Halogen Bonding: An Effective Tool in Anion Coordination and Anion Templated Assembly Giuseppe Resnati Nanostructured Fluorinated Materials Laboratory, Department of Chemistry, Materials, and Chemical Engineering “Giulio Natta”, Politecnico di Milano, 7 via Mancinelli, I-20131 Milan (Italy) E-mail: [email protected] The halogen bonding (XB), namely the interactions where halogen atoms function as electrophilic species [1], has proven its efficiency and reliability in supramolecular chemistry, crystal engineering, and materials science [2]. Its potential and use in anion coordination and anion-templated assembly has been discovered and investigated only recently [3]. In this contribution, we report some examples of anion binding driven by halogen bonding where halides anions act as halogen bonding acceptors. We will also present how XB directs the self-assembly of oxyanions, by far the most numerous class of anions in organic chemistry, forming discrete adducts and 1D, 2D, or 3D supramolecular networks with halocarbons. Some specific examples will be discussed in order to identify new supramolecular synthons based on halogen bonding and to outline some general principles for the design of effective and selective receptors based on this interaction. Figure 1. The cryptand-like heteroditopic receptor gives the endo-recognition of sodium cation and the exo-recognition of iodide anion (JACS 2005, 127, 14972). Figure 2. The caging of 1,4-diiodoperfluorobutane with decamethonium iodide allows for its effective separation via solid-gas reaction (Science 2009, 323, 1461). Figure 3. Homochiral and fluorous double helix formed on spontaneous resolution of 1,8-diiodoperfluorooctane (Angew. Chem. Int. Ed. 2006, 45, 191). Figure 4. Halogen bonding in 2-iodoimidazolium dihydrogenphosphate (Org. Biomol. Chem. 2012, 10, 1329). [1] P. Metrangolo, G. Resnati Science 2008, 321, 918. P. Metrangolo, T. Pilati and G. Resnati CrystEngComm, 2006, 8, 946–947. [2]. P. Metrangolo, F. Meyer, T. Pilati, G. Resnati, G. Terraneo, Angew. Chem. Int. Ed. 2008, 47, 6114 – 6127. [3] G. Cavallo, P. Metrangolo, T. Pilati, G. Resnati, M. Sansotera, G. Terraneo Chem. Soc. Rev., 2010, 39, 3772–3783. A. Abate, J. Martí-Rujas, P. Metrangolo, T. Pilati, G. Resnati, G. Terraneo Cryst. Growth Des. 2011, 11, 4220–4226.
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![Page 1: Halogen(Bonding:(( An(Effective(Toolin(Anion(Coordination ......The halogen bonding (XB), namely the interactions where halogen atoms function as electrophilic species [1], has proven](https://reader034.cupdf.com/reader034/viewer/2022050507/5f98522b6666ea1f3772a610/html5/thumbnails/1.jpg)
Halogen Bonding:
An Effective Tool in Anion Coordination and Anion Templated Assembly
Giuseppe Resnati Nanostructured Fluorinated Materials Laboratory, Department of Chemistry, Materials, and Chemical Engineering “Giulio
Natta”, Politecnico di Milano, 7 via Mancinelli, I-20131 Milan (Italy) E-mail: [email protected]
The halogen bonding (XB), namely the interactions where halogen atoms function as electrophilic species [1], has proven its efficiency and reliability in supramolecular chemistry, crystal engineering, and materials science [2]. Its potential and use in anion coordination and anion-templated assembly has been discovered and investigated only recently [3].
In this contribution, we report some examples of anion binding driven by halogen bonding where halides anions act as halogen bonding acceptors. We will also present how XB directs the self-assembly of oxyanions, by far the most numerous class of anions in organic chemistry, forming discrete adducts and 1D, 2D, or 3D supramolecular networks with halocarbons. Some specific examples will be discussed in order to identify new supramolecular synthons based on halogen bonding and to outline some general principles for the design of effective and selective receptors based on this interaction.
Figure 1. The cryptand-like heteroditopic receptor gives the endo-recognition of sodium cation and the exo-recognition of iodide anion (JACS 2005, 127, 14972).
Figure 2. The caging of 1,4-diiodoperfluorobutane with decamethonium iodide allows for its effective separation via solid-gas reaction (Science 2009, 323, 1461).
Figure 3. Homochiral and fluorous double helix formed on spontaneous resolution of 1,8-diiodoperfluorooctane (Angew. Chem. Int. Ed. 2006, 45, 191).
Figure 4. Halogen bonding in 2-iodoimidazolium dihydrogenphosphate (Org. Biomol. Chem. 2012, 10, 1329).
[1] P. Metrangolo, G. Resnati Science 2008, 321, 918. P. Metrangolo, T. Pilati and G. Resnati CrystEngComm, 2006, 8, 946–947. [2]. P. Metrangolo, F. Meyer, T. Pilati, G. Resnati, G. Terraneo, Angew. Chem. Int. Ed. 2008, 47, 6114 – 6127. [3] G. Cavallo, P. Metrangolo, T. Pilati, G. Resnati, M. Sansotera, G. Terraneo Chem. Soc. Rev., 2010, 39, 3772–3783. A. Abate, J. Martí-Rujas, P. Metrangolo, T. Pilati, G. Resnati, G. Terraneo Cryst. Growth Des. 2011, 11, 4220–4226.
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