Antiaromaticity-promoted radical anion stability in α-vinyl heterocyclics

Abstract

As an electron-rich species, radical anions have a wide range of applications in organic synthesis. In addition, aromaticity is an essential concept in chemistry that has attracted considerable attention from...

Probing Near-infrared Absorbance of E and Z Diazene Isomers via Antiaromaticity

“…We have demonstrated that the antiaromaticity contributes to significant red shifts at the main transition bands through TD-DFT calculations, in line with the experimental study by Zhang’s group very recently . This work highlights a potential application of antiaromaticity in photochemistry, similar to our previous finding on the application of such a concept in stabilizing radicals and radical anions. ,, …”

“…58 This work highlights a potential application of antiaromaticity 71 in photochemistry, similar to our previous finding on the application of such a concept in stabilizing radicals and radical anions. 61,72,73 ■ COMPUTATIONAL DETAILS The PBE0 functional is widely regarded as a well-performing functional for molecules of this size. 74,75 The PBE0 hybrid functional provides excellent results, the electronic vertical transitions in particular, in many benchmarks compared with other functionals.…”

Unravelling the factors affecting the stability and reactivity of dehydro-pyrazole, isothiazole and isoxazole radical isomers: a computational study

“…36 Zhu and coworkers have investigated the relationship between the aromaticity and radical stability of a-methyl and a-vinyl heterocycles by DFT calculations. 37,38 Moreover, given the recent discovery of multiple heterocyclic species, the ring-opening of heterocyclic radicals via unimolecular reactions can result in many intermediates, ring-opening products, and fragmentation products that are highly valuable for numerous applications. [39][40][41] Previously, we reported the factors stabilizing the five-membered heterocyclic radicals, where competition between the delocalization of radical electrons or spin and the ring strain governed the overall stability.…”

Exploiting heterocycle aromaticity to fabricate new hot exciton materials

“…[21][22][23] In recent years, aromaticity studies on polycyclic hydrocarbons have attracted broad theoretical and synthetic attention and made a series of important leaps forward with increasing interest in their application as organic semiconductors, especially antiaromatics and diradicaloids. [24][25][26][27] Some theoretical studies have shown that excited state aromaticity could be used to rationalize the low triplet energy levels in several molecular systems [28][29][30][31] and subsequently Fallon et al 32 and Wang et al 33,34 have successfully applied excited state aromaticity to design singlet fission materials. [35][36][37] Accordingly, exploiting aromaticity rules for the rational design of optical function materials with tunable optoelectronic characteristics is a formidable work and still remains largely unexplored.…”