Chem. J. Chinese Universities ›› 2020, Vol. 41 ›› Issue (9): 2018.doi: 10.7503/cjcu20200339

• Physical Chemistry • Previous Articles     Next Articles

Spectroscopic Characterization of Solvation Effect for a Polarity-Sensitive BDP

ZHAO Yuhui, LI Mingle, LONG Saran(), FAN Jiangli, PENG Xiaojun   

  1. State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian 116024, China
  • Received:2020-06-09 Online:2020-09-10 Published:2020-09-02
  • Contact: LONG Saran E-mail:srlong@dlut.edu.cn
  • Supported by:
    Supported by the National Natural Science Foundation of China(21703025)

Abstract:

Polarity is an important physical and chemical property of solvent systems. Hence it is of a great significance to study the dynamics mechanism of excited photosensitizers influenced by the solvent polarity. A push-pull molecule BDP, which contains dipyrrometheneboron difluoride(BDPIPY) and carbazole groups, was synthesized. Measurements such as steady-state spectra, fluorescence lifetime and femtosecond/nano- second transient absorption were performed on BDP in different polar solvents in order to research spectrosco- pic characters of its excited states. The red-shifted fluorescence spectra with increasing solvent polarity show that it is possible to form an intramolecular charge transfer(ICT) state in excited BDP. Furthermore, fluorescence lifetimes measured by means of time-correlated single photon counting(TCSPC) also prove the existence of ICT state since the fluorescence lifetime of BDP in high-polar solvent is shorter than that in low-polar solvent. Femtosecond transient absorption experiments reveal that a solvation-stabilized relaxed ICT state(ICT′) is formed only in high-polar solvent because of its solvation effect. The time constant of solvation-stabilized process is 3.14 ps obtained by global analysis of the transient absorption spectra based on the sequential model. In addition, nanosecond transient absorption measurements show different lifetimes of the first excited triplet state(T1 state) for BDP in high/low-polar solvent under air or N2 condition. The lifetime of T1 state in low-polar solvent with oxygen is much shorter than that without oxygen, indicating the generation of singlet oxygen by energy transfer. However, there is only a small difference between the lifetimes of T1 state in high-polar solvent with or without oxygen, which indicates that it is difficult to generate singlet oxygen by energy transfer. This result proves that the energy of T1 state in high-polar solvent becomes lower accordingly, which will cause a lower singlet oxygen yield because of the disadvantage in energy transfer. The following DPBF experiment confirms the result above, BDP in low-polar solvent can generate more singlet oxygen than in high-polar solvent. This study provides an effective method for the design of molecular structures and the investigation of polarity effect of photosensitizers.

Key words: Polarity, Solvation, Transient absorption, Photosensitizer, Singlet oxygen

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