Origin of intersystem crossing in highly distorted organic molecules: a case study with red light-absorbing N,N,O,O-boron-chelated Bodipys

被引:15
作者
Zhang, Xue [1 ]
Sukhanov, Andrey A. [2 ]
Liu, Xi [3 ]
Taddei, Maria [4 ]
Zhao, Jianzhang [1 ]
Harriman, Anthony [5 ]
Voronkova, Violeta K. [2 ]
Wan, Yan [3 ]
Dick, Bernhard [6 ]
Di Donato, Mariangela [4 ,7 ]
机构
[1] Dalian Univ Technol, Frontiers Sci Ctr Smart Mat, Sch Chem Engn, State Key Lab Fine Chem, Dalian 116024, Peoples R China
[2] Russian Acad Sci, Zavoisky Phys Tech Inst, FRC Kazan Sci Ctr, Kazan 420029, Russia
[3] Beijing Normal Univ, Coll Chem, Beijing 100875, Peoples R China
[4] LENS European Lab Nonlinear Spect, Via N Carrara 1, I-50019 Sesto Fiorentino, FI, Italy
[5] Newcastle Univ, Sch Nat & Environm Sci, Mol Photon Lab, Newcastle Upon Tyne NE1 7RU, England
[6] Univ Regensburg, Inst Phys & Theoret Chem, Lehrstuhl Phys Chem, D-93053 Regensburg, Germany
[7] Ist Chim Complessi OrganoMetall, ICCOM, Via Madonna Piano 10, I-50019 Sesto Fiorentino, FI, Italy
关键词
TRIPLET EXCITED-STATE; INTRAMOLECULAR CHARGE-TRANSFER; PHOTOINDUCED ELECTRON-TRANSFER; ANNIHILATION UP-CONVERSION; SINGLET OXYGEN; VISIBLE-LIGHT; FRANCK-CONDON; PHOTOSENSITIZERS; EFFICIENT; DYADS;
D O I
10.1039/d3sc00854a
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
To explore the relationship between the twisted pi-conjugation framework of aromatic chromophores and the efficacy of intersystem crossing (ISC), we have studied a N,N,O,O-boron-chelated Bodipy derivative possessing a severely distorted molecular structure. Surprisingly, this chromophore is highly fluorescent, showing inefficient ISC (singlet oxygen quantum yield, phi<INF>Delta</INF> = 12%). These features differ from those of helical aromatic hydrocarbons, where the twisted framework promotes ISC. We attribute the inefficient ISC to a large singlet-triplet energy gap (Delta E<INF>S<INF>1</INF>/T<INF>1</INF></INF> = 0.61 eV). This postulate is tested by critical examination of a distorted Bodipy having an anthryl unit at the meso-position, for which phi<INF>Delta</INF> is increased to 40%. The improved ISC yield is rationalized by the presence of a T<INF>2</INF> state, localized on the anthryl unit, with energy close to that of the S<INF>1</INF> state. The electron spin polarization phase pattern of the triplet state is (e, e, e, a, a, a), with the T<INF>z</INF> sublevel of the T<INF>1</INF> state overpopulated. The small zero-field splitting D parameter (-1470 MHz) indicates that the electron spin density is delocalized over the twisted framework. It is concluded that twisting of pi-conjugation framework does not necessarily induce ISC, but S<INF>1</INF>/T<INF>n</INF> energy matching may be a generic feature for increasing ISC for a new-generation of heavy atom-free triplet photosensitizers.
引用
收藏
页码:5014 / 5027
页数:14
相关论文
共 124 条
  • [21] BODIPY-Pyrene and Perylene Dyads as Heavy-Atom-Free Singlet Oxygen Sensitizers
    Filatov, Mikhail A.
    Karuthedath, Safakath
    Polestshuk, Pavel M.
    Callaghan, Susan
    Flanagan, Keith J.
    Wiesner, Thomas
    Laquai, Frederic
    Senge, Mathias O.
    [J]. CHEMPHOTOCHEM, 2018, 2 (07): : 606 - 615
  • [22] Control of triplet state generation in heavy atom-free BODIPY-anthracene dyads by media polarity and structural factors
    Filatov, Mikhail A.
    Karuthedath, Safakath
    Polestshuk, Pavel M.
    Callaghan, Susan
    Flanagan, Keith J.
    Telitchko, Maxime
    Wiesner, Thomas
    Laquai, Frederic
    Senge, Mathias O.
    [J]. PHYSICAL CHEMISTRY CHEMICAL PHYSICS, 2018, 20 (12) : 8016 - 8031
  • [23] Generation of Triplet Excited States via Photoinduced Electron Transfer in meso-anthra-BODIPY: Fluorogenic Response toward Singlet Oxygen in Solution and in Vitro
    Filatov, Mikhail A.
    Karuthedath, Safakath
    Polestshuk, Pavel M.
    Savoie, Huguette
    Flanagan, Keith J.
    Sy, Cindy
    Sitte, Elisabeth
    Telitchko, Maxime
    Laquai, Frederic
    Boyle, Ross W.
    Senge, Mathias O.
    [J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2017, 139 (18) : 6282 - 6285
  • [24] PHOTOCHEMISTRY OF 3,4,9,10-PERYLENETETRACARBOXYLIC DIANHYDRIDE DYES .3. SINGLET AND TRIPLET EXCITED-STATE PROPERTIES OF THE BIS(2,5-DI-TERT-BUTYLPHENYL)IMIDE DERIVATIVE
    FORD, WE
    KAMAT, PV
    [J]. JOURNAL OF PHYSICAL CHEMISTRY, 1987, 91 (25) : 6373 - 6380
  • [25] Time-Resolved EPR of Photoinduced Excited States in a Semiconducting Polymer/PCBM Blend
    Franco, Lorenzo
    Toffoletti, Antonio
    Ruzzi, Marco
    Montanari, Luciano
    Carati, Claudio
    Bonoldi, Lucia
    Po, Riccardo
    [J]. JOURNAL OF PHYSICAL CHEMISTRY C, 2013, 117 (04) : 1554 - 1560
  • [26] Frisch M. J. ea., 2016, Gaussian 16 , Rev. A.03
  • [27] Selective photocatalytic reactions with organic photocatalysts
    Fukuzumi, Shunichi
    Ohkubo, Kei
    [J]. CHEMICAL SCIENCE, 2013, 4 (02) : 561 - 574
  • [28] Making triplets from photo-generated charges: observations, mechanisms and theory
    Gibbons, Daire J.
    Farawar, Aram
    Mazzella, Paul
    Leroy-Lhez, Stephanie
    Williams, Rene M.
    [J]. PHOTOCHEMICAL & PHOTOBIOLOGICAL SCIENCES, 2020, 19 (02) : 136 - 158
  • [29] Discovery and high-throughput screening of heteroleptic iridium complexes for photoinduced hydrogen production
    Goldsmith, JI
    Hudson, WR
    Lowry, MS
    Anderson, TH
    Bernhard, S
    [J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2005, 127 (20) : 7502 - 7510
  • [30] In vitro demonstration of the heavy-atom effect for photodynamic therapy
    Gorman, A
    Killoran, J
    O'Shea, C
    Kenna, T
    Gallagher, WM
    O'Shea, DF
    [J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2004, 126 (34) : 10619 - 10631