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
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