8-(4-Anilino) Bodipy

Collect

BASIC PARAMETERS Find an error

CAS: 321895-93-6
MF: C19H9BN3F2
MW: 328.10266
Synonyms: 8-(4-Anilino) Bodipy

REPORT BY

Yu-Bin Huang

Chinese Academy of Sciences
follow

ZhiGang Xie

Changchun Institute of Applied Chemistry, Chinese Academy of Sciences
follow

Xiang Zhou

Wuhan University
follow

XiaoCheng Weng

Wuhan University
follow

Jianzhang Zhao

University of Bath
follow
Co-reporter: Kejing Xu, Yun Xie, Xiaoneng Cui, Jianzhang Zhao, and Ksenija D. Glusac
pp: 4175-4187
Publication Date(Web):February 20, 2015
DOI: 10.1021/jp509858t
Iodo-bodipy/rhodamine dyads with cyanuric chloride linker were prepared with the goal of achieving pH switching of the triplet excited state formation. The pH switching takes advantage of the acid-activated reversible cyclic lactam↔opened amide transformation of the rhodamine unit and the fluorescence resonance energy transfer (FRET). The photophysical properties of the dyads were studied with steady-state and femtosecond/nanosecond time-resolved transient absorption spectroscopies, electrochemical methods, as well as TD-DFT calculations. Our results show that the model dyad is an efficient triplet state generator under neutral condition, when the rhodamine unit adopts the closed form. The triplet generation occurs at the iodo-bodipy moiety and the triplet state is long-lived, with a lifetime of 51.7 μs. In the presence of the acid, the rhodamine unit adopts an opened amide form, and in this case, the efficient FRET occurs from iodo-bodipy to the rhodamine moiety. The FRET is much faster (τFRET = 81 ps) than the intersystem crossing of iodo-bodipy (τISC = 178 ps), thus suppressing the triplet generation is assumed. However, we found that the additional energy transfer occurs at the longer timescale, which eventually converts the rhodamine-based S1 state to the T1 state localized on the iodo-bodipy unit.

Marcin Ptaszek

University of Maryland
follow

Zhen Shen

Nanjing University
follow

Zhigang Xie

Changchun Institute of Applied Chemistry
follow

Bo Tang

College of Chemistry
follow

Francis D'Souza

University of North Texas
follow
Co-reporter: Gary N. Lim;Dr. Era Maligaspe; Melvin E. Zler;Dr. Francis D'Souza
pp: 17089-17099
Publication Date(Web):
DOI: 10.1002/chem.201404671

Abstract

A novel photosynthetic-antenna–reaction-center model compound, comprised of BF2-chelated dipyrromethene (BODIPY) as an energy-harvesting antenna, zinc porphyrin (ZnP) as the primary electron donor, ferrocene (Fc) as a hole-shifting agent, and phenylimidazole-functionalized fulleropyrrolidine (C60Im) as an electron acceptor, has been synthesized and characterized. Optical absorption and emission, computational structure optimization, and cyclic voltammetry studies were systematically performed to establish the role of each entity in the multistep photochemical reactions. The energy-level diagram established from optical and redox data helped identifying different photochemical events. Selective excitation of BODIPY resulted in efficient singlet energy transfer to the ZnP entity. Ultrafast electron transfer from the 1ZnP* (formed either as a result of singlet–singlet energy transfer or direct excitation) or 1C60* of the coordinated fullerene resulting into the formation of the Fc–(C60.Im:ZnP.+)–BODIPY radical ion pair was witnessed by femtosecond transient absorption studies. Subsequent hole migration to the ferrocene entity resulted in the Fc+–(C60.+Im:ZnP)–BODIPY radical ion pair that persisted for 7–15 μs, depending upon the solvent conditions and contributions from the triplet excited states of ZnP and ImC60, as revealed by the nanosecond transient spectral studies. Better utilization of light energy in generating the long-lived charge-separated state with the help of the present “antenna–reaction-center” model system has been successfully demonstrated.