Halogen and Chalcogen Bond in HPLC on Chiral Stationary Phase

In collaboration with P. Peluso (ICB, Sassari), we have demonstrated that stereoselective XBs and ChBs are able to control enantioseparation of polyhalogenated atropisomeric 4,4’-bipyridines and planar chiral ferrocenyl iodoalkynes by HPLC on cellulose-based chiral stationary phases (CSPs).

Axially Chiral 4,4′-bipyridines

Planar Chiral Ferrocenes

Selected publications:

1) Peluso, P.; Mamane, V.; Aubert, E.; Cossu, S. Insights into the impact of shape and electronic properties on the enantioseparation of polyhalogenated 4,4′-bipyridines on polysaccharide-type selectors. Evidence of stereoselective halogen bonding interactions. J. Chromatogr. A 2014, 1345, 182.

2) Peluso, P.; Mamane, V.; Aubert, E.; Dessì, A.; Dallocchio, R.; Dore, A.; Pale, P.; Cossu, S. Insights into halogen bond-driven enantioseparations. J. Chromatogr. A 2016, 1467, 228.

3) Peluso, P.; Mamane, V.; Dallocchio, R.; Dessì, A.; Villano, R.; Sanna, D.; Aubert, E.; Pale, P.; Cossu, S. Polysaccharide-based chiral stationary phases as halogen bond acceptors: a novel strategy for detection of stereoselective s-hole bonds in solution. J. Sep. Sci. 2018, 41, 1247.

4) Dallocchio, R.; Dessì, A.; Solinas, M.; Arras, A.; Cossu, S.; Aubert, E.; Mamane, V.; Peluso, P. Halogen bond in high-performance liquid chromatography enantioseparations: Description, features and modelling. J. Chromatogr. A 2018, 1563, 71 (Review).

5) Peluso, P.; Gatti, C.; Dessì, A.; Dallocchio, R.; Weiss, R.; Aubert, E.; Pale, P.; Cossu, S.; Mamane, V. Enantioseparation of fluorinated 3-arylthio-4,4’-bipyridines: Insights into chalcogen and π-hole bonds in high-performance liquid chromatography. J. Chromatogr. A 2018, 1567, 119.

6) Peluso, P.; Mamane, V.; Dessì, A.; Dallocchio, R.; Aubert, E.; Gatti, C.; Mangelings, D.; Cossu, S. Halogen bond in separation science: a critical analysis across experimental and theoretical results. J. Chromatogr. A 2020, 1616, 460788 (Review).

7) Peluso, P.; Mamane, V.; Dallocchio, R.; Dessì, A.; Cossu, S. Noncovalent interactions in high-performance liquid chromatography enantioseparations on polysaccharide-based chiral selectors. J. Chromatogr. A 2020, 1623, 461202 (Review).

8) Peluso, P.; Dessì, A.; Dallocchio, R.; Sechi, B.; Gatti, C.; Chankvetadze, B.; Mamane V.; Weiss, R.; Pale, P.; Aubert, E.; Cossu, S. Enantioseparation of 5,5’-dibromo-2,2’-dichloro-3-selanyl-4,4’-bipyridines on polysaccharide-based chiral stationary phases: exploring chalcogen bonds in liquid-phase chromatography. Molecules 2021, 26, 221.

9) Dessì, A.; Sechi, B.; Dallocchio, R.; Chankvetadze, B.; Pérez-Baeza, M.; Cossu, S.; Mamane, V.; Pale, P.; Peluso, P. Comparative enantioseparation of planar chiral ferrocenes on polysaccharide-based chiral stationary phases. Chirality 2022, 34, 609-619.

10) Sechi, B.; Dessi, A.; Gatti, C.; Dallocchio, R.; Chankvetadze, B.; Cossu, S.; Mamane, V.; Pale, P.; Peluso, P. Unravelling functions of halogen substituents in the enantioseparation of halogenated planar chiral ferrocenes on polysaccharide-based chiral stationary phases: experimental and electrostatic potential analyses. J. Chromatogr. A 2022, 1673, 463097.

11) Dallocchio, R; Dessì, A.; Sechi, B.; Chankvetadze, B.; Jibuti, G.; Cossu, S.; Mamane, V.; Peluso, P. Enantioseparation of planar chiral ferrocenes on cellulose-based chiral stationary phases: Benzoate versus carbamate pendant groups. Electrophoresis 2023, 44, 203.

12) Peluso, P.; Mamane, V. Ferrocene derivatives with planar chirality and their enantioseparation by liquid-phase techniques. Electrophoresis 2023, 44, 158 (Review).

13) Sechi, B.; Dessì, A.; Dallocchio, R.; Tsetskhladze, N.; Chankvetadze, B.; Pérez-Baeza, M.; Cossu, S.; Jibuti, G.; Mamane, V.; Peluso, P. Unravelling dispersion forces in liquid-phase enantioseparation. Part I: Impact of ferrocenyl versus phenyl groups. Anal. Chim. Acta 2023, 1278, 341725.