Photoelectron spectrum of 1,1-dithiomethyl-2-nitro-ethene: A combination of push-pull effect and cross-conjugation

Novak, Igor

doi:10.1016/j.elspec.2020.146956

Cited by 3 publications

(1 citation statement)

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“…Cross-conjugated molecules have incomplete π-delocalization, which has been shown to impact photophysical properties by increasing molecular band gaps and lowering λ max absorption. [52][53][54][55] Cross-conjugation has also been found to affect the reversibility and activation free energy barriers of Diels-Alder and thiol addition reactions. [56][57][58] The delocalization effect in 1-E and 3-E leads to higher-lying HOMOs and lower-lying LUMOs relative to 2-E and 4-E, leading to increased HOMO-LUMO gaps.…”

Section: Resultsmentioning

confidence: 99%

Cross-conjugation controls the stabilities and photophysical properties of heteroazoarene photoswitches

Adrion

Lopez

2022

Org. Biomol. Chem.

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Section: Resultsmentioning

confidence: 99%

Cross-conjugation controls the stabilities and photophysical properties of heteroazoarene photoswitches

Adrion

Lopez

2022

Org. Biomol. Chem.

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A new insight into the push‐pull effect of substituents via the stilbene‐like model compounds

Cao

Zeng

2022

J of Physical Organic Chem

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In this paper, authors report on 1‐pyridyl‐2‐arylethenes, 1‐furyl‐2‐arylethylenes, 1,2‐diphenylpropylenes and substituted cinnamyl anilines as stilbene‐like model compounds to investigate the factors dominating the push‐pull effect of substituents via using the nuclear magnetic resonance chemical shift of bridging bond carbon atoms. It is demonstrated that the maximum push‐pull effect is not always between the strong electron‐donating D and strong electron‐accepting A groups in D‐π‐A compounds. The action mode of push‐pull effect of substituents in D‐π‐A compounds is dominated by their molecular parent structure. The contribution of field/inductive effect and conjugative effect of a group to the push‐pull effect is unequal. When the D‐π‐A parent molecule is in a plane, the influence of field/inductive effect of a group on the push‐pull effect is greater than or close to that of its conjugative effect does. Although the parent molecule is sterically twisted, the push‐pull effect is mainly dependent on the conjugative effect of a group. The results of this paper can provide us a new insight into the push‐pull effect of substituents.

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Cross-conjugation controls the stabilities and photophysical properties of heteroazoarene photoswitches

Adrion

Lopez

2021

Preprint

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Azoarene photoswitches are versatile molecules that interconvert from their E-isomer to their Z-isomer with light. Azobenzene is a prototypical photoswitch but its derivatives can be poorly suited for in vivo applications such as photopharmacology due to undesired photochemical reactions promoted by ultraviolet light and its relatively short half-life (t1/2) of the Z-isomer (2 days). Experimental and computational studies suggest that these properties (λmax of the E isomer and t1/2 of the Z-isomer) are inversely related. We identified isomeric azobisthiophenes and azobisfurans from a high-throughput screening study of 1700 azoarenes as photoswitch candidates with improved λmax and t1/2 values relative to azobenzene. We used density functional theory to predict the activation free energies, reaction free energies, and vertical excitation energies of the E- and Z-isomers of 2,2- and 3,3-substituted azobisthiophenes and azobisfurans. The half-lives depend on whether the heterocycles are 𝜋-conjugated or cross-conjugated with the diazo 𝜋-bond. The 2,2-substituted azoarenes both have t1/2 values on the scale of 1 hour, while the 3,3-analogues have computed half-lives of 40 (thiophene) and 230 (furan) years. The 2,2-substituted heteroazoarenes have significantly higher λmax absorptions than their 3,3-substituted analogs: 76 nm for azofuran and 77 nm for azothiophene.

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Photoelectron spectrum of 1,1-dithiomethyl-2-nitro-ethene: A combination of push-pull effect and cross-conjugation

Cited by 3 publications

References 12 publications

Cross-conjugation controls the stabilities and photophysical properties of heteroazoarene photoswitches

Cross-conjugation controls the stabilities and photophysical properties of heteroazoarene photoswitches

A new insight into the push‐pull effect of substituents via the stilbene‐like model compounds

Cross-conjugation controls the stabilities and photophysical properties of heteroazoarene photoswitches

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