Research Progress in Synthesis, Properties and Application of Subphthalocyanine

doi:10.6023/cjoc202211020

Abstract

Subphthalocyanine, as a typical contracted analogue of phthalocyanine, exhibits novel cone structure, excellent luminescent properties and high flexibility of modification, which enables it as a new type of fluorescent dye with great research prospects. It has been proved that simple modifications of the axial, peripheral or central ring structure of subphthalocyanine can effectively regulate its physical and chemical properties, such as solubility, absorption/fluorescence emission, fluorescence quantum yield and singlet oxygen yield, and these properties have attracted extensive attentions from chemists in recent years. This review introduces the structures, properties and research significance of subphthalocyanine. Then, the progress in the synthesis, the relationship between properties and molecular structure of subphthalocyanin, and their applications in the area of biochemistry, material chemistry and environmental chemistry are reviewed emphatically. Finally, the development status of subphthalocyanine is summarized, and the further development of subphthalocyanine is discussed and proposed.

Key words: subphthalocyanine, structures, photoelectric properties, application

Cite this article

Shutong Zhou, Shengnan Tu, Zijian Gao, Yemei Wang, Shasha Sun. Research Progress in Synthesis, Properties and Application of Subphthalocyanine[J]. Chinese Journal of Organic Chemistry, 2023, 43(8): 2628-2646.

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Fig. & Tab. 34

Figure 1. Structures of phthalocyanine, metal-phthalocyanine and subphthalocyanine

Figure 2. Structures of co-crystal 1, 2 and inclusion compound 3 Reprinted with permission from Ref. [24]. Copyright ? 2018, American Chemical Society and from Ref. [25]. Copyright ? The Royal Society of Chemistry 2022.

Figure 3. Typical UV/vis absorption spectra of Pc and SubPc

Figure 4. Structures of C3 or C1-symmetric SubPcs 5~8

Figure 5. Structures of SubPc 9~11

Figure 6. Structures of SubPc 12 and 13

Scheme 1. Synthesis of axially substituted SubPcs via a triflate-SubPc 14 intermediate

Figure 7. Structures of SubPc 15~18

Scheme 2. Synthesis of axially substituted SubPcs via a SubPc(Cl)?AlCl3 19 intermediate

Figure 8. Structures of SubPc 20~24

Scheme 3. Synthesis of axially substituted SubPcs via a SubPc(Cl)?Me3SiNu 25 intermediate

Figure 9. Structures of SubPc 26 and 27

Figure 10. Structures of SubPc 28 and 29

Figure 11. Structures of SubPc 30~32

Figure 12. Structures of SubPc 33~36

Figure 13. Structures of SubPc 38~40

Figure 14. (a) Structures of SubPc 41 and 42; (b) model of 41 and 42, and the corresponding homochiral columnar stacks Reprinted with permission from Ref. [48]. Copyright ? 2020, American Chemical Society.

Figure 15. Structures of SubPc 43~46

Figure 16. Structures of SubPc 47~51

Figure 17. Schematic energy level diagram for devices with (a) CuPc or (b) SubPc 4 as the donor layer Reprinted with permission from Ref. [62]. Copyright ? 2006, American Chemical Society.

Compound	X	λ_abs/nm	λ_em/nm
4	Cl	564	569
52	F	562	568
53	Br	566	572
54		561	570
55		564	571
56		567	575
57		569	577
58		566	581
59		562	571
60		563	592

Table 1. Structures of SubPcs 4 and 52~60, and their absorption/emission wavelength

Figure 18. Structures of SubPc 30 and 61

Figure 19. (a) Structures of SubPc 4, SubNc 62 and α-6T; (b) Schematic representation of α-6T/SubPc/SubNc architecture

Figure 20. Structures of SubPc 30 and 63~65

Figure 21. Structures of SubPc 66 and 67

Figure 22. Structures of SubPc 68, 69 and PBDBT-2F

Figure 23. Structures of SubPc 70~74

Figure 24. Structures of SubPc 75~77

Figure 25. Structures of SubPc 78~85

Figure 26. Structures of SubPc 86

Figure 27. (a) Structures of SubPc 87~89; (b)Visualization of the intracellular fluorescence of SubPc 87~89 (after incubation for 4 h) and various subcellular trackers in HeLa cells The corresponding bright-field and merged images are given in lines 1 and 5, respectively. The figures in line 2 show the fluorescence intensity profiles of 87~89 and the corresponding images of Hoechst 33342 and Lyso Tracker Green DND-26 in lines 3 and 4, respectively. Scale bar: 5 μm.

Figure 28. Structures of SubPc 90

Figure 29. (a) Structures of SubPc 91; (b) The absorption spectral change of SubPc 91 upon addition of tetrabutylammonium fluoride (TBAF); (c) Absorption ratio of SubPc 91 between 696 nm and 565 nm to the anions; (d) Normalized absorption spectra of 91 in the presence of anions Reprinted with permission from Ref. [80]. Copyright ? 2007 The Chemical Society of Japan.

Figure 30. Structures of SubPc 92

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