Synthesis, Photophysical Properties, and Reactive Oxygen Species Generation Mechanism of Type I and Type II D-π-A Hemicyanine Photosensitizers

doi:10.6023/cjoc202411024

Chinese Journal of Organic Chemistry ›› 2025, Vol. 45 ›› Issue (7): 2509-2519.DOI: 10.6023/cjoc202411024 Previous Articles Next Articles

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I型和II型D-π-A半花菁光敏剂的合成、光物理性质与活性氧生成机制

张威光^a^,^†, 张国锋^a^,^†, 李梦^a, 李雪莲^c, 包书红^a, 葛李宵^a, 施志平^a, 申强强^a, 姚李^a^,^*(), 朱三娥^a^,^b^,^*()

^a 合肥大学能源材料与化工学院合肥 230601
^b 中国科学技术大学火灾科学国家重点实验室合肥 230026
^c 中国科学技术大学化学与材料科学学院合肥 230026

收稿日期:2024-11-29 修回日期:2025-01-06 发布日期:2025-02-07
作者简介:
^† 共同第一作者
基金资助:
安徽省高校优秀青年科研项目(2023AH030099); 安徽省自然科学基金(2408085MB044); 安徽省自然科学基金(2308085QB59); 中国博士后科学基金(2023M733378); 国家自然科学基金(21702042); 国家自然科学基金(22305059); 国家自然科学基金(22103010); 国家大学生创新创业训练计划(202411059042); 国家大学生创新创业训练计划(202311059024); 安徽省优秀科研和创新团队(2022AH010096); 安徽省大学生创新创业训练计划(S202411059089); 安徽省大学生创新创业训练计划(S202411059063); 安徽省大学生创新创业训练计划(S202411059069); 安徽省大学生创新创业训练计划(S202411059091); 安徽省大学生创新创业训练计划(S202411059083)

Synthesis, Photophysical Properties, and Reactive Oxygen Species Generation Mechanism of Type I and Type II D-π-A Hemicyanine Photosensitizers

Weiguang Zhang^a, Guofeng Zhang^a, Meng Li^a, Xuelian Li^c, Shuhong Bao^a, Lixiao Ge^a, Zhiping Shi^a, Qiangqiang Shen^a, Li Yao^a^,^*(), San E Zhu^a^,^b^,^*()

^a School of Energy, Materials and Chemical Engineering, Hefei University, Hefei 230601
^b State Key Laboratory of Fire Science, University of Science and Technology of China, Hefei 230026
^c School of Chemistry and Materials Science, University of Science and Technology of China, Hefei 230026

Received:2024-11-29 Revised:2025-01-06 Published:2025-02-07
Contact: *E-mail: yaoli@hfuu.edu.cn; zhuse@hfuu.edu.cn
About author:
^† These authors contributed equally to this work
Supported by:
Research Project for Outstanding Young People in Universities of Anhui Province(2023AH030099); Anhui Provincial Natural Science Foundation(2408085MB044); Anhui Provincial Natural Science Foundation(2308085QB59); China Postdoctoral Science Foundation(2023M733378); National Natural Science Foundation of China(21702042); National Natural Science Foundation of China(22305059); National Natural Science Foundation of China(22103010); National College Students’Innovation and Entrepreneurship Training Program(202411059042); National College Students’Innovation and Entrepreneurship Training Program(202311059024); Anhui Provincial Excellent Scientific Research and Innovation Team(2022AH010096); Anhui Provincial College Student Innovation and Entrepreneurship Training Program(S202411059089); Anhui Provincial College Student Innovation and Entrepreneurship Training Program(S202411059063); Anhui Provincial College Student Innovation and Entrepreneurship Training Program(S202411059069); Anhui Provincial College Student Innovation and Entrepreneurship Training Program(S202411059091); Anhui Provincial College Student Innovation and Entrepreneurship Training Program(S202411059083)

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Abstract

The development of photosensitizers (PSs) with the ability to generate multiple reactive oxygen species (ROS) is of great significance for enhancing the efficacy of photodynamic therapy (PDT). Incorporating a donor (D)-π-acceptor (A) structure within a molecule extends its conjugation system and broadens its light-harvesting range. This design effectively separates the electron clouds of the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO), reduces the singlet-triplet energy gap (ΔE_S-T), promotes intersystem crossing (ISC), and enhances ROS generation efficiency. In this study, triphenylamine was utilized as the donor, indolium iodide as the acceptor, and styrene as the π-bridge to successfully synthesize the D-π-A structured hemicyanine photosensitizer (E)-2-(2-(4'-(diphenylamino)-[1,1'-biphenyl]- 4-yl)vinyl)-1-ethyl-3,3-dimethyl-3H-indol-1-ium iodide (TC). Compared to the monomers 4'-(diphenylamino)-[1,1'-biphenyl]- 4-carbaldehyde (T-CHO) and 1-ethyl-2,3,3-trimethyl-3H-indol-1-ium iodide (YD) (T-CHO: 400~456 nm, YD: 400~440 nm), TC exhibits a significantly expanded light-harvesting range of 400~745 nm. Steady-state and transient fluorescence measurements indicate that both the fluorescence intensity and lifetime of TC are notably reduced in comparison to T-CHO and YD. Theoretical calculations revealed that TC had a ΔE_S-T of 0.73 eV, significantly lower than that of T-CHO (1.50 eV). ROS generation studies further showed that TC exhibited superior performance in generating Type I ROS, Type II ROS, and total ROS compared to the monomers and indocyanine green (ICG). This study provides a solid theoretical foundation and experimental support for the design of novel PSs.

Key words: D-π-A, Type I photosensitizers (PSs), Type II PSs, reactive oxygen species (ROS), triphenylamine, hemicyanine

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Weiguang Zhang, Guofeng Zhang, Meng Li, Xuelian Li, Shuhong Bao, Lixiao Ge, Zhiping Shi, Qiangqiang Shen, Li Yao, San E Zhu. Synthesis, Photophysical Properties, and Reactive Oxygen Species Generation Mechanism of Type I and Type II D-π-A Hemicyanine Photosensitizers[J]. Chinese Journal of Organic Chemistry, 2025, 45(7): 2509-2519.

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Fig. & Tab. 10

Figure 1. Structures of compounds TC, T-CHO and YD

Scheme 1. Synthesis procedures for TC, T-CHO and YD

Figure 2. (a) Steady-state absorption spectra of compounds TC, T-CHO, and YD in CHCl3; (b) Fluorescence emission spectra of compounds TC, T-CHO, and YD in CHCl3 (inset showing an enlarged view of the fluorescence emission spectrum of TC in the 600~700 nm range (excitation wavelength: 400 nm, concentration: 1.0×10－5 mol/L); (c) Fluorescence emission spectrum of compound TC in CHCl3 (excitation wavelength: 540 nm, concentration: 1.0×10－5 mol/L)

Figure 3. Fluorescence decay traces of TC (a), T-CHO (c), and YD (d) obtained by TCSPC in CHCl3 (excited at 400 nm and recorded at 478, 516, and 509 nm, respectively), along with their corresponding biexponential fitting results; (b) Fluorescence decay trace of TC obtained by TCSPC in CHCl3 (excited at 540 nm and recorded at 632 nm), along with its corresponding single-exponential fitting result The red curve, characterized by a narrow half-width at half-maximum and rapid decay, represents the IRF.

Figure 4. Frontier molecular orbitals associated with the singlet and triplet excited states of TC (a) and T-CHO (b) (the orbital diagrams show the configurations of TC and T-CHO in their respective optimized states)

Figure 5. Steady-state absorption spectra showing the changes in ABDA under illumination for 100 s when compounds TC (a), T-CHO (b), and YD (c) are used as PSs; (d) Fitting plot of the changes in ABDA absorption at 377 nm using the equation ln(A/A0) (the concentration of PSs was 1×10－5 mol/L and the ABDA concentration was 1.25×10－5 mol/L. A represents the absorption at 377 nm at different time intervals, A0 is the initial absorption value without illumination, and the light intensity is 10 mW/cm²)

Photosensitizer	k_obs^b/s^－1	v_i^c	Φ_∆^d
TC	1.760	0.1760	0.766
T-CHO YD	0.072 0.048	0.0072 0.0048	0.152 —^e
ICG	0.045	0.0045	0.002

Table 1. The quantum yield of 1O2 for the PSsa

Figure 6. Fluorescence emission spectra of DHR123 under illumination for 100 s when compounds TC (a), T-CHO (b), and YD (c) are used as PSs; (d) Fitting plot of the changes in fluorescence intensity of DHR123 at 525 nm using the equation I/I0 (during testing, the concentration of PSs and DHR123 are both 1×10－5 mol/L. I represents the fluorescence intensity at 525 nm at different time intervals, I0 is the initial fluorescence intensity without illumination, and the light intensity is 10 mW/cm²)

Figure 7. Fluorescence emission spectra of HPF under illumination for 100 s when compounds TC (a), T-CHO (b), and YD (c) are used as PSs; (d) Fitting plot of the changes in fluorescence intensity of HPF at 515 nm using the equation I/I0 (during testing, the concentration of PSs was 1×10－5 mol/L, with a HPF concentration of 1×10－6 mol/L. Here, I represents the fluorescence intensity at 515 nm at different time intervals, I0 is the initial fluorescence intensity without illumination, and the light intensity is 10 mW/cm²

Figure 8. Fluorescence emission spectra of DCFH-DA under illumination for 100 s when compounds TC (a), T-CHO (b), and YD (c) are used as PSs; (d) Fitting plot of the changes in fluorescence intensity of DCFH-DA at 525 nm using the equation I/I0 (during testing, the concentration of PSs was 1×10－5 mol/L, with an DCFH-DA concentration of 4×10－5 mol/L. I represents the fluorescence intensity at 525 nm at different time intervals, I0 is the initial fluorescence intensity without illumination, and the light intensity is 10 mW/cm²)

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I型和II型D-π-A半花菁光敏剂的合成、光物理性质与活性氧生成机制

Synthesis, Photophysical Properties, and Reactive Oxygen Species Generation Mechanism of Type I and Type II D-π-A Hemicyanine Photosensitizers

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