Spin-Vibronic Coupling Controls the Intersystem Crossing of Iodine-Substituted BODIPY Triplet Chromophores
The result's identifiers
Result code in IS VaVaI
<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F60461373%3A22340%2F23%3A43928100" target="_blank" >RIV/60461373:22340/23:43928100 - isvavai.cz</a>
Result on the web
<a href="https://chemistry-europe.onlinelibrary.wiley.com/doi/10.1002/chem.202303154" target="_blank" >https://chemistry-europe.onlinelibrary.wiley.com/doi/10.1002/chem.202303154</a>
DOI - Digital Object Identifier
<a href="http://dx.doi.org/10.1002/chem.202303154" target="_blank" >10.1002/chem.202303154</a>
Alternative languages
Result language
angličtina
Original language name
Spin-Vibronic Coupling Controls the Intersystem Crossing of Iodine-Substituted BODIPY Triplet Chromophores
Original language description
4,4-Difluoro-4-borata-3a-azonia-4a-aza-s-indacene (BODIPY) dyes are extensively used in various applications of their triplet states, ranging from photoredox catalysis, through triplet sensitization to photodynamic therapy. However, the rational design of BODIPY triplet chromophores by ab initio modelling is limited by their strong interactions of spin, electronic and vibrational dynamics. In particular, spin-vibronic coupling is often overlooked when estimating intersystem crossing (ISC) rates. In this study, a combined experimental and theoretical approach using spin-vibronic coupling to correctly describe ISC in BODIPY dyes was developed. For this purpose, seven π-extended BODIPY derivatives with iodine atoms in different positions were examined. It was found that the heavy-atom effect of iodine atoms is site specific, causing high triplet yields in only some positions. This site-specific ISC was explained by El-Sayed rules, so both the contribution and character of the molecular orbitals involved in the excitation must be considered when predicting the ISC rates. Overall, the rational design of BODIPY triplet chromophores requires using (i) the high-quality electronic structure theory, including both static and dynamical correlations; and (ii) the two-component wave function Hamiltonian, and rationalizing; and (iii) ISC based on the character of the molecular orbitals of heavy atoms involved in the excitation, expanding El-Sayed rules beyond their traditional applications. © 2023 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.
Czech name
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Czech description
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Classification
Type
J<sub>imp</sub> - Article in a specialist periodical, which is included in the Web of Science database
CEP classification
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OECD FORD branch
10403 - Physical chemistry
Result continuities
Project
<a href="/en/project/GA23-07066S" target="_blank" >GA23-07066S: Time-dependent simulations for time-resolved electronic spectroscopies</a><br>
Continuities
P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)
Others
Publication year
2023
Confidentiality
S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů
Data specific for result type
Name of the periodical
CHEMISTRY-A EUROPEAN JOURNAL
ISSN
0947-6539
e-ISSN
1521-3765
Volume of the periodical
30
Issue of the periodical within the volume
4
Country of publishing house
DE - GERMANY
Number of pages
10
Pages from-to
"e202303154"
UT code for WoS article
001108881800001
EID of the result in the Scopus database
2-s2.0-85178118983