The disorder of perfluoroalkyl chains in crystals: Two case histories of interpretation and refinement

Dey, Archan; Metrangolo, Pierangelo; Pilati, Tullio; Resnati, Giuseppe; Terraneo, Giancarlo; Wlassics, I.

doi:10.1016/j.jfluchem.2009.06.018

Cited by 18 publications

(14 citation statements)

References 53 publications

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“…With the formation of new intermolecular interactions between donor and acceptor, some of the original stretching bonds are affected although it is sometimes difficult to find obvious patterns to the way in which some of modes are red or blue shifts compared to their original positions. This is consistent with previously reported observations of halogen bonds in the solid state [41,42].…”

Section: Discussionsupporting

confidence: 94%

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: 94%

Halogen-Bond Preferences in Co-crystal Synthesis

et al. 2015

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“…As the PFAFs include larger and larger R f radicals they become more and more challenging for computational studies as well. Finally, even if one succeeds in growing suitable for crystallography single crystals, more complications arise in solving their structures due to challenging modeling of rotational disorder of long perfluoroalkyl chains [35]. We conclude that at present the most complete set of structural data for PFAFs is that of C 60 (C 2 F 5 ) 6,8,10 .…”

Section: Structural Studiesmentioning

confidence: 93%

High-temperature and photochemical syntheses of C60 and C70 fullerene derivatives with linear perfluoroalkyl chains

Shustova

Kareev

Kuvychko

et al. 2010

Journal of Fluorine Chemistry

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“…During the last decade, Metrangolo et al1–6, 15–18 have fully exploited the wide applications of halogen bonding in molecular recognition and supramolecular architectures. In particular, they demonstrated the general ability of iodo‐ and bromo‐perfluorocarbons (PFCs) to behave as robust tectons in crystal engineering induced by halogen bonding2–6.…”

Section: Introductionmentioning

confidence: 99%

Effects of solvent on weak halogen bonds: Density functional theory calculations

Lu¹,

Li²,

Zhu³

et al. 2011

Int J of Quantum Chemistry

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In recent years, many applications of solution-phase halogen bonding in anion recognition, catalysis, and pseudorotaxane formation have been reported. Moreover, a number of thermodynamic data of halogen bonding interactions in organic solution are now available. To obtain detailed information of the influence of the surrounding medium on weak halogen bonds, a series of dimeric complexes of halobenzene (PhX) with three electron donors (H 2 O, HCHO, and NH 3 ) were investigated by means of DFT/PBE calculations in this work. The PCM implicit solvation approach was utilized to include the effects of three solvents (cyclohexane, chloroform, and water) as representatives for a wide range of dielectric constant. In some cases, halogen-bond distances are shown to shorten in solution, accompanied by concomitant elongation of the CAX bonds. For the remaining systems, the intermolecular distances tend to increase or remain almost unchanged under solvent effects. In general, the solvent has a slight destabilizing effect on weak halogen bonds; the strength order of halogen bonds observed in vacuum remains unchanged in liquid phases. Particularly, the interaction strength attenuates in the order I > Br > Cl in solution, consistent with the experimental measurements of weak halogen bond door abilities. The similarities between halogen and hydrogen bonding in solution were also elucidated. The results presented herein would be very useful in future applications of Correspondence

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The disorder of perfluoroalkyl chains in crystals: Two case histories of interpretation and refinement

Cited by 18 publications

References 53 publications

Halogen-Bond Preferences in Co-crystal Synthesis

Halogen-Bond Preferences in Co-crystal Synthesis

High-temperature and photochemical syntheses of C60 and C70 fullerene derivatives with linear perfluoroalkyl chains

Effects of solvent on weak halogen bonds: Density functional theory calculations

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