Triplet Excited State Mechanistic Study of meso-Substituted Methylthio Bodipy Derivative: Time-Resolved Optical and Electron Paramagnetic Resonance Spectral Studies

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F00216305%3A26620%2F24%3APU151447" target="_blank" >RIV/00216305:26620/24:PU151447 - isvavai.cz</a>

Výsledek na webu

<a href="https://chemistry-europe.onlinelibrary.wiley.com/doi/10.1002/cptc.202300320" target="_blank" >https://chemistry-europe.onlinelibrary.wiley.com/doi/10.1002/cptc.202300320</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1002/cptc.202300320" target="_blank" >10.1002/cptc.202300320</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Triplet Excited State Mechanistic Study of meso-Substituted Methylthio Bodipy Derivative: Time-Resolved Optical and Electron Paramagnetic Resonance Spectral Studies

Popis výsledku v původním jazyce

Understanding the intersystem crossing (ISC) mechanism of organic compounds is essential for designing new triplet photosensitizers. Herein, we investigated the ISC mechanism of a heavy atom-free Bodipy derivative with thiomethyl substitution (S-BDP). A long-lived triplet state was observed with nanosecond transient absorption spectroscopy with lifetime of 7.5 ms in a polymer film and 178 mu s intrinsic lifetime in fluid solution, much longer as compared with what was previously reported (apparent triplet lifetime=15.5 mu s). Femtosecond transient absorption studies retrieved an ISC time constant of similar to 3 ns. Time-resolved electron paramagnetic resonance (TREPR) indicated a special triplet electron spin polarization phase (ESP) pattern (a, e, a, e, a, e) for S-BDP, different from the ESP (e, e, e, a, a, a) typical for the spin-orbital coupling (SOC) mechanism. This indicates that the electron spin selectivity of the ISC of S-BDP is different from that of the normal SOC effect in iodo-Bodipy. Simulations of the TREPR spectra give a zero-field-splitting D parameter of -2257 MHz, much smaller as compared to the reference 2,6-diiodo-Bodipy (D=-4380 MHz). The computed SOC matrix elements (0.28-1.59 cm(-1)) and energy gaps for the S-1/T-n states suggest that the energy matching between the S-1 and T-2/T-3 states (supported by the largest k(ISC) similar to 10(9) s(-1)) enhances the ISC for this compound.

Název v anglickém jazyce

Triplet Excited State Mechanistic Study of meso-Substituted Methylthio Bodipy Derivative: Time-Resolved Optical and Electron Paramagnetic Resonance Spectral Studies

Popis výsledku anglicky

Understanding the intersystem crossing (ISC) mechanism of organic compounds is essential for designing new triplet photosensitizers. Herein, we investigated the ISC mechanism of a heavy atom-free Bodipy derivative with thiomethyl substitution (S-BDP). A long-lived triplet state was observed with nanosecond transient absorption spectroscopy with lifetime of 7.5 ms in a polymer film and 178 mu s intrinsic lifetime in fluid solution, much longer as compared with what was previously reported (apparent triplet lifetime=15.5 mu s). Femtosecond transient absorption studies retrieved an ISC time constant of similar to 3 ns. Time-resolved electron paramagnetic resonance (TREPR) indicated a special triplet electron spin polarization phase (ESP) pattern (a, e, a, e, a, e) for S-BDP, different from the ESP (e, e, e, a, a, a) typical for the spin-orbital coupling (SOC) mechanism. This indicates that the electron spin selectivity of the ISC of S-BDP is different from that of the normal SOC effect in iodo-Bodipy. Simulations of the TREPR spectra give a zero-field-splitting D parameter of -2257 MHz, much smaller as compared to the reference 2,6-diiodo-Bodipy (D=-4380 MHz). The computed SOC matrix elements (0.28-1.59 cm(-1)) and energy gaps for the S-1/T-n states suggest that the energy matching between the S-1 and T-2/T-3 states (supported by the largest k(ISC) similar to 10(9) s(-1)) enhances the ISC for this compound.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10400 - Chemical sciences

Projekt

—

Návaznosti

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2024

Kód důvěrnosti údajů

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

Název periodika

ChemPhotoChem

ISSN

2367-0932

e-ISSN

—

Svazek periodika

8

Číslo periodika v rámci svazku

7

Stát vydavatele periodika

DE - Spolková republika Německo

Počet stran výsledku

11

Strana od-do

„“-„“

Kód UT WoS článku

001228234800001

EID výsledku v databázi Scopus

2-s2.0-85193989779