Electron affinity of perhalogenated benzenes: A theoretical DFT study

Volatron, François; Roche, Cécile

doi:10.1016/j.cplett.2007.07.078

Cited by 4 publications

(5 citation statements)

References 31 publications

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“…exactly C 2v ), however, its SOMO has a pure s* character. 13 Note that the C 6 Cl 6 À geometry optimised at the DFT:B3LYP level (obtained here and previously described 46 ) is very close to those predicted by a high level B2PLYP-D/aug-cc-pVTZ method. ‡ The geometry optimisation of C 6 Cl 5 OMe À in DMF resulted in a spontaneous C-Cl cleavage with the formation of a radicalion pair, (Cl À Á Á ÁC 6 Cl 4 OMe ) solv (see the caption of Fig.…”

Section: Molecular and Electronic Properties Of The Investigated Chlo...supporting

confidence: 80%

Dissociative electron transfer in polychlorinated aromatics. Reduction potentials from convolution analysis and quantum chemical calculations

Romańczyk

Rotko

Kurek

2016

Phys. Chem. Chem. Phys.

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Formal potentials of the first reduction leading to dechlorination in dimethylformamide were obtained from convolution analysis of voltammetric data and confirmed by quantum chemical calculations for a series of polychlorinated benzenes: hexachlorobenzene (-2.02 V vs. Fc(+)/Fc), pentachloroanisole (-2.14 V), and 2,4-dichlorophenoxy- and 2,4,5-trichlorophenoxyacetic acids (-2.35 V and -2.34 V, respectively). The key parameters required to calculate the reduction potential, electron affinity and/or C-Cl bond dissociation energy, were computed at both DFT-D and CCSD(T)-F12 levels. Comparison of the obtained gas-phase energies and redox potentials with experiment enabled us to verify the relative energetics and the performance of various implicit solvent models. Good agreement with the experiment was achieved for redox potentials computed at the DFT-D level, but only for the stepwise mechanism owing to the error compensation. For the concerted electron transfer/C-Cl bond cleavage process, the application of a high level coupled cluster method is required. Quantum chemical calculations have also demonstrated the significant role of the π*ring and σ*C-Cl orbital mixing. It brings about the stabilisation of the non-planar, C2v-symmetric C6Cl6˙(-) radical anion, explains the experimentally observed low energy barrier and the transfer coefficient close to 0.5 for C6Cl5OCH3 in an electron transfer process followed by immediate C-Cl bond cleavage in solution, and an increase in the probability of dechlorination of di- and trichlorophenoxyacetic acids due to substantial population of the vibrational excited states corresponding to the out-of-plane C-Cl bending at ambient temperatures.

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Section: Molecular and Electronic Properties Of The Investigated Chlo...supporting

confidence: 80%

Dissociative electron transfer in polychlorinated aromatics. Reduction potentials from convolution analysis and quantum chemical calculations

Romańczyk

Rotko

Kurek

2016

Phys. Chem. Chem. Phys.

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“…Indeed, in the series C 6 R 6 (R=F, Cl, Br, I) a gas‐phase v EA 1 is positive and equal (experiment/CCCSD(T)+ZPE calculations) to 0.53/0.55, 0.92/0.86, −/1.17, −/1.82 eV, respectively (exp. for C 6 H 6 : −1.17 eV), i. e ., revealing the same χ A ‐contradictive trend which, however, was not explained [53] . Accordingly, unexplained CV data reveal that amongst C 6 F 6 , [54] C 6 Cl 6 [55] and C 6 Br 6 [56] the former is the weakest, and the latter the strongest, one‐electron acceptor (C 6 I 6 was, seemingly, never studied due to very poor solubility in suitable solvents); for C 6 R 6 , E 1/2 =−2.49, −1.99 and −1.66 V (R=F, Cl and Br, respectively, vs .…”

Section: Resultsmentioning

confidence: 82%

Section: Discussionmentioning

confidence: 99%

“…The findings of this work clarify the previously unexplained situation with the EAA of C 6 R 6 (R = F, Cl, Br, I) benzenes, amongst which C 6 I 6 is a stronger electron acceptor than C 6 F 6 . [53][54][55][56] It is expected that the discovered counterintuitive effect might be of the general character within main group chemistry and find applications in the design and synthesis of new functional materials. Particularly, E/R and E/R' heavier derivatives (E = Se, Te; R = Cl, Br, I) can be used in the design and synthesis of new CT complexes with tetrachalcogenafulvalenes (chalcogen = S, Se, Te) proposed as molecular (photo) conductors; [57,58] and, as in-chain or/and pendant/side groups, in the design and synthesis of redox active ambipolar polymers for organic memristors.…”

Section: Discussionmentioning

confidence: 99%

“…for C 6 H 6 : À 1.17 eV), i. e., revealing the same χ A -contradictive trend which, however, was not explained. [53] Accordingly, unexplained CV data reveal that amongst C 6 F 6 , [54] C 6 Cl 6 [55] and C 6 Br 6 [56] the former is the weakest, and the latter the strongest, one-electron acceptor (C 6 I 6 was, seemingly, never studied due to very poor solubility in suitable solvents); for C 6 R 6 , E 1/2 = À 2.49, À 1.99 and À 1.66 V (R = F, Cl and Br, respectively, vs. Fc/Fc + in DMF). [53][54][55][56]…”

Section: Chemphyschemmentioning

confidence: 99%

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Tuning Molecular Electron Affinities against Atomic Electronegativities by Spatial Expansion of a π‐System

et al. 2023

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2,1,3‐Benzochalcogenadiazoles C6R4N2E (E/R; E=S, Se, Te; R=H, F, Cl, Br, I) and C6H2R2N2E (E/R’; E=S, Se, Te; R=Br, I) are 10π‐electron hetarenes. By CV/EPR measurements, DFT calculations, and QTAIM and ELI‐D analyses, it is shown that their molecular electron affinities (EAs) increase with decreasing Allen electronegativities and electron affinities of the E and non‐hydrogen R (except Cl) atoms. DFT calculations for E/R+e⋅−→[E/R]⋅− electron capture reveal negative ΔG values numerically increasing with increasing atomic numbers of the E and R atoms; positive ΔS has a minor influence. It is suggested that the EA increase is caused by more effective charge/spin delocalization in the radical anions of heavier derivatives due to contributions from diffuse (a real‐space expanded) p‐AOs of the heavier E and R atoms; and that this counterintuitive effect might be of the general character.

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Study of physisorption of aromatic molecules on hydroxylated α-SiO2 (0 0 1) surface using dispersion-corrected density functional theory

Wang

2023

Computational and Theoretical Chemistry

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Electron affinity of perhalogenated benzenes: A theoretical DFT study

Cited by 4 publications

References 31 publications

Dissociative electron transfer in polychlorinated aromatics. Reduction potentials from convolution analysis and quantum chemical calculations

Dissociative electron transfer in polychlorinated aromatics. Reduction potentials from convolution analysis and quantum chemical calculations

Tuning Molecular Electron Affinities against Atomic Electronegativities by Spatial Expansion of a π‐System

Study of physisorption of aromatic molecules on hydroxylated α-SiO2 (0 0 1) surface using dispersion-corrected density functional theory

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