Interaction of B12F122– with All-cis 1,2,3,4,5,6 Hexafluorocyclohexane in the Gas Phase

Lecours, Michael J.; Marta, Rick A.; Steinmetz, Vincent; Keddie, Neil S.; Fillion, Eric; O’Hagan, David; McMahon, T. B.; Hopkins, W. Scott

doi:10.1021/acs.jpclett.6b02629

Cited by 34 publications

(21 citation statements)

References 29 publications

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“…The results show that these alkalides not only possess strong electrostatic interaction between 1 and alkali‐metal ions but also exhibit remarkably large β 0 up to 1.45 × 10 6 au . Besides, the interactions of F 6 C 6 H 6 with

{normalB}_{12} {normalF}_{12}^{2 -}

, flue gases, benzene, aromatic molecules, and materials have been investigated using experimental or quantum chemical approaches …”

Section: Introductionmentioning

confidence: 99%

Investigation on the electronic structures and nonlinear optical properties of alkali metal atom doped all‐cis 1,2,3,4,5,6‐hexafluorocyclohexane

Hou

Wang

et al. 2018

Int J of Quantum Chemistry

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On the basis of stable all‐cis 1,2,3,4,5,6‐hexafluorocyclohexane, a series of alkali metal atom doped MF6C6H6 (M = Li, Na, and K) compounds were theoretically constructed and studied by using ab initio quantum chemistry method. The calculated results show that the HOMO–LUMO gap of the MF6C6H6 conspicuously narrowed from 10.41 eV of pure F6C6H6 to about 2.00 eV of MF6C6H6. The electride characteristics of MF6C6H6 are verified by their electronic structures, HOMOs, and small VIE values. As expected, these electrides possess considerable static first hyperpolarizabilities (β0). Among the studied electrides, the largest β0 of the LiF6C6H6 is 7.00 × 105 au, which is about 3030 times larger than pure F6C6H6. TD‐M06‐2X calculations show that these larger β0 values are attributed to lower transition energies for the crucial excited states of MF6C6H6 systems. Further, the vibrational contributions to the static first hyperpolarizabilities of these molecules are also estimated. Moreover, Li atom doped dimer and trimer of F6C6H6 also present unusual electride's features and exhibit dramatically large β0. Thus, the F6C6H6 interacting with the alkali metal atoms may be a potential promising NLO nanomaterial.

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{normalB}_{12} {normalF}_{12}^{2 -}

, flue gases, benzene, aromatic molecules, and materials have been investigated using experimental or quantum chemical approaches …”

Section: Introductionmentioning

confidence: 99%

Investigation on the electronic structures and nonlinear optical properties of alkali metal atom doped all‐cis 1,2,3,4,5,6‐hexafluorocyclohexane

Hou

Wang

et al. 2018

Int J of Quantum Chemistry

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“…Further, the limited use of small molecules may be due to their thermal stability for such purposes. Recently, all‐ cis 1,2,3,4,5,6‐hexafluorocyclohexane has been studied for the interaction of cations and anions together and on the solvent binding of B 12 F 12 2− with all‐ cis 1,2,3,4,5,6‐hexafluorocyclohexane using gas phase studies ,…”

Section: Introductionmentioning

confidence: 99%

“…All‐ cis 1,2,3,4,5,6‐hexafluorocyclohexane system has been used to bind the cations or anions. However, the adsorption of neutral molecules has not reported ,. We have examined the adsorption of flue gases, such as CO 2 , CH 4 and N 2 molecules with fluoro‐substituted cyclohexane or adamantane for the flue gas recognition process.…”

Section: Introductionmentioning

confidence: 99%

Exploiting CF Bond of Hexafluorocyclohexane and Decafluoroadamantane Systems to Capture Flue Gases: A Computational Study

Pradhan

Ganguly

2017

ChemistrySelect

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The interaction of flue gases (CO 2 , CH 4, and N 2 ) with all-cis 1,2,3,4,5,6-hexafluorocyclohexane(1) and decafluoroadamantane system have been exploited through a systematic computational study to evaluate the capturing efficacy using B3LYP-D3/6-31G(d) level of theory. The DFT results show that 1 is selective for the CO 2 . 1 can adsorb 6 CO 2 molecules with reasonable strength, i. e.,~6.0 to~10.0 kcal/mol. First report with adamantane systems (2, 3), which can adsorb twelve CO 2 molecules with reasonable adsorption energy~À5.0 to À10.0 kcal/mol. Among the three flue gases, CO 2 and CH 4 preferably bind with the polar ÀCÀF bonds whereas N 2 prefers to bind with the ÀCÀH bonds of above systems. The nature of the interaction of CO 2 with these systems has investigated using Atoms In Molecules (AIM), Molecular Electrostatic Potential Surface (MESP), and Energy Decomposition Analysis (EDA) analyses. The dispersive interaction is predominantly responsible for the binding of CO 2 molecule with the ÀCÀF bonds of 1 and AIM calculations also corroborate the noncovalent interactions. The calculated desorption energies suggest that these molecules would be kinetically active to exploit as novel materials to capture flue gases.

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“…This compound is highly crystalline with a very high melting point (208 °C) for a fluorinated hydrocarbon. The facial polarity of cyclohexane 1 gives it the unique ability to coordinate alkali metal cations to the fluorine face and anions (e.g., Cl − , B 12 F 12 2− ) to the hydrogen face . Cyclohexane 1 is the prototypical example, however despite its intriguing properties it is not readily derivatised and is not an obvious starting point for introducing this ring system into higher molecular architectures.…”

Section: Introductionmentioning

confidence: 99%

“…The facial polarity of cyclohexane 1 gives it the unique abilityt oc oordinate alkali metal cations to the fluorine face and anions( e.g.,C l À ,B 12 F 12 2À )t ot he hydrogenf ace. [8,9] Cyclohexane 1 is the prototypical example,h owever despite its intriguing properties it is not readily derivatised and is not an obvious starting point for introducing this ring system into higher molecular architectures. In that context we have focusedo n phenyl all-cis-2, 3, 5, 6-tetrafluorocyclohexane 2.…”

Section: Introductionmentioning

confidence: 99%

Benzylic Functionalisation of Phenyl all‐cis‐2,3,5,6‐Tetrafluorocyclohexane Provides Access to New Organofluorine Building Blocks

Bykova

Al‐Maharik

Slawin

et al. 2018

Chemistry A European J

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Selectively fluorinated hydrocarbons continue to attract attention for tuning pharmacokinetic properties in agrochemical and pharmaceutical discovery programmes. This study identifies benzylic bromination of phenyl all-cis-2,3,5,6-tetrafluorocyclohexane 2 as a key reaction for accessing building blocks containing the all-cis-2,3,5,6-tetrafluorocyclohexane ring system. These cyclohexanes are of interest as the fluorines are only on one face of the cyclohexane, and this imparts an unusual polar aspect, very different to an otherwise hydrophobic cyclohexane. Ritter type reactions of benzyl bromide 4 with DMF and acetonitrile generated the corresponding benzyl alcohol 6 and benzylacetamide 7 respectively. Benzylacetamide 7 was hydrolysed to benzyl amine 8 and syn-amino-alcohol 9, and separately the phenyl ring was oxidatively cleaved to furnish carboxylic acid acetamide 10, which after hydrolysis gave the tetrafluorocyclohexyl amino acid 11. A trans-halogenation of benzylbromide 4 with AgF gave benzyl fluoride 13. Oxidative cleavage of the aryl ring then gave pentafluorocyclohexyl carboxylic acid 14. This carboxylic acid was readily converted to amides 23-26 and the preferred conformations of these α-fluoroamides were explored by DFT, X-ray structure and H- F HOESY NMR analysis.

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Interaction of B₁₂F₁₂^2– with All-cis 1,2,3,4,5,6 Hexafluorocyclohexane in the Gas Phase

Cited by 34 publications

References 29 publications

Investigation on the electronic structures and nonlinear optical properties of alkali metal atom doped all‐cis 1,2,3,4,5,6‐hexafluorocyclohexane

Investigation on the electronic structures and nonlinear optical properties of alkali metal atom doped all‐cis 1,2,3,4,5,6‐hexafluorocyclohexane

Exploiting CF Bond of Hexafluorocyclohexane and Decafluoroadamantane Systems to Capture Flue Gases: A Computational Study

Benzylic Functionalisation of Phenyl all‐cis‐2,3,5,6‐Tetrafluorocyclohexane Provides Access to New Organofluorine Building Blocks

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