极性敏感的BDP分子溶剂化效应的光谱性质

doi:10.7503/cjcu20200339

摘要/Abstract

摘要：

合成了具有分子内电荷转移(ICT)性质的三重态光敏剂分子BDP, 研究了其稳态吸收光谱、荧光光谱、荧光寿命、飞秒/纳秒瞬态吸收光谱及诱导产生单线态氧的能力等性质, 发现强极性溶剂对BDP分子的溶剂化效应降低了其ICT态和第一激发三重态(T₁态)的能量, 从而降低了BDP分子单线态氧的产量.

关键词: 极性, 溶剂化, 瞬态吸收, 光敏剂, 单线态氧

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

中图分类号:

O644.1

TrendMD:

赵宇辉, 李明乐, 龙飒然, 樊江莉, 彭孝军. 极性敏感的BDP分子溶剂化效应的光谱性质. 高等学校化学学报, 2020, 41(9): 2018.

ZHAO Yuhui, LI Mingle, LONG Saran, FAN Jiangli, PENG Xiaojun. Spectroscopic Characterization of Solvation Effect for a Polarity-Sensitive BDP. Chem. J. Chinese Universities, 2020, 41(9): 2018.

图/表 7

Scheme 1 Synthetic route of BDP

Fig.1 Absorption(A) and fluorescence(B) spectra of BDP in five solvents with different polarities

Fig.2 Single?exponential fluorescence lifetime decays and fitting results of BDP in toluene(A) and DMSO(B)

Fig.3 Transient absorption spectra at delay time of 1 ps, 100 ps, 1 ns and 5 ns for BDP in toluene(A) and DMSO(B)

Fig.4 EADS of BDP fitted with the sequential model(A, C) and the associated population evolution curves of the EADS components for BDP(B, D)(A, B) Toluene; (C, D) DMSO. Insets of (B) and (D) show the initial stages of evolution of the excited stated relaxation.

Scheme 2 Dynamic scheme of relaxation pathways for BDP after excitation in toluene and DMSO

Fig.5 Changes of characteristic absorption maximums for DPBF

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