; Yaghi, O. M. Acc. Chem. Res. 2005, 38, 176. (i) Maspoch, D.; Ruiz-Molina, D.; Veciana, J. Chem. Soc. Rev. 2007, 36, 770. (j) Tanaka, D.; Kitagawa, S. Chem. Mater. 2008, 20, 922. (k) F erey, G. Chem. Soc. Rev. 2008, 37, 191. (l) Ma, L.; Abney, C.; Lin, W. Chem. Soc. Rev. 2009, 38, 1248. (m) Chen, B.; Xiang, S.; Qian, G. Acc. Chem. Res. 2010, 43, 1115. (2) (a) Chen, Z.; Xiang, S.; Liao, T.; Yang, Y.; Chen, Y.-S.; Zhou, Y.; Zhao, D.; Chen, B. Cryst. Growth Des. 2010, 10, 2775. (b) Ma, L.; Mihalcik, D. J.; Lin, W. J. Am. Chem. Soc. 2009, 131, 4610. (c) Wu, C.-D.; Hu, A.; Zhang, L.; Lin, W. J. Am. Chem. Soc. 2005, 127, 8940. (d) Cui, Y.; Lee, S. J.; Lin, W. J. Am. Chem. Soc. 2003, 125, 6014. (e) Liu, Y.; Xu, X.; Zheng, F.; Cui, Y. Angew. Chem., Int. Ed. 2008, 47, 4538. (f) Ma, S.; Sun, D.; Ambrogio, M.; Fillinger, J. A.; Parkin, S.; Zhou, H.-C. J. Am. Chem. Soc. 2007, 129, 1858. (g) Sun, D.; Ma, S.; Ke, Y.; Collins, D. J.; Zhou, H.-C. J. Am. Chem. Soc. 2006, 128, 3896. (h) Nouar, F.; Eubank, J. F.; Bousquet, T.; Wojtas, L.; Zaworotko, M. J.; Eddaoudi, M. J. Am. Chem. Soc. 2008, 130, 1833. (i) Lin, X.; Blake, A. J.; Wilson, C.; Sun, X. Z.; Champness, N. R.; George, M. W.; Hubberstey, P.; Mokaya, R.; Schr€ oder, M. J. Am. Chem. Soc. 2006, 128, 10745. (j) Koh, K.; Wong-Foy, A., G.; Matzger, A. J. J. Am. Chem. Soc. 2009, 131, 4184. (k) Zharkouskaya, A.; Buchholz, A.; Plass, W. Eur. J. Inorg. Chem. 2005, 4875. (l) Liu, Y.; Xuan, W.; Zhang, H.; Cui, Y. Inorg. Chem. 2009, 48, 10018.