Subtle Role of Polyatomic Anions in Molecular Construction: Structures and Properties of AgX Bearing 2,4′-Thiobis(pyridine) (X - ) NO 3 - , BF 4 - , ClO 4 - , PF 6 - , CF 3 CO 2 - , and CF 3 SO 3 - ) Ok-Sang Jung,* ,† Yun Ju Kim, † Young-A Lee, † Ki-Min Park, ‡ and Shim Sung Lee ‡ Materials Chemistry Laboratory, Korea Institute of Science and Technology, Seoul 136-791, Korea, and Department of Chemistry and Research Institute of Natural Science, Gyeongsang National UniVersity, Chinju 660-701, Korea Received August 8, 2002 Studies on the subtle effects and roles of polyatomic anions in the self-assembly of a series of AgX complexes with 2,4′-Py 2 S (X - ) NO 3 - , BF 4 - , ClO 4 - , PF 6 - , CF 3 CO 2 - , and CF 3 SO 3 - ; 2,4′-Py 2 S ) 2,4′-thiobis(pyridine)) have been carried out. The formation of products appears to be primarily associated with a suitable combination of the skewed conformers of 2,4′-Py 2 S and a variety of coordination geometries of Ag(I) ions. The molecular construction via self-assembly is delicately dependent upon the nature of the anions. Coordinating anions afford the 1:1 adducts [Ag(2,4′-Py 2 S)X] (X - ) NO 3 - and CF 3 CO 2 - ), whereas noncoordinating anions form the 3:4 adducts [Ag 3 (2,4′- Py 2 S) 4 ]X 3 (X - ) ClO 4 - and PF 6 - ). Each structure seems to be constructed by competition between π-π interactions of 2,4′-Py 2 S spacers vs Ag‚‚‚X interactions. For ClO 4 - and PF 6 - , an anion-free network consisting of linear Ag(I) and trigonal Ag(I) in a 1:2 ratio has been obtained whereas, for the coordinating anions NO 3 - and CF 3 CO 2 - , an anion-bridged helix sheet and an anion-bridged cyclic dimer chain, respectively, have been assembled. For a moderately coordinating anion, CF 3 SO 3 - , the 3:4 adduct [Ag 3 (2,4′-Py 2 S) 4 ](CF 3 SO 3 ) 3 has been obtained similarly to the noncoordinating anions, but its structure is a double strand via both face-to-face (π-π) stackings and Ag‚‚‚Ag interactions, in contrast to the noncoordinating anions. The anion exchanges of [Ag 3 (2,4′-Py 2 S) 4 ]X 3 (X - ) BF 4 - , ClO 4 - , and PF 6 - ) with BF 4 - , ClO 4 - , and PF 6 - in aqueous media indicate that a [BF 4 - ] analogue is isostructural with [Ag 3 (2,4′-Py 2 S) 4 ]X 3 (X - ) ClO 4 - and PF 6 - ). Furthermore, the anion exchangeability for the noncoordinating anion compounds and the X-ray data for the coordinating anion compounds establish the coordinating order to be NO 3 - > CF 3 CO 2 - > CF 3 SO 3 - > PF 6 - > ClO 4 - > BF 4 - . Introduction Various intriguing molecular frames have been designed and assembled by the selection of basic components such as the coordination geometry of metal ions, the binding site of donating atoms, and the length of spacers or/and by the induction of weak intra- or intermolecular interactions. 1-10 Rational control of molecular frameworks via (counter)anions is rare due to the less effective electrostatic binding interac- tions. 11 Recently, however, anion coordination chemistry has become a rapidly emerging field owing to a timely interest from environmental pollution, industrial chemical, biological process, ionic liquids, catalysis, lithium battery, and health- related perspectives. 12-18 More recent developments include exciting advances in anion template assembly, ion-pair * To whom correspondence should be addressed. E-mail: oksjung@ kist.re.kr. ² Korea Institute of Science and Technology. ‡ Gyeongsang National University. (1) Stang, P. J.; Olenyuk, B. Acc. Chem. Res. 1997, 30, 502-518. (2) Albrecht, M. Angew. Chem., Int. Ed. 1999, 38, 3463-3465. (3) Jones, C. J. Chem. Soc. ReV. 1998, 27, 289-299. (4) Fujita, M. Chem. Soc. ReV. 1998, 27, 417-425. (5) Batten, S. R.; Robson, R. Angew. Chem., Int. Ed. 1998, 37, 1460- 1494. (6) Constable, E. C. Tetrahedron 1992, 48, 10013-10059. (7) Chui, S. S.-Y.; Lo, S. M.-F.; Charmant, J. P. H.; Orpen, A. G.; Williams, I. D. Science 1999, 283, 1148-1150. (8) Kiang, Y.-H.; Gardener, G. B.; Lee, S.; Xu, Z. J. Am. Chem. Soc. 2000, 122, 6871-6883. (9) Braga, D.; Grepioni, F. Acc. Chem. Res. 2000, 33, 601-608. (10) Jansen, M. Angew. Chem., Int. Ed. Engl. 1987, 26, 1098-1110. (11) Beer, P. D.; Gale, P. A. Angew. Chem., Int. Ed. 2001, 40, 486-516. (12) Gale, P. A. Coord. Chem. ReV. 2001, 213, 79-128. (13) Beer, P. B.; Smith, D. K. Prog. Inorg. Chem. 1997, 46,1-96. (14) Schmidtchen, F. P.; Berger, M. Chem. ReV. 1997, 97, 1609-1646. (15) Lapointe, R. E.; Roof, G. R.; Abboud, K. A.; Klosin, J. J. Am. Chem. Soc. 2000, 122, 9560-9561. Inorg. Chem. 2003, 42, 844-850 844 Inorganic Chemistry, Vol. 42, No. 3, 2003 10.1021/ic025935q CCC: $25.00 © 2003 American Chemical Society Published on Web 01/10/2003