Azomethine phthalimides fluorescent E -> Z photoswitches

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F00216305%3A26310%2F20%3APU139542" target="_blank" >RIV/00216305:26310/20:PU139542 - isvavai.cz</a>

Výsledek na webu

<a href="https://www.sciencedirect.com/science/article/abs/pii/S1010603020302422" target="_blank" >https://www.sciencedirect.com/science/article/abs/pii/S1010603020302422</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1016/j.jphotochem.2020.112443" target="_blank" >10.1016/j.jphotochem.2020.112443</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Azomethine phthalimides fluorescent E -> Z photoswitches

Popis výsledku v původním jazyce

Herein, we report the synthesis and E -> Z photoswitching behavior of two 4-substituted azomethine phthalimides containing anthracenyl and 4-(dimethylamino)phenyl moieties (EAMP1 and EAMP2). These compounds represent newly synthesized and unstudied photoswitches with dual fluorescence properties as E-isomers and at photostationary state (PSS) depending on the solvent polarity. Steady-state fluorescence measurements were performed in various solvents and the results show strong sensitivity on the environmental polarity. The kinetics of E -> Z photoswitching to PSS was studied in AcCN by visible light activation at 410 nm (EAMP1) and long wavelength UV-light activation at 350 nm (EAMP2). The quantitative and qualitative performance of the switching behavior was evaluated by the degree of photoisomerization (R) and the rate constant (k). It was found for EAMP1 R = 6.95 %, k = 8.87 x 10(-4) s(-1) and EAMP2 R = 88.72 %, k = 4.00 x 10(-4) s(-1), respectively. The reason for the lower photoconversion of EAMP1 compared to the EAMP2 was analyzed through optimization of the molecular geometry of E- and Z-isomers in the ground state (S-0) and first excited state (S-1) by DFT/TD-DFT calculations with B3LYP/6-31 + G(d,p) level of theory using IEFPCM in AcCN. It was found that Eisomers in the S-0 have nonplanar conformation, while the Z-isomer of EAMP1 prefers twisted conformation and the Z-isomer of EAMP2 T-shaped conformation is energetically advantageous compared to the twisted one. The reason is the weak H.....pi noncovalent interaction (NCI) between 4-(dimethylamino)phenyl moiety and phthalimide ring. Moreover, the Z-isomer of EAMP2 is unusual stable up to 600 min at room temperature in dark compared to the EAMP1, which undergoes full Z -> E relaxation for less than 60 min at the same conditions. The Z -> E relaxation of EAMP2 is achieved for 90 min at 60 degrees C. The fluorescence E -> Z switching behavior was studied by emission measurements in AcCN and 1,4-DOX as E-isome

Název v anglickém jazyce

Azomethine phthalimides fluorescent E -> Z photoswitches

Popis výsledku anglicky

Herein, we report the synthesis and E -> Z photoswitching behavior of two 4-substituted azomethine phthalimides containing anthracenyl and 4-(dimethylamino)phenyl moieties (EAMP1 and EAMP2). These compounds represent newly synthesized and unstudied photoswitches with dual fluorescence properties as E-isomers and at photostationary state (PSS) depending on the solvent polarity. Steady-state fluorescence measurements were performed in various solvents and the results show strong sensitivity on the environmental polarity. The kinetics of E -> Z photoswitching to PSS was studied in AcCN by visible light activation at 410 nm (EAMP1) and long wavelength UV-light activation at 350 nm (EAMP2). The quantitative and qualitative performance of the switching behavior was evaluated by the degree of photoisomerization (R) and the rate constant (k). It was found for EAMP1 R = 6.95 %, k = 8.87 x 10(-4) s(-1) and EAMP2 R = 88.72 %, k = 4.00 x 10(-4) s(-1), respectively. The reason for the lower photoconversion of EAMP1 compared to the EAMP2 was analyzed through optimization of the molecular geometry of E- and Z-isomers in the ground state (S-0) and first excited state (S-1) by DFT/TD-DFT calculations with B3LYP/6-31 + G(d,p) level of theory using IEFPCM in AcCN. It was found that Eisomers in the S-0 have nonplanar conformation, while the Z-isomer of EAMP1 prefers twisted conformation and the Z-isomer of EAMP2 T-shaped conformation is energetically advantageous compared to the twisted one. The reason is the weak H.....pi noncovalent interaction (NCI) between 4-(dimethylamino)phenyl moiety and phthalimide ring. Moreover, the Z-isomer of EAMP2 is unusual stable up to 600 min at room temperature in dark compared to the EAMP1, which undergoes full Z -> E relaxation for less than 60 min at the same conditions. The Z -> E relaxation of EAMP2 is achieved for 90 min at 60 degrees C. The fluorescence E -> Z switching behavior was studied by emission measurements in AcCN and 1,4-DOX as E-isome

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10403 - Physical chemistry

Projekt

<a href="/cs/project/GA19-22783S" target="_blank" >GA19-22783S: Molekulární materiály pro získávání energie: směrem k překročení limitů</a><br>

Návaznosti

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

Rok uplatnění

2020

Kód důvěrnosti údajů

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

Název periodika

Journal of Photochemistry and Photobiology A:Chemistry

ISSN

1010-6030

e-ISSN

—

Svazek periodika

393

Číslo periodika v rámci svazku

112443

Stát vydavatele periodika

CH - Švýcarská konfederace

Počet stran výsledku

14

Strana od-do

1-14

Kód UT WoS článku

000528279200010

EID výsledku v databázi Scopus

—