Publication detail

Azomethine phthalimides fluorescent E -> Z photoswitches

GEORGIEV, A. YORDANOV, D. ZHIVKOV, I. DIMOV, D. NAZAROVA, D. WEITER, M. .

Original Title

Azomethine phthalimides fluorescent E -> Z photoswitches

Type

journal article in Web of Science

Language

English

Original Abstract

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-isomers and at PSS in room and liquid nitrogen (77 K) temperatures. In the polar and nonpolar solvents, red-shifted emissions with increased fluorescence quantum (Phi(fl)) yields have been observed at PSS compared to the E-isomers. The molecular rotor behavior was studied in the binary mixture of glycerol:ethanol and the results show a sensitivity of the emission bands depending on the environmental viscosity. Time-resolved fluorescence decay measurements were performed in AcCN and 1,4-DOX as E-isomers and at PSS to estimate the mechanism of fundamental fluorescence bands. We found that dyes at PSS have longer lifetime (tau) compared to the E-isomers, especially in less polar 1,4-DOX.

Keywords

Phthalimides; Fluorescence photoswitches; E -> Z photoisomerization; Rate constant; Molecular rotors

Authors

GEORGIEV, A.; YORDANOV, D.; ZHIVKOV, I.; DIMOV, D.; NAZAROVA, D.; WEITER, M.; .

Released

15. 4. 2020

Publisher

ELSEVIER SCIENCE SA

Location

LAUSANNE

ISBN

1010-6030

Periodical

Journal of Photochemistry and Photobiology A:Chemistry

Year of study

393

Number

112443

State

Swiss Confederation

Pages from

1

Pages to

14

Pages count

14

URL

https://www.sciencedirect.com/science/article/abs/pii/S1010603020302422

BibTex

@article{BUT169571,
  author="GEORGIEV, A. and YORDANOV, D. and ZHIVKOV, I. and DIMOV, D. and NAZAROVA, D. and WEITER, M. and .",
  title="Azomethine phthalimides fluorescent E -> Z photoswitches",
  journal="Journal of Photochemistry and Photobiology A:Chemistry",
  year="2020",
  volume="393",
  number="112443",
  pages="1--14",
  doi="10.1016/j.jphotochem.2020.112443",
  issn="1010-6030",
  url="https://www.sciencedirect.com/science/article/abs/pii/S1010603020302422"
}