Research output: Contribution to journal › Article › peer-review
Twisted BODIPY derivative : intersystem crossing, electron spin polarization and application as a novel photodynamic therapy reagent. / Dong, Yu; Kumar, Prashant; Maity, Partha et al.
In: Physical Chemistry Chemical Physics, Vol. 23, No. 14, 14.04.2021, p. 8641-8652.Research output: Contribution to journal › Article › peer-review
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TY - JOUR
T1 - Twisted BODIPY derivative
T2 - intersystem crossing, electron spin polarization and application as a novel photodynamic therapy reagent
AU - Dong, Yu
AU - Kumar, Prashant
AU - Maity, Partha
AU - Kurganskii, Ivan
AU - Li, Shujing
AU - Elmali, Ayhan
AU - Zhao, Jianzhang
AU - Escudero, Daniel
AU - Wu, Huijian
AU - Karatay, Ahmet
AU - Mohammed, Omar F.
AU - Fedin, Matvey
N1 - Funding Information: J. Z. thanks the NSFC (U2001222, 21673031, 21761142005 and 21911530095) 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) for financial support. D. E. thanks funding from KU Leuven Internal Funds. Publisher Copyright: © the Owner Societies 2021. Copyright: Copyright 2021 Elsevier B.V., All rights reserved.
PY - 2021/4/14
Y1 - 2021/4/14
N2 - The photophysical properties of a heavy atom-free BODIPY derivative with a twisted p-conjugated framework were studied. Efficient intersystem crossing (ISC quantum yield: 56%) and an exceptionally long-lived triplet state were observed (4.5 ms in solid polymer film matrix and 197.5 µs in solution). Time-resolved electron paramagnetic resonance (TREPR) spectroscopy and DFT computations confirmed the delocalization of the triplet state on the whole twisted p-conjugated framework and the zero-field-splitting (ZFS)Dparameter ofD= -69.5 mT, which is smaller than that of 2,6-diiodoBODIPY (D= -104.6 mT). The electron spin polarization (ESP) phase pattern of the triplet state TREPR spectrum of the twisted BODIPY is (a, a, e, a, e, e), which is different from that of 2,6-diiodo BODIPY (e, e, e, a, a, a), indicating that the electron spin selectivity of the ISC of the twisted structure is different from that of the spin orbital coupling effect. According to the computed spin-orbit coupling matrix elements (0.154-1.964 cm-1), together with the matched energy of the S1/Tnstates, ISC was proposed to occurviaS1?T2/T3. The computational results were consistent with TREPR results on the electron spin selectivity (the overpopulation of the TYsublevel of the T1state). The advantage of the long-lived triplet state of the twisted BODIPY was demonstrated by its efficient singlet oxygen (1O2) photosensitizing (F?= 50.0%) even under a severe hypoxia atmosphere (pO2= 0.2%, v/v). A high light toxicity (EC50= 1.0 µM) and low dark toxicity (EC50= 78.5 µM) were observed for the twisted BODIPY, and thus the cellular studies demonstrate its potential as a novel potent heavy atom-free photodynamic therapy (PDT) agent.
AB - The photophysical properties of a heavy atom-free BODIPY derivative with a twisted p-conjugated framework were studied. Efficient intersystem crossing (ISC quantum yield: 56%) and an exceptionally long-lived triplet state were observed (4.5 ms in solid polymer film matrix and 197.5 µs in solution). Time-resolved electron paramagnetic resonance (TREPR) spectroscopy and DFT computations confirmed the delocalization of the triplet state on the whole twisted p-conjugated framework and the zero-field-splitting (ZFS)Dparameter ofD= -69.5 mT, which is smaller than that of 2,6-diiodoBODIPY (D= -104.6 mT). The electron spin polarization (ESP) phase pattern of the triplet state TREPR spectrum of the twisted BODIPY is (a, a, e, a, e, e), which is different from that of 2,6-diiodo BODIPY (e, e, e, a, a, a), indicating that the electron spin selectivity of the ISC of the twisted structure is different from that of the spin orbital coupling effect. According to the computed spin-orbit coupling matrix elements (0.154-1.964 cm-1), together with the matched energy of the S1/Tnstates, ISC was proposed to occurviaS1?T2/T3. The computational results were consistent with TREPR results on the electron spin selectivity (the overpopulation of the TYsublevel of the T1state). The advantage of the long-lived triplet state of the twisted BODIPY was demonstrated by its efficient singlet oxygen (1O2) photosensitizing (F?= 50.0%) even under a severe hypoxia atmosphere (pO2= 0.2%, v/v). A high light toxicity (EC50= 1.0 µM) and low dark toxicity (EC50= 78.5 µM) were observed for the twisted BODIPY, and thus the cellular studies demonstrate its potential as a novel potent heavy atom-free photodynamic therapy (PDT) agent.
UR - http://www.scopus.com/inward/record.url?scp=85104324220&partnerID=8YFLogxK
U2 - 10.1039/d1cp00948f
DO - 10.1039/d1cp00948f
M3 - Article
C2 - 33876025
AN - SCOPUS:85104324220
VL - 23
SP - 8641
EP - 8652
JO - Physical Chemistry Chemical Physics
JF - Physical Chemistry Chemical Physics
SN - 1463-9076
IS - 14
ER -
ID: 28499679