Spin–Orbit Charge-Transfer Intersystem Crossing (ISC) in Compact Electron Donor

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Spin–Orbit Charge-Transfer Intersystem Crossing (ISC) in Compact Electron Donor–Acceptor Dyads : ISC Mechanism and Application as Novel and Potent Photodynamic Therapy Reagents. / Wang, Zhijia; Ivanov, Mikhail; Gao, Yuting et al.

In: Chemistry - A European Journal, Vol. 26, No. 5, 22.01.2020, p. 1091-1102.

Research output: Contribution to journal › Article › peer-review

BibTeX

@article{44515af85b3e4a0e80ebb3a409330ced,

title = "Spin–Orbit Charge-Transfer Intersystem Crossing (ISC) in Compact Electron Donor–Acceptor Dyads: ISC Mechanism and Application as Novel and Potent Photodynamic Therapy Reagents",

abstract = "Spin–orbit charge-transfer intersystem crossing (SOCT-ISC) is useful for the preparation of heavy atom-free triplet photosensitisers (PSs). Herein, a series of perylene-Bodipy compact electron donor/acceptor dyads showing efficient SOCT-ISC is prepared. The photophysical properties of the dyads were studied with steady-state and time-resolved spectroscopies. Efficient triplet state formation (quantum yield ΦT=60 %) was observed, with a triplet state lifetime (τT=436 μs) much longer than that accessed with the conventional heavy atom effect (τT=62 μs). The SOCT-ISC mechanism was unambiguously confirmed by direct excitation of the charge transfer (CT) absorption band by using nanosecond transient absorption spectroscopy and time-resolved electron paramagnetic resonance (TREPR) spectroscopy. The factors affecting the SOCT-ISC efficiency include the geometry, the potential energy surface of the torsion, the spin density for the atoms of the linker, solvent polarity, and the energy matching of the 1CT/3LE states. Remarkably, these heavy atom-free triplet PSs were demonstrated as a new type of efficient photodynamic therapy (PDT) reagents (phototoxicity, EC50=75 nm), with a negligible dark toxicity (EC50=78.1 μm) compared with the conventional heavy atom PSs (dark toxicity, EC50=6.0 μm, light toxicity, EC50=4.0 nm). This study provides in-depth understanding of the SOCT-ISC, unveils the design principles of triplet PSs based on SOCT-ISC, and underlines their application as a new generation of potent PDT reagents.",

keywords = "Bodipy, electron spin polarization, perylenes, photodynamic therapy, spin–orbital charge-transfer intersystem crossing (SOCT-ISC), RECOMBINATION, EXCITED-STATE, UP-CONVERSION, TIME-RESOLVED EPR, PHOTOSENSITIZERS, PARAMAGNETIC-RESONANCE, TRIPLET-STATE FORMATION, spin-orbital charge-transfer intersystem crossing (SOCT-ISC), SINGLET OXYGEN GENERATION, RADICAL-ION PAIRS, BODIPY DERIVATIVES",

author = "Zhijia Wang and Mikhail Ivanov and Yuting Gao and Laura Bussotti and Paolo Foggi and Huimin Zhang and Nino Russo and Bernhard Dick and Jianzhang Zhao and {Di Donato}, Mariangela and Gloria Mazzone and Liang Luo and Matvey Fedin",

note = "{\textcopyright} 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.",

year = "2020",

month = jan,

day = "22",

doi = "10.1002/chem.201904306",

language = "English",

volume = "26",

pages = "1091--1102",

journal = "Chemistry - A European Journal",

issn = "0947-6539",

publisher = "Wiley-VCH Verlag",

number = "5",

}

RIS

TY - JOUR

T1 - Spin–Orbit Charge-Transfer Intersystem Crossing (ISC) in Compact Electron Donor–Acceptor Dyads

T2 - ISC Mechanism and Application as Novel and Potent Photodynamic Therapy Reagents

AU - Wang, Zhijia

AU - Ivanov, Mikhail

AU - Gao, Yuting

AU - Bussotti, Laura

AU - Foggi, Paolo

AU - Zhang, Huimin

AU - Russo, Nino

AU - Dick, Bernhard

AU - Zhao, Jianzhang

AU - Di Donato, Mariangela

AU - Mazzone, Gloria

AU - Luo, Liang

AU - Fedin, Matvey

PY - 2020/1/22

Y1 - 2020/1/22

N2 - Spin–orbit charge-transfer intersystem crossing (SOCT-ISC) is useful for the preparation of heavy atom-free triplet photosensitisers (PSs). Herein, a series of perylene-Bodipy compact electron donor/acceptor dyads showing efficient SOCT-ISC is prepared. The photophysical properties of the dyads were studied with steady-state and time-resolved spectroscopies. Efficient triplet state formation (quantum yield ΦT=60 %) was observed, with a triplet state lifetime (τT=436 μs) much longer than that accessed with the conventional heavy atom effect (τT=62 μs). The SOCT-ISC mechanism was unambiguously confirmed by direct excitation of the charge transfer (CT) absorption band by using nanosecond transient absorption spectroscopy and time-resolved electron paramagnetic resonance (TREPR) spectroscopy. The factors affecting the SOCT-ISC efficiency include the geometry, the potential energy surface of the torsion, the spin density for the atoms of the linker, solvent polarity, and the energy matching of the 1CT/3LE states. Remarkably, these heavy atom-free triplet PSs were demonstrated as a new type of efficient photodynamic therapy (PDT) reagents (phototoxicity, EC50=75 nm), with a negligible dark toxicity (EC50=78.1 μm) compared with the conventional heavy atom PSs (dark toxicity, EC50=6.0 μm, light toxicity, EC50=4.0 nm). This study provides in-depth understanding of the SOCT-ISC, unveils the design principles of triplet PSs based on SOCT-ISC, and underlines their application as a new generation of potent PDT reagents.

AB - Spin–orbit charge-transfer intersystem crossing (SOCT-ISC) is useful for the preparation of heavy atom-free triplet photosensitisers (PSs). Herein, a series of perylene-Bodipy compact electron donor/acceptor dyads showing efficient SOCT-ISC is prepared. The photophysical properties of the dyads were studied with steady-state and time-resolved spectroscopies. Efficient triplet state formation (quantum yield ΦT=60 %) was observed, with a triplet state lifetime (τT=436 μs) much longer than that accessed with the conventional heavy atom effect (τT=62 μs). The SOCT-ISC mechanism was unambiguously confirmed by direct excitation of the charge transfer (CT) absorption band by using nanosecond transient absorption spectroscopy and time-resolved electron paramagnetic resonance (TREPR) spectroscopy. The factors affecting the SOCT-ISC efficiency include the geometry, the potential energy surface of the torsion, the spin density for the atoms of the linker, solvent polarity, and the energy matching of the 1CT/3LE states. Remarkably, these heavy atom-free triplet PSs were demonstrated as a new type of efficient photodynamic therapy (PDT) reagents (phototoxicity, EC50=75 nm), with a negligible dark toxicity (EC50=78.1 μm) compared with the conventional heavy atom PSs (dark toxicity, EC50=6.0 μm, light toxicity, EC50=4.0 nm). This study provides in-depth understanding of the SOCT-ISC, unveils the design principles of triplet PSs based on SOCT-ISC, and underlines their application as a new generation of potent PDT reagents.

KW - Bodipy

KW - electron spin polarization

KW - perylenes

KW - photodynamic therapy

KW - spin–orbital charge-transfer intersystem crossing (SOCT-ISC)

KW - RECOMBINATION

KW - EXCITED-STATE

KW - UP-CONVERSION

KW - TIME-RESOLVED EPR

KW - PHOTOSENSITIZERS

KW - PARAMAGNETIC-RESONANCE

KW - TRIPLET-STATE FORMATION

KW - spin-orbital charge-transfer intersystem crossing (SOCT-ISC)

KW - SINGLET OXYGEN GENERATION

KW - RADICAL-ION PAIRS

KW - BODIPY DERIVATIVES

UR - http://www.scopus.com/inward/record.url?scp=85077975932&partnerID=8YFLogxK

U2 - 10.1002/chem.201904306

DO - 10.1002/chem.201904306

M3 - Article

C2 - 31743947

AN - SCOPUS:85077975932

VL - 26

SP - 1091

EP - 1102

JO - Chemistry - A European Journal

JF - Chemistry - A European Journal

SN - 0947-6539

IS - 5

ER -

ID: 23209884

Spin–Orbit Charge-Transfer Intersystem Crossing (ISC) in Compact Electron Donor–Acceptor Dyads: ISC Mechanism and Application as Novel and Potent Photodynamic Therapy Reagents

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