Exploring radical formation and ultrafast intersystem crossing in a heavy-atom-free thiophene derivative

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F10974938%3A_____%2F25%3A25_88_18" target="_blank" >RIV/10974938:_____/25:25_88_18 - isvavai.cz</a>

Nalezeny alternativní kódy

RIV/62156489:43210/25:43927332

Výsledek na webu

<a href="https://doi.org/10.1039/d5cp01512j" target="_blank" >https://doi.org/10.1039/d5cp01512j</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1039/d5cp01512j" target="_blank" >10.1039/d5cp01512j</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Exploring radical formation and ultrafast intersystem crossing in a heavy-atom-free thiophene derivative

Popis výsledku v původním jazyce

The photophysical study of decarboxyranelic acid (DRAc), a thiophene derivative made from strontium ranelate, shows that it can form long-lived radical cation species through a pathway involving triplet states. Femtosecond transient absorption spectroscopy and computational modeling reveal a fast intersystem crossing (ISC) process in water, with a time constant of 1.1 ps and a quantum yield of 27%. The small energy gap between the S1 and T1 states, along with the mixed pi sigma* character of the S1 state, contributes to this rapid ISC, in line with El-Sayed's rule. The results indicate that DRAc's photoreactivity is strongly influenced by the solvent: in water, the high hydrogen-bond donor capacity stabilizes the S1 state, narrows the energy gap, and creates an almost barrier-free ISC pathway. Studies using deuterated solvents show that the ISC rate increases due to stronger stabilization of the S1 state by deuterium bonds. Overall, these results make DRAc a useful model for studying heavy-atom-free molecules with efficient ISC and radical formation, with potential applications in photodynamic therapy and catalysis.

Název v anglickém jazyce

Exploring radical formation and ultrafast intersystem crossing in a heavy-atom-free thiophene derivative

Popis výsledku anglicky

The photophysical study of decarboxyranelic acid (DRAc), a thiophene derivative made from strontium ranelate, shows that it can form long-lived radical cation species through a pathway involving triplet states. Femtosecond transient absorption spectroscopy and computational modeling reveal a fast intersystem crossing (ISC) process in water, with a time constant of 1.1 ps and a quantum yield of 27%. The small energy gap between the S1 and T1 states, along with the mixed pi sigma* character of the S1 state, contributes to this rapid ISC, in line with El-Sayed's rule. The results indicate that DRAc's photoreactivity is strongly influenced by the solvent: in water, the high hydrogen-bond donor capacity stabilizes the S1 state, narrows the energy gap, and creates an almost barrier-free ISC pathway. Studies using deuterated solvents show that the ISC rate increases due to stronger stabilization of the S1 state by deuterium bonds. Overall, these results make DRAc a useful model for studying heavy-atom-free molecules with efficient ISC and radical formation, with potential applications in photodynamic therapy and catalysis.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10608 - Biochemistry and molecular biology

Projekt

<a href="/cs/project/GM21-09692M" target="_blank" >GM21-09692M: Stanovení kvantových limitů v biomolekulách pomocí entanglovaných fotonů generovaných z navázaného kofaktorů, modelováno na OCP proteinu.</a><br>

Návaznosti

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

Rok uplatnění

2025

Kód důvěrnosti údajů

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

Název periodika

PHYSICAL CHEMISTRY CHEMICAL PHYSICS

ISSN

1463-9076

e-ISSN

1463-9084

Svazek periodika

27

Číslo periodika v rámci svazku

33

Stát vydavatele periodika

GB - Spojené království Velké Británie a Severního Irska

Počet stran výsledku

10

Strana od-do

17303-17312

Kód UT WoS článku

001541281900001

EID výsledku v databázi Scopus

2-s2.0-105013669235