Halogen bonding has gained considerable attention over the last decade as a significant intermolecular interaction particularly in materials and medicinal chemistry. The directionality and predictability of halogen bonds enable the design of diverse supramolecular networks.1 Consequently, halogen bonding has become an important asset in the construction of crystalline assemblies, but understanding the complex and often different type of behavior in solution has remained very much in its infancy. The well-defined and preorganized macrocyclic structure of resorcinarene2 is an inspiring building block to construct multidimensional networks since the scaffold provides an intrinsic dimensionality and order to the supramolecular assembly. This presentation will present the use of specifically designed resorcinarene derivatives as three-dimensional tetravalent building blocks in the construction of nanosized networks held together by halogen bonds.3 Interactions between resorcinarene derivatives and mono and bivalent aryl halides are studied both in solid state and in solution. When in solid state the building blocks form multidimensional network structures, in solution interactions are not unambiguous (Figure 1). Thus, density functional theory computations were performed to help explaining the trends of NMR shifts caused by the complex behavior of these multivalent building blocks in solution. The study highlights the use of resorcinarenes as a blueprint for supramolecular network development. References 1. For review (a) P. Metrangolo, F. Meyer, T. Pilati, G. Resnati and G. Terraneo, Angew. Chem., Int. Ed. 2008, 47, 6114–6127; (b) A. Priimagi, G. Cavallo, P. Metrangolo and G. Resnati, Acc. Chem. Res. 2013, 46, 2686–2695. 2. P. Timmerman, W. Verboom, and D. N. Reinhoudt, Tetrahedron 1996, 52, 2663–2704. 3. T.-R. Tero, K. Salorinne, S. Malola, H. Häkkinen and M. Nissinen, CrystEngComm 2015 doi: 10.1039/C5CE01144B, in press (front cover).

Resorcinarenes as tetravalent halogen bond acceptors: Networks in solid state vs. dynamic assemblies in solution

251st National Meeting (2016)

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