Photochemistry Driven by Excited-State Aromaticity Gain or Antiaromaticity Relief

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388963%3A_____%2F23%3A00569687" target="_blank" >RIV/61388963:_____/23:00569687 - isvavai.cz</a>

Výsledek na webu

<a href="https://doi.org/10.1002/chem.202203748" target="_blank" >https://doi.org/10.1002/chem.202203748</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1002/chem.202203748" target="_blank" >10.1002/chem.202203748</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Photochemistry Driven by Excited-State Aromaticity Gain or Antiaromaticity Relief

Popis výsledku v původním jazyce

Gain of aromaticity or relief of antiaromaticity along a reaction path are important factors to consider in mechanism studies. Analysis of such changes along potential energy surfaces has historically focused on reactions in the electronic ground state (S0), but can also be used for excited states. In the lowest ππ* states, the electron counts for aromaticity and antiaromaticity follow Baird's rule where 4n π-electrons indicate aromaticity and 4n+2 π-electrons antiaromaticity. Yet, there are also cases where Hückel's rule plays a role in the excited state. The electron count reversals of Baird's rule compared to Hückel's rule explain many altered physicochemical properties upon excitation of (hetero)annulene derivatives. Here we illustrate how the gain of excited-state aromaticity (ESA) and relief of excited-state antiaromaticity (ESAA) have an impact on photoreactivity and photostability. Emphasis is placed on recent findings supported by the results of quantum chemical calculations, and photoreactions in a wide variety of areas are covered.

Název v anglickém jazyce

Photochemistry Driven by Excited-State Aromaticity Gain or Antiaromaticity Relief

Popis výsledku anglicky

Gain of aromaticity or relief of antiaromaticity along a reaction path are important factors to consider in mechanism studies. Analysis of such changes along potential energy surfaces has historically focused on reactions in the electronic ground state (S0), but can also be used for excited states. In the lowest ππ* states, the electron counts for aromaticity and antiaromaticity follow Baird's rule where 4n π-electrons indicate aromaticity and 4n+2 π-electrons antiaromaticity. Yet, there are also cases where Hückel's rule plays a role in the excited state. The electron count reversals of Baird's rule compared to Hückel's rule explain many altered physicochemical properties upon excitation of (hetero)annulene derivatives. Here we illustrate how the gain of excited-state aromaticity (ESA) and relief of excited-state antiaromaticity (ESAA) have an impact on photoreactivity and photostability. Emphasis is placed on recent findings supported by the results of quantum chemical calculations, and photoreactions in a wide variety of areas are covered.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10401 - Organic chemistry

Projekt

Výsledek vznikl pri realizaci vícero projektů. Více informací v záložce Projekty.

Návaznosti

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2023

Kód důvěrnosti údajů

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Název periodika

Chemistry - A European Journal

ISSN

0947-6539

e-ISSN

1521-3765

Svazek periodika

29

Číslo periodika v rámci svazku

19

Stát vydavatele periodika

DE - Spolková republika Německo

Počet stran výsledku

30

Strana od-do

e202203748

Kód UT WoS článku

000937908600001

EID výsledku v databázi Scopus

2-s2.0-85148621163