Spin-Vibronic Coupling Controls the Intersystem Crossing of Iodine-Substituted BODIPY Triplet Chromophores

Result code in IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388963%3A_____%2F24%3A00577471" target="_blank" >RIV/61388963:_____/24:00577471 - isvavai.cz</a>

Alternative codes found

RIV/60461373:22340/23:43928100

Result on the web

<a href="https://doi.org/10.1002/chem.202303154" target="_blank" >https://doi.org/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>

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, we developed a combined experimental and theoretical approach using spin-vibronic coupling to correctly describe ISC in BODIPY dyes. For this purpose, we examined seven π-extended BODIPY derivatives with iodine atoms in different positions. We 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 explainedby 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 (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.

Czech name

—

Czech description

—

Type

J_imp - Article in a specialist periodical, which is included in the Web of Science database

CEP classification

—

OECD FORD branch

10403 - Physical chemistry

Project

<a href="/en/project/GJ19-20467Y" target="_blank" >GJ19-20467Y: Light-Controlled Reversible Formation of Charge-Separated States</a><br>

Continuities

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Publication year

2024

Confidentiality

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

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