Halogen bond directionality translates tecton geometry into self-assembled architecture geometry

Saccone, Marco; Cavallo, Gabriella; Metrangolo, Pierangelo; Pace, Andrea; Pibiri, Ivana; Pilati, Tullio; Resnati, Giuseppe; Terraneo, Giancarlo

doi:10.1039/c3ce40268a

Cited by 62 publications

(40 citation statements)

References 42 publications

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“…[45]. Finally, in a study of oxadiazole based molecules the best acceptor is favored, which was explained by a combination of basicity and the greater steric accessibility of the pyridine nitrogen atoms relative to the oxadiazolic core [46]. Again, a purely electrostatic is also consistent with the observed interactions.…”

Section: Discussionsupporting

confidence: 66%

Halogen-Bond Preferences in Co-crystal Synthesis

et al. 2015

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To examine the possibility of establishing a hierarchy of the relative importance of different halogen bonds in the solid state, twelve co-crystallization experiments were performed between three different ditopic halogen-bond acceptors, 1,1 0 -bis(pyridin-4-ylmethyl)-2,2 0 -biimidazole (A1), 1,1 0 -bis(pyridin-3-ylmethyl)-2,2 0 -biimidazole (A2) and 1,1 0 -bis(pyridin-2-ylmethyl)-2,2 0 -biimidazole (A3) and four perfluoroiodoalkanes. A ranking of potentially competing acceptor-sites was based on calculated molecular electrostatic surface potentials using DFT; the pyridine nitrogen atom found to be the best acceptor in all three acceptor molecules. An analysis of the outcome of all twelve attempted reactions using IR spectroscopy showed that eight of the twelve attempts resulted in a cocrystal, the equivalent of a 67 % total supramolecular yield. Six crystal structures were obtained and all show that halogen bonding involves the best acceptor site (pyridine) as ranked by the electrostatic potentials. The supramolecular yield increased with increasing charge on the acceptor site thereby underlying the importance of electrostatics in practical supramolecular synthesis of co-crystals driven by halogen bonding. Graphical Abstract A ranking of potentially competing halogen bond acceptor-sites was achieved using calculated molecular electrostatic surface potentials and successfully implemented in the practical synthesis of co-crystals with the desired connectivity.

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Section: Discussionsupporting

confidence: 66%

Halogen-Bond Preferences in Co-crystal Synthesis

et al. 2015

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“…As anticipated, thanks to the directionality of halogen bonding, the geometry of the synthons involved in the non-covalent interaction is translated in the geometry of the final supramolecular structure [4]. This is clearly evident in the crystal packing of (cis-7)(10) and (trans-7)(10).…”

Section: Halogen-bonded Crystals That Movementioning

confidence: 83%

Halogen-Bonded Photoresponsive Materials

Saccone

Cavallo

Metrangolo

et al. 2014

Topics in Current Chemistry

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The aim of the present review is to illustrate to the reader the state of the art on the construction of supramolecular azobenzene-containing materials formed by halogen bonding. These materials include several examples of polymeric, liquid crystalline or crystalline species whose performances are either superior to the corresponding performances of their hydrogen-bonded analogues or simply distinctive of the halogen-bonded species.

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“…a,vDihaloperfluoroalkanes typically adopt an all-trans conformation and the two CZX bonds are nearly parallel; moreover, the two lone pairs on the oxygen atom of HMPA adopt an angled arrangement. The XB directionality (22) translates these geometrical features of starting tectons 1 and 2 into the geometrical features of the self-assembled architecture 3, and the halogen-bonded infinite chains adopt an undulated shape wherein HMPA imposes the angulation and dihalotetrafluoroethanes work as linear spacers of bending sites.…”

Section: Resultsmentioning

confidence: 99%

C–halogen…O supramolecular synthons: in situ cryocrystallisation of 1,2-dihalotetrafluoroethane/HMPA adducts

Bertolotti

Cavallo

Metrangolo

et al. 2013

Supramolecular Chemistry

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The in situ cryocrystallisation technique has been used to obtain four adducts between hexamethylphosphortriamide and 1,2-dihalotetrafluoroethanes having iodine, bromine and chlorine as halogen-bonding donor atoms. These systems allowed for a precise comparison of different CZX· · ·O synthons. The effectiveness and reliability of the pharmacologically important CZCl· · ·O synthons are proven.

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Halogen bond directionality translates tecton geometry into self-assembled architecture geometry

Abstract: The structures of halogen-bonded infinite chains involving two diiodoperfluoroalkanes and a bent bis(pyrid-4′-yl)oxadiazole show that the geometry of the pyridyl pendant rings is translated into the angle between the formed halogen bonds. © 2013 The Royal Society of Chemistry

Cited by 62 publications

References 42 publications

Halogen-Bond Preferences in Co-crystal Synthesis

Halogen-Bond Preferences in Co-crystal Synthesis

Halogen-Bonded Photoresponsive Materials

C–halogen…O supramolecular synthons: in situ cryocrystallisation of 1,2-dihalotetrafluoroethane/HMPA adducts

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