TY - JOUR

T1 - Recombination of X-ray-Generated Radical Ion Pairs in Alkane Solution Assembles Optically Inaccessible Exciplexes from a Series of Perfluorinated para-Oligophenylenes with N,N-Dimethylaniline

AU - Nikul'shin, Pavel V

AU - Fedunov, Roman G

AU - Kuibida, Leonid V

AU - Maksimov, Alexander M

AU - Glebov, Evgeni M

AU - Stass, Dmitri V

N1 - Funding: This work was supported by the Ministry of Science and Higher Education of the Russian Federation (contract 075-15-2021-580). The synthesis of compounds was performed in the framework of the state assignment no. 075-01081-23-00.

PY - 2023/4/20

Y1 - 2023/4/20

N2 - We demonstrate that a series of perfluorinated para-oligophenylenes C6F5-(C6F4)n-C6F5 (n = 1-3) produce exciplexes with N,N-dimethylaniline (DMA) in degassed X-irradiated n-dodecane solutions. The optical characterization of the compounds shows that their short fluorescence lifetimes (ca. 1.2 ns) and UV-Vis absorption spectra, overlapping with the spectrum of DMA with molar absorption coefficients of 2.7-4.6 × 104 M-1cm-1, preclude the standard photochemical exciplex formation pathway via selective optical generation of the local excited state of the donor and its bulk quenching by the acceptor. However, under X-rays, the efficient assembly of such exciplexes proceeds via the recombination of radical ion pairs, which delivers the two partners close to each other and ensures a sufficient energy deposition. The exciplex emission is completely quenched by the equilibration of the solution with air, providing a lower bound of exciplex emission lifetime of ca. 200 ns. The recombination nature of the exciplexes is confirmed by the magnetic field sensitivity of the exciplex emission band inherited from the magnetic field sensitivity from the recombination of spin-correlated radical ion pairs. Exciplex formation in such systems is further supported by DFT calculations. These first exciplexes from fully fluorinated compounds show the largest known red shift of the exciplex emission from the local emission band, suggesting the potential of perfluoro compounds for optimizing optical emitters.

AB - We demonstrate that a series of perfluorinated para-oligophenylenes C6F5-(C6F4)n-C6F5 (n = 1-3) produce exciplexes with N,N-dimethylaniline (DMA) in degassed X-irradiated n-dodecane solutions. The optical characterization of the compounds shows that their short fluorescence lifetimes (ca. 1.2 ns) and UV-Vis absorption spectra, overlapping with the spectrum of DMA with molar absorption coefficients of 2.7-4.6 × 104 M-1cm-1, preclude the standard photochemical exciplex formation pathway via selective optical generation of the local excited state of the donor and its bulk quenching by the acceptor. However, under X-rays, the efficient assembly of such exciplexes proceeds via the recombination of radical ion pairs, which delivers the two partners close to each other and ensures a sufficient energy deposition. The exciplex emission is completely quenched by the equilibration of the solution with air, providing a lower bound of exciplex emission lifetime of ca. 200 ns. The recombination nature of the exciplexes is confirmed by the magnetic field sensitivity of the exciplex emission band inherited from the magnetic field sensitivity from the recombination of spin-correlated radical ion pairs. Exciplex formation in such systems is further supported by DFT calculations. These first exciplexes from fully fluorinated compounds show the largest known red shift of the exciplex emission from the local emission band, suggesting the potential of perfluoro compounds for optimizing optical emitters.

KW - X-Rays

KW - Aniline Compounds/chemistry

KW - Alkanes/chemistry

KW - Recombination, Genetic

UR - https://www.scopus.com/record/display.uri?eid=2-s2.0-85158051467&origin=inward&txGid=dea4b67eecdca6bd3ea38f6158fc85dd

U2 - 10.3390/ijms24087568

DO - 10.3390/ijms24087568

M3 - Article

C2 - 37108728

VL - 24

JO - International Journal of Molecular Sciences

JF - International Journal of Molecular Sciences

SN - 1661-6596

IS - 8

M1 - 7568

ER -