Spin-Vibronic Control of Intersystem Crossing in Iodine-Substituted Heptamethine Cyanines

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F60461373%3A22340%2F23%3A43928105" target="_blank" >RIV/60461373:22340/23:43928105 - isvavai.cz</a>

Nalezeny alternativní kódy

RIV/00216224:14310/23:00132203

Výsledek na webu

<a href="https://pubs.acs.org/doi/full/10.1021/acs.joc.3c00005" target="_blank" >https://pubs.acs.org/doi/full/10.1021/acs.joc.3c00005</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1021/acs.joc.3c00005" target="_blank" >10.1021/acs.joc.3c00005</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Spin-Vibronic Control of Intersystem Crossing in Iodine-Substituted Heptamethine Cyanines

Popis výsledku v původním jazyce

Spin-orbit coupling between electronic states of different multiplicity can be strongly coupled to molecular vibrations, and this interaction is becoming recognized as an important mechanism for controlling the course of photochemical reactions. Here, we show that the involvement of spin-vibronic coupling is essential for understanding the photophysics and photochemistry of heptamethine cyanines (Cy7), bearing iodine as a heavy atom in the C3′ position of the chain and/or a 3H-indolium core, as potential triplet sensitizers and singlet oxygen producers in methanol and aqueous solutions. The sensitization efficiency was found to be an order of magnitude higher for the chain-substituted than the 3H-indolium core-substituted derivatives. Our ab initio calculations demonstrate that while all optimal structures of Cy7 are characterized by negligible spin-orbit coupling (tenths of cm-1) with no dependence on the position of the substituent, molecular vibrations lead to its significant increase (tens of cm-1for the chain-substituted cyanines), which allowed us to interpret the observed position dependence. © 2023 American Chemical Society. All rights reserved.

Název v anglickém jazyce

Spin-Vibronic Control of Intersystem Crossing in Iodine-Substituted Heptamethine Cyanines

Popis výsledku anglicky

Spin-orbit coupling between electronic states of different multiplicity can be strongly coupled to molecular vibrations, and this interaction is becoming recognized as an important mechanism for controlling the course of photochemical reactions. Here, we show that the involvement of spin-vibronic coupling is essential for understanding the photophysics and photochemistry of heptamethine cyanines (Cy7), bearing iodine as a heavy atom in the C3′ position of the chain and/or a 3H-indolium core, as potential triplet sensitizers and singlet oxygen producers in methanol and aqueous solutions. The sensitization efficiency was found to be an order of magnitude higher for the chain-substituted than the 3H-indolium core-substituted derivatives. Our ab initio calculations demonstrate that while all optimal structures of Cy7 are characterized by negligible spin-orbit coupling (tenths of cm-1) with no dependence on the position of the substituent, molecular vibrations lead to its significant increase (tens of cm-1for the chain-substituted cyanines), which allowed us to interpret the observed position dependence. © 2023 American Chemical Society. All rights reserved.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10403 - Physical chemistry

Projekt

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

Návaznosti

P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)

Rok uplatnění

2023

Kód důvěrnosti údajů

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

Název periodika

JOURNAL OF ORGANIC CHEMISTRY

ISSN

0022-3263

e-ISSN

1520-6904

Svazek periodika

88

Číslo periodika v rámci svazku

11

Stát vydavatele periodika

US - Spojené státy americké

Počet stran výsledku

13

Strana od-do

6716-6728

Kód UT WoS článku

000982941400001

EID výsledku v databázi Scopus

2-s2.0-85159565768