Результаты исследований: Научные публикации в периодических изданиях › статья › Рецензирование
Intersystem Crossing and Electron Spin Selectivity in Anthracene-Naphthalimide Compact Electron Donor-Acceptor Dyads Showing Different Geometry and Electronic Coupling Magnitudes. / Chen, Kepeng; Kurganskii, Ivan V.; Zhang, Xue и др.
в: Chemistry - A European Journal, Том 27, № 27, 12.05.2021, стр. 7572-7587.Результаты исследований: Научные публикации в периодических изданиях › статья › Рецензирование
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TY - JOUR
T1 - Intersystem Crossing and Electron Spin Selectivity in Anthracene-Naphthalimide Compact Electron Donor-Acceptor Dyads Showing Different Geometry and Electronic Coupling Magnitudes
AU - Chen, Kepeng
AU - Kurganskii, Ivan V.
AU - Zhang, Xue
AU - Elmali, Ayhan
AU - Zhao, Jianzhang
AU - Karatay, Ahmet
AU - Fedin, Matvey V.
N1 - Funding Information: J.Z. thanks the NSFC (U2001222, 21673031 and 21761142005) for financial support. M.F. thanks the Ministry of High Education and Science of Russia for access to EPR equipment. I.K. thanks RFBR (grant no. 19‐29‐10035). Publisher Copyright: © 2021 Wiley-VCH GmbH Copyright: Copyright 2021 Elsevier B.V., All rights reserved.
PY - 2021/5/12
Y1 - 2021/5/12
N2 - Anthracene-naphthalimide (An-NI) compact electron donor-acceptor dyads were prepared, in which the orientation and distance between the two subunits were varied by direct connection or with intervening phenyl linker. Efficient intersystem crossing (ISC) and long triplet state lifetime (ΦΔ=92 %, τT=438 μs) were observed for the directly connected dyads showing a perpendicular geometry (81°). This efficient spin-orbit charge transfer ISC (SOCT-ISC) takes 376 fs, inhibits the direct charge recombination (CR) to ground state (1CT→S0, takes 3.04 ns). Interestingly, efficient SOCT-ISC for dyads with intervening phenyl linker (ΦΔ=40 % in DCM) was also observed, although the electron donor and acceptor adopt almost coplanar geometry (dihedral angle: 15°). Time-resolved electron paramagnetic resonance (TREPR) spectroscopy shows that the electron spin polarization of the triplet state, i. e. the electron spin selectivity of ISC, is highly dependent on the dihedral angle and the linker. For the dyads showing weaker coupling between the donor and acceptors, the charge separation and the intramolecular triplet energy transfer are inhibited at 80 K (frozen solution), because both the 3An and 3NI states were observed and the ESP are same as compared to the native anthracene and naphthalimide, which unravel their origin. The dyads were used as triplet photosensitizers for triplet−triplet annihilation upconversion (TTA UC). High UC quantum yield (ΦUC=12.9 %) as well as a large anti-Stokes shift (0.72 eV) was attained by excitation into the CT absorption band.
AB - Anthracene-naphthalimide (An-NI) compact electron donor-acceptor dyads were prepared, in which the orientation and distance between the two subunits were varied by direct connection or with intervening phenyl linker. Efficient intersystem crossing (ISC) and long triplet state lifetime (ΦΔ=92 %, τT=438 μs) were observed for the directly connected dyads showing a perpendicular geometry (81°). This efficient spin-orbit charge transfer ISC (SOCT-ISC) takes 376 fs, inhibits the direct charge recombination (CR) to ground state (1CT→S0, takes 3.04 ns). Interestingly, efficient SOCT-ISC for dyads with intervening phenyl linker (ΦΔ=40 % in DCM) was also observed, although the electron donor and acceptor adopt almost coplanar geometry (dihedral angle: 15°). Time-resolved electron paramagnetic resonance (TREPR) spectroscopy shows that the electron spin polarization of the triplet state, i. e. the electron spin selectivity of ISC, is highly dependent on the dihedral angle and the linker. For the dyads showing weaker coupling between the donor and acceptors, the charge separation and the intramolecular triplet energy transfer are inhibited at 80 K (frozen solution), because both the 3An and 3NI states were observed and the ESP are same as compared to the native anthracene and naphthalimide, which unravel their origin. The dyads were used as triplet photosensitizers for triplet−triplet annihilation upconversion (TTA UC). High UC quantum yield (ΦUC=12.9 %) as well as a large anti-Stokes shift (0.72 eV) was attained by excitation into the CT absorption band.
KW - anthracene
KW - charge transfer
KW - electron spin polarization
KW - intersystem crossing
KW - upconversion
UR - http://www.scopus.com/inward/record.url?scp=85105671694&partnerID=8YFLogxK
U2 - 10.1002/chem.202100611
DO - 10.1002/chem.202100611
M3 - Article
C2 - 33780070
AN - SCOPUS:85105671694
VL - 27
SP - 7572
EP - 7587
JO - Chemistry - A European Journal
JF - Chemistry - A European Journal
SN - 0947-6539
IS - 27
ER -
ID: 28554158