The crystal structures of 1-(4-halo-2,3,5,6-tetrafluorophenyl)-3-benzylimidazolium bromides: The relative importance of anion–π, lone pair–π, π π stacking and halogen bonding interactions

Althagbi, Hanan I.; Bernstein, Daniel Richard; Crombie, Winifred; Lane, Joseph R.; McQuiston, Dylan K.; Oosterwijk, Melissa A.; Saunders, Graham C.; Zou, W. Q.

doi:10.1016/j.jfluchem.2017.12.006

Cited by 13 publications

(19 citation statements)

References 47 publications

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“…The 2,6-disubstituted phenylmethylimidazolium bromide salts [MeNC 3 H 3 NCH 2 C 6 H 3 X-2-F-6] + .Br -[X = F (1), Cl (2), Br (3), I (4), CF 3 (5)] were 5 prepared by treatment of 1-methylimidazole with the appropriate benzyl bromide. The salts were characterized by mass spectrometry and 1 H, 13 C and 19 F NMR spectroscopy.…”

Section: Resultsmentioning

confidence: 99%

“…The bond distances and angles are similar to those calculated using the B97X-D functional [13] with the 6-311++G(2d,2p) basis set for the isolated cations in the gas phase. (5) indicating the positions of the bromide anions close to C(1), C(2) and C (3). Thermal ellipsoids are at the 50% level.…”

Section: Resultsmentioning

confidence: 99%

“…The crystal structures of fluoroaryl-substituted imidazolium salts are a valuable source of information on a range of non-covalent interactions, in particular, π-π stacking [1][2][3][4][5] and anion-π interactions [2,3,[5][6][7][8], arising from the presence of fluorine atoms, along with charge-assisted hydrogen bonding [3,9]. These interactions have importance in crystal engineering and through the judicious choice of fluoroaryl substituents polar crystal structures can be realized [1][2][3][4][5]. Furthermore, the incorporation of other halogen atoms into the polyfluoroaryl group provides the opportunity for halogen bonding when the anion is a halide [5,6].…”

Section: Introductionmentioning

confidence: 99%

“…These interactions have importance in crystal engineering and through the judicious choice of fluoroaryl substituents polar crystal structures can be realized [1][2][3][4][5]. Furthermore, the incorporation of other halogen atoms into the polyfluoroaryl group provides the opportunity for halogen bonding when the anion is a halide [5,6].…”

Section: Introductionmentioning

confidence: 99%

“…It is expected that non-covalent interactions can be turned on or off for imidazolium halide salts by variation of the substituent aryl group. As an example, although the structures of the related cations of 1-pentafluorophenylmethyl-3-methylimidazolium bromide (ROTMEU) [7] and 1-(2-bromophenylmethyl)-3-methylimidazolium bromide (EVACIO) [11] adopt similar conformations, because of the difference in the electronic nature of the phenyl ring the crystal structure of the former possesses an anion-π interaction [2,3,[5][6][7][8]12], whereas that of the latter does not (Figure 1). In order to further probe these structural features and non-covalent interactions we are investigating fluoroaryl-substituted imidazolium salts.…”

Section: Introductionmentioning

confidence: 99%

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The structures of 1-(2-halo-6-fluorophenylmethyl)-1-methylimidazolium bromide salts

Lorenzini

Marr

Saunders

et al. 2018

Journal of Fluorine Chemistry

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The crystal structures of 1-(2-halo-6-fluorophenylmethyl)-1-methylimidazolium bromide salts and 1-(2-trifluoromethyl-6-fluorophenylmethyl)-1-methylimidazolium bromide [MeNC 3 H 3 NCH 2 C 6 H 3 X-2-F-6] + .Br-[X = F (1), Cl (2), Br (3), I (4), CF 3 (5)] have been determined. The crystal structure of the hydrate of salt 1 contains π-π stacked imidazolium•••difluorophenyl•••difluorophenyl•••imidazolium units. Those of salts 2, 4 and 5 possess bromide•••halofluorophenyl•••halofluorophenyl•••bromide motifs comprising anion-π and π-π stacking interactions. That of salt 4 also contains bromide•••iodide halogen bonding. The crystal structure of the sesquihydrate of salt 3 possesses bromine•••halofluorophenyl•••halofluorophenyl•••bromine motifs.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

The structures of 1-(2-halo-6-fluorophenylmethyl)-1-methylimidazolium bromide salts

Lorenzini

Marr

Saunders

et al. 2018

Journal of Fluorine Chemistry

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PAH/PAH(CF₃)_n Donor/Acceptor Charge‐Transfer Complexes in Solution and in Solid‐State Co‐Crystals

Castro

Bukovsky

Kuvychko

et al. 2019

Chemistry A European J

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A solution, solid‐state, and computational study is reported of polycyclic aromatic hydrocarbon PAH/PAH(CF3)n donor/acceptor (D/A) charge‐transfer complexes that involve six PAH(CF3)n acceptors with known gas‐phase electron affinities that range from 2.11(2) to 2.805(15) eV and four PAH donors, including seven CT co‐crystal X‐ray structures that exhibit hexagonal arrays of mixed π‐stacks with 1/1, 1/2, or 2/1 D/A stoichiometries (PAH=anthracene, azulene, coronene, perylene, pyrene, triphenylene; n=5, 6). These are the first D/A CT complexes with PAH(CF3)n acceptors to be studied in detail. The nine D/A combinations were chosen to allow several structural and electronic comparisons to be made, providing new insights about controlling D/A interactions and the structures of CT co‐crystals. The comparisons include, among others, CT complexes of the same PAH(CF3)n acceptor with four PAH donors and CT complexes of the same donor with four PAH(CF3)n acceptors. All nine CT complexes exhibit charge‐transfer bands in solution with λ max between 467 and 600 nm. A plot of E(λ max) versus [IE(donor)−EA(acceptor)] for the nine CT complexes studied is linear with a slope of 0.72±0.03 eV eV−1. This plot is the first of its kind for CT complexes with structurally related donors and acceptors for which precise experimental gas‐phase IEs and EAs are known. It demonstrates that conclusions based on the common assumption that the slope of a CT E(λ max) versus [IE−EA] plot is unity may be incorrect in at least some cases and should be reconsidered.

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Fluorination‐Induced Evolution of Columnar Packing in Fluorous Triphenylenes and Benzotriphenylenes

et al. 2018

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What is the main focuso fy our research?We develop "top-down" synthetic methodologies for organic electron-acceptor materials that become components in aw ide variety of organic optoelectronic devices. Our syntheses are based on one-step, high-temperature, gas-or solution-phase reactions between polycyclic aromatic hydrocarbons (PAHs) and perfluoroalkyl or -aryl halides. While dozens of PAH(RF)n derivatives with electron affinities that range from 1.0 to 3.3 eV have been prepared in this manner in our lab, optimizing these reactions to produce primarily as ingle product has remained challenging until now.T his paper provides the first examples of highly selective syntheses of polysubstituted fluorous triphenylenes. Our finding that copper metal promotes specific substitution sites on triphenylene can now be applied to other PAHs ubstrates that have triphenylene-like structural elements to achieve higher selectivity in the preparation of particular PAH(RF/ArF) n targets of interest. With the myriad of fluorous PAHs at hand, we also study how various types and various numbers of fluorous groups affect their solid-state packing, which can greatly influence charge transport kinetics and thermodynamics. An unanticipated example of this is reported in this paper:r eplacing one Fa tom with an Ha tom in ac yclo-C 4 F 8 substituent resulted in ashift in columnar stacking of 508.Invited for thism onth'sc over are the groupso fS tevenS trauss/Olga Boltalina at Colorado State University,a nd Yu-Sheng Chen at the NSF'sC hemMatCARS. The cover pictures hows the evolution of fluorous triphenylenec rystalp ackingm otifs against the backdrop of the Very Large Array near Magdalena in New Mexico, where scientists studyt he evolution of the universe. The stepwise structural evolution in columnar packingo bserved was possible because of the development of a one-stepselectives ynthesis for triphenylene(C 4 F 8 ) n derivatives (n = 1-3). These compounds are expected to find application in liquid crystal displaysa nd organic electronics. Read the fulltext of the article at

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The crystal structures of 1-(4-halo-2,3,5,6-tetrafluorophenyl)-3-benzylimidazolium bromides: The relative importance of anion–π, lone pair–π, π π stacking and halogen bonding interactions

Cited by 13 publications

References 47 publications

The structures of 1-(2-halo-6-fluorophenylmethyl)-1-methylimidazolium bromide salts

The structures of 1-(2-halo-6-fluorophenylmethyl)-1-methylimidazolium bromide salts

PAH/PAH(CF₃)_n Donor/Acceptor Charge‐Transfer Complexes in Solution and in Solid‐State Co‐Crystals

Fluorination‐Induced Evolution of Columnar Packing in Fluorous Triphenylenes and Benzotriphenylenes

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The crystal structures of 1-(4-halo-2,3,5,6-tetrafluorophenyl)-3-benzylimidazolium bromides: The relative importance of anion–π, lone pair–π, π π stacking and halogen bonding interactions

Cited by 13 publications

References 47 publications

The structures of 1-(2-halo-6-fluorophenylmethyl)-1-methylimidazolium bromide salts

The structures of 1-(2-halo-6-fluorophenylmethyl)-1-methylimidazolium bromide salts

PAH/PAH(CF3)n Donor/Acceptor Charge‐Transfer Complexes in Solution and in Solid‐State Co‐Crystals

Fluorination‐Induced Evolution of Columnar Packing in Fluorous Triphenylenes and Benzotriphenylenes

Contact Info

Product

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PAH/PAH(CF₃)_n Donor/Acceptor Charge‐Transfer Complexes in Solution and in Solid‐State Co‐Crystals