The potential of main-group secondary-bonding in supramolecular chemistry is well illustrated by the derivatives of the 1,2,5-Telluradiazole ring.1 Their dimers and supramolecular ribbons are assembled by the [Te-N]2 supramolecular synthon, a virtual four-membered ring defined by two antiparallel Te--N contacts. Such interactions are strong enough to overcome moderate steric hindrance by allowing structural distortions that simultaneously confer functionality to the structure. For example, a twist of the supramolecular synthon creates a noncentrosymmetric feature that propagates generating a lattice with measurable second-order nonlinear optical response. Despite their versatility, the widespread application of telluradiazoles is hampered by their sensitivity to moisture. Their selenium congeners are considerably more robust but form much weaker intermolecular links. However, investigations of alkylated derivatives suggest that the attachment of a methyl group to one nitrogen atom enhances the interactions formed by the other nitrogen and the selenium atoms.2 We have extended this concept by developing syntheses for a wide range of functionalized benzoselenadiazoles, including dicationic molecules capable to infinite catenation. DFT calculations have provided a rationale for the strengthening of the secondary links and explained the ability of halide binding to compete with the [Se-N]2 supramolecular synthon.(1) (a) Cozzolino, A.; Vargas-Baca, I.; Mansour, S.; Mahmoudkhani, A. J. Am. Chem. Soc. 2005  , 127, 3184. (b) Cozzolino, A.; Elder, P.; Vargas-Baca, I. Coord. Chem. Rev. 2011  , 255, 1426. (c) Cozzolino, A.; Whitfield, P.; Vargas-Baca, I. J. Am. Chem. Soc. 2010  , 132, 17265. (d) Cozzolino, A.; Yang, Q.; Vargas-Baca, I. Cryst. Growth Des. 2010  , 10, 4959.(2) (a) Berionni, G.; Pegot, B.; Marrot, J.; Goumont, R. CrystEngComm. 2009  , 11, 986. (b) Dutton, J.; Tindale, J.; Jennings, M.; Ragogna, P. Chem. Commun. 2006  , 2474. (c) Risto, M.; Reed, R.; Robertson, C.; Oilunkaniemi, R.; Laitinen, R.; Oakley, R. Chem. Commun. 2008  , 3278.

Supramolecular chemistry of N-substituted benzo-2,1,3-selenadiazoles

247th National Meeting (2014)

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