Solving the enigma of weak fluorine contacts in the solid state: a periodic DFT study of fluorinated organic crystals

Levina, Elena O.; Chernyshov, Ivan Yu.; Voronin, Alexander P.; Алексейко, Л. Н.; Сташ, А. И.; Vener, Mikhail V.

doi:10.1039/c9ra02116g

Cited by 40 publications

(38 citation statements)

References 120 publications

(149 reference statements)

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“…The present study demonstrates that the F atoms not only increase the TCNQ electron affinity, but also have an active role in the crystal packing through F … H bonds. The importance of halogen bonding is of course well known in crystal engineering, although the role of weak intermolecular bonding involving F and HC is still an active matter of study [28]. Here, we have an example of the interplay of F … HC intermolecular bonding with 1-dimensional CT interaction that favors the face-toface molecular arrangement of the π-molecules.…”

Section: Resultsmentioning

confidence: 94%

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(Perylene)3-(TCNQF1)2: Yet Another Member in the Series of Perylene–TCNQFx Polymorphic Charge Transfer Crystals

et al. 2020

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The 3:2 Charge Transfer (CT) co-crystal (Perylene)3(TCNQF1)2 is grown by the Physical Vapor Transport (PVT) method, and characterized structurally and spectroscopically. Infrared analysis of the charge sensitive modes reveals a low degree of charge transfer (less than 0.1) between donor and acceptor molecules. The crystal is isostructural to the other 3:2 CT crystals formed by Perylene with TCNQF2 and TCNQF4, whereas such stoichiometry and packing is not known for the CT crystals with non-fluorinated TCNQ. The analysis of the isostructural family of 3:2 Perylene–TCNQFx (x = 1,2,4) co-crystal put in evidence the role of weak F…HC bonding in stabilizing this type of structure

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Section: Resultsmentioning

confidence: 94%

“…H bonds. The importance of halogen bonding is of course well known in crystal engineering, although the role of weak intermolecular bonding involving F and HC is still an active matter of study [28]. Here, we have an example of the interplay of F .…”

Section: Resultsmentioning

confidence: 97%

(Perylene)3-(TCNQF1)2: Yet Another Member in the Series of Perylene–TCNQFx Polymorphic Charge Transfer Crystals

et al. 2020

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“…The electrostatic character and partial directionality of C–H/F interactions stipulate the structure‐directing role of these interactions in crystals containing C, H, and F atoms. This was recently manifested in the differences in the crystalline packing of partially fluorinated aromatic molecules . In several cases ( 16h , 16i ) the mixture of solvents (toluene, hexanes) was used to suppress the solubility of the product and increase the yield.…”

Section: Methodsmentioning

confidence: 99%

Stereoselective Mannich Reaction Driven by Crystallization

Čierna¹,

Markus²,

Doháňošová

et al. 2020

Eur J Org Chem

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Herein we disclose an efficient and experimentally straightforward method for the stereoselective synthesis of a variety of α‐substituted Mannich salts. This direct three‐component Mannich reaction operates on readily available reagents in almost stoichiometric ratio and enables the preparation of both enantiomers. Crystallization controlled epimerization allows isolation of the target compounds in high enantio‐ and diastereomeric purities by a simple filtration. The efficiency of this chromatography‐free approach predestines it for the gram‐scale synthesis and industrial applications.

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“…FÁ Á Á interactions (towards the system of a the macrocycle), and one severely slipped -stacking interaction between two pentafluorophenyl rings. The most prominent C-HÁ Á ÁF interactions (Levina et al, 2019) involve the two methyl groups of the 2,3-dimethoxymorpholino unit (Fig. 5a).…”

Section: Figurementioning

confidence: 99%

Crystal structure of 2,3-dimethoxy-meso-tetrakis(pentafluorophenyl)morpholinochlorin methylene chloride 0.44-solvate

et al. 2020

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The title morpholinochlorin, C46H16F20N4O3, was crystallized from hexane/methylene chloride as its 0.44 methylene chloride solvate, C46H16F20N4O3·0.44CH2Cl2. The morpholinochlorin was synthesized by stepwise oxygen insertion into a porphyrin using a `breaking and mending strategy': NaIO4-induced diol cleavage of the corresponding 2,3-dihydroxychlorin with in situ methanol-induced, acid-catalyzed intramolecular ring closure of the intermediate secochlorins bisaldehyde. Formally, one of the pyrrolic building blocks was thus replaced by a 2,3-dimethoxymorpholine moiety. Like other morpholinochlorins, the macrocycle of the title compound adopts a ruffled conformation, and the modulation of the porphyrinic π-system chromophore induces a red-shift of its optical spectrum compared to its corresponding chlorin analog. Packing in the crystal is governed by interactions involving the fluorine atoms of the pentafluorophenyl substituents, dominated by C—H...F interactions, and augmented by short fluorine...fluorine contacts, C—F...π interactions, and one severely slipped π-stacking interaction between two pentafluorophenyl rings. The solvate methylene chloride molecule is disordered over two independent positions around an inversion center with occupancies of two × 0.241 (5) and two × 0.199 (4), for a total site occupancy of 88%.

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Solving the enigma of weak fluorine contacts in the solid state: a periodic DFT study of fluorinated organic crystals

Abstract: The nature and strength of weak C–H⋯F–C and C–F⋯F–C interactions and their role in organofluorine molecular crystals were studied using periodic DFT coupled with CSD data mining and experimental sublimation enthalpies.

Cited by 40 publications

References 120 publications

(Perylene)3-(TCNQF1)2: Yet Another Member in the Series of Perylene–TCNQFx Polymorphic Charge Transfer Crystals

(Perylene)3-(TCNQF1)2: Yet Another Member in the Series of Perylene–TCNQFx Polymorphic Charge Transfer Crystals

Stereoselective Mannich Reaction Driven by Crystallization

Crystal structure of 2,3-dimethoxy-meso-tetrakis(pentafluorophenyl)morpholinochlorin methylene chloride 0.44-solvate

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