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Sequential halogen bonding with ditopic donors: σ hole evolutions upon halogen bond formation

Abstract : The halogen bonding ability of ditopic halogen bond donors can be evaluated from the maximum value of the molecular surface electrostatic potential, called the σ hole, at the two possibly different halogen atoms. We show here that in N,N'-diodo-dimethylhydantoin (DIH), the halogen bonding (XB) ability of the two nitrogen-bound iodine atoms does not follow this σ-hole rule. The co-crystallization of DIH with a series of para-substituted pyridines, Py-R (R = pyrrolidinyl, NMe2, Me, H, CO2Me, CF3, CN), affords bis-adducts DIH?(Py-R)2 with the most electron-rich pyridines while mono-adducts DIH?(Py-R) are favored with the most electron poor pyridines (R = CO2Me, CF3, CN). Analysis of the structural characteristics of these mono- and bis-adducts, combined with theoretical calculations, demonstrates that the formation of a first N?I???N'Py-R XB deeply modifies the XB ability (and associated σ-hole) of the second uncoordinated iodine atom. Under these conditions, the latter might associate through I???O XB to the carbonyl oxygen atom of a neighboring mono-adduct in the crystal rather than to a second pyridine. These studies show that when working with di-, tri- or tetratopic XB donors, one should always consider the deactivation of the remaining halogen atoms following sequential XB formation
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https://hal-univ-rennes1.archives-ouvertes.fr/hal-01302507
Contributor : Laurent Jonchère <>
Submitted on : Thursday, April 14, 2016 - 2:41:49 PM
Last modification on : Thursday, March 5, 2020 - 2:03:28 PM

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Irène Nicolas, Frédéric Barrière, Olivier Jeannin, Marc Fourmigué. Sequential halogen bonding with ditopic donors: σ hole evolutions upon halogen bond formation. Crystal Growth and Design, American Chemical Society, 2016, 16 (5), pp.2963-2971. ⟨10.1021/acs.cgd.6b00333⟩. ⟨hal-01302507⟩

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