Solvent-Dependent Excited-State Evolution of Prodan Dyes

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388955%3A_____%2F21%3A00549945" target="_blank" >RIV/61388955:_____/21:00549945 - isvavai.cz</a>

Výsledek na webu

<a href="http://hdl.handle.net/11104/0325840" target="_blank" >http://hdl.handle.net/11104/0325840</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1021/acs.jpcb.1c09030" target="_blank" >10.1021/acs.jpcb.1c09030</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Solvent-Dependent Excited-State Evolution of Prodan Dyes

Popis výsledku v původním jazyce

Excited-state character and dynamics of two 6-(dimethylamino)-2-acylnaphthalene dyes (Prodan and Badan-SCH2CH2OH) were studied by picosecond time-resolved IR spectroscopy (TRIR) in solvents of different polarity and relaxation times: hexane, CD3OD, and glycerol-d8. In all these solvents, near-UV excitation initially produced the same S1(ππ*) excited state characterized by a broad TRIR signal. A very fast decay (3, ∼100 ps) followed in hexane, whereas conversion to a distinct IR spectrum with a ν(C═O) band downshifted by 76 cm–1 occurred in polar/H-bonding solvents, slowing down on going from CD3OD (1, 23 ps) to glycerol-d8 (5.5, 51, 330 ps). The final relaxed excited state was assigned as planar Me2N → C═O intramolecular charge transfer S1(ICT) by comparing experimental and TDDFT-calculated spectra. TRIR conversion kinetics are comparable to those of early stages of multiexponential fluorescence decay and dynamic fluorescence red-shift. This work presents a strong evidence that Prodan-type dyes undergo solvation-driven charge separation in their S1 state, which is responsible for the dynamic fluorescence Stokes shift observed in polar/H-bonding solvents. The time evolution of the optically prepared S1(ππ*) state to the S1(ICT) final state reflects environment relaxation and solvation dynamics. This finding rationalizes the widespread use of Prodan-type dyes as probes of environment dynamics and polarity.

Název v anglickém jazyce

Solvent-Dependent Excited-State Evolution of Prodan Dyes

Popis výsledku anglicky

Excited-state character and dynamics of two 6-(dimethylamino)-2-acylnaphthalene dyes (Prodan and Badan-SCH2CH2OH) were studied by picosecond time-resolved IR spectroscopy (TRIR) in solvents of different polarity and relaxation times: hexane, CD3OD, and glycerol-d8. In all these solvents, near-UV excitation initially produced the same S1(ππ*) excited state characterized by a broad TRIR signal. A very fast decay (3, ∼100 ps) followed in hexane, whereas conversion to a distinct IR spectrum with a ν(C═O) band downshifted by 76 cm–1 occurred in polar/H-bonding solvents, slowing down on going from CD3OD (1, 23 ps) to glycerol-d8 (5.5, 51, 330 ps). The final relaxed excited state was assigned as planar Me2N → C═O intramolecular charge transfer S1(ICT) by comparing experimental and TDDFT-calculated spectra. TRIR conversion kinetics are comparable to those of early stages of multiexponential fluorescence decay and dynamic fluorescence red-shift. This work presents a strong evidence that Prodan-type dyes undergo solvation-driven charge separation in their S1 state, which is responsible for the dynamic fluorescence Stokes shift observed in polar/H-bonding solvents. The time evolution of the optically prepared S1(ππ*) state to the S1(ICT) final state reflects environment relaxation and solvation dynamics. This finding rationalizes the widespread use of Prodan-type dyes as probes of environment dynamics and polarity.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10403 - Physical chemistry

Projekt

<a href="/cs/project/GA21-05180S" target="_blank" >GA21-05180S: Přenos náboje v chromofor-proteinových komplexech tryptofanovými drahami</a><br>

Návaznosti

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2021

Kód důvěrnosti údajů

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

Název periodika

Journal of Physical Chemistry B

ISSN

1520-6106

e-ISSN

1520-5207

Svazek periodika

125

Číslo periodika v rámci svazku

51

Stát vydavatele periodika

US - Spojené státy americké

Počet stran výsledku

10

Strana od-do

13858-13867

Kód UT WoS článku

000733785900001

EID výsledku v databázi Scopus

2-s2.0-85121981821