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首页> 外文期刊>Acta Crystallographica, Section B. Structural science, crystal engineering and materials >Coordination chemistry of anions through halogenbonding interactions
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Coordination chemistry of anions through halogenbonding interactions

机译：通过卤素互动协调阴离子的化学

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摘要

While an IUPAC definition for hydrogen bonding was only released in 2011 after decades of discussions in the scientific community (Arunann et al., 2011), it did not take such a long time to come up with an analogous definition of halogen bonding (Desiraju et al., 2013), following a revival of this interaction in the literature, which can be traced back to the early 1990s. The identification of this interaction is, however, not recent, as illustrated by the isolation of the H_3N·I_2 adduct (Colin, 1814). Two centuries later, several review articles (Cavallo et al., 2016; Gilday et al., 2015; Fourmigué, 2009) have gathered together most available data. The halogen-bonding interaction (noted XB) is essentially described as an electrostatic interaction between a charge concentration (Lewis base) and a chargedepleted area, called an σ-hole, that a covalently bound halogen atom exhibits in the extension of this bond. Note that a charge-transfer covalent contribution can be found in the strongest halogen bonds, as illustrated for example in the triiodide anion following: I_2 + I~-→(I—I—I)~-. The presence of a halogen bond is characterized by a shortening of the interatomic distance, relative to the sum of the van der Waals (or ionic) radii of the interacting atoms, which is defined as the reduction ratio. The halogen-bond donor character of halogenated molecules is modulated by the nature of the halogen with I > Br Cl F, by the hybridization of the substituted C atom with C≡C—I > C＝CH—I > C—CH_2—I, and by the electron-withdrawing ability of the carbon substituents, with a strong activation in aliphatic and aromatic perfluorinated substrates such as F_(2n + 1)C_n—I or C_6F_(6 - n)I_n. Besides, dihalogens (I_2, Br_2, Cl_2), interhalogens (I—Cl, I—CN) and Niodoimides (N-iodosuccinimide, N-iodosaccharin) are also strong halogen-bond donors. All Lewis bases are potentially XB acceptors and among them, anionic species, and particularly halide anions (Cl~-, Br~-, I~-) thanks to a maximal charge concentration (Metrangolo et al., 2008a; Cavallo et al., 2010).
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