Research Progress in Design， Synthesis and Properties of Organic Octupolar Two-Photon Excited Fluorescence Materials

doi:10.19894/j.issn.1000-0518.240258

Chinese Journal of Applied Chemistry ›› 2025, Vol. 42 ›› Issue (1): 29-41.DOI: 10.19894/j.issn.1000-0518.240258

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Research Progress in Design， Synthesis and Properties of Organic Octupolar Two-Photon Excited Fluorescence Materials

Liang XU¹(), Jian-Peng LIU², Jian QING¹

^1.School of New Energy and Materials，Southwest Petroleum University，Chengdu 610500，China
^2.College of Chemistry and Chemical Engineering，Shantou University，Shantou 515063，China

Received:2024-08-11 Accepted:2024-10-26 Published:2025-01-01 Online:2025-01-24
Contact: Liang XU
About author:liangxu@swpu.edu.cn
Supported by:
the National Natural Science Foundation of China(52073167)

Abstract

Abstract:

Two-photon fluorescence has the advantages of large penetration depth and high spatial resolution， and has an important application prospect in the field of biological imaging. With the continuous innovation and development of related research， organic dipole and quadrupole molecules cannot exhibit the desired two-photon excited fluorescence properties due to the limitations of their own structure and properties， and cannot be designed and regulated in their structure properties. So it is increasingly unable to meet the needs of practical applications. Compared with organic dipole and quadrupole molecules， organic octupolar molecules have obvious advantages in this aspect. Through the diversified structural “clipping” on the multiple structural units （central core， branches and π-conjugate bridges）， the coupling between different branches can be greatly improved and the two-photon absorption cross section can be also improved. At the same time， the water solubility， membrane permeability， biocompatibility and laser stability of the molecule can be further optimized. Therefore， in recent years， more and more research has focused on organic octupole two-photon excited fluorescence materials. The research progress in design， synthesis and properties of organic octupolar two-photon excited fluorescence materials in recent five years is reviewed. The discussion focuses on the design and synthesis of novel central core structure， the improvement of two-photon absorption response of organic blue two-photon excited fluorescence materials， the improvement of photostability and water solubility of two-photon excited fluorescence materials， and the expansion of excitation wavelength from near infrared region 1 to near infrared region 2. The further development trend of this field is also discussed， which provides a basis for the further development and application of organic octupolar two-photon excited fluorescence materials.

Key words: Two-photon excited fluorescence, Organic octupolar molecule, Design and synthesis, Structure and performance, Bioimaging

CLC Number:

O621

Liang XU, Jian-Peng LIU, Jian QING. Research Progress in Design， Synthesis and Properties of Organic Octupolar Two-Photon Excited Fluorescence Materials[J]. Chinese Journal of Applied Chemistry, 2025, 42(1): 29-41.

Figures/Tables 8

Fig.1 （A） The molecular structure of octupolar molecules 1c and 2c；（B） One-photon （full line） and two-photon （dots） absorption spectra of octupolar molecules 1c and 2c in dichloromethane， where the lower abscissa represents the one-photon absorption wavelength， the upper abscissa represents the two-photon absorption wavelength， and the ordinate represents the two-photon absorption cross section［20］

Fig.2 （A） The molecular structure of octupolar molecules CZ-Py2 and CZ-BI2；（B） One-photon excited fluorescence spectra of octupolar molecules CZ-Py2 and CZ-BI2 in different polar solvents （toluene， tetrahydrofuran， dichloromethane， N，N'-dimethylformamide）［22］

Fig.3 （A） The molecular structure of octupolar molecules TA?（TL）?-Ph?（3）?-NPh， TA?（TL）?-Ph?（3）?-CBZ and TA（TL）-Ph（3）-ODZ；（B） Plots of integrated emission intensity vs. input pumping energy for TA（TL）-Ph（3）-CBZ in toluene. Inset： 2PP ASE spectrum of TA（TL）-Ph（3）-CBZ in toluene；（C） Plots of the 2PP ASE efficiency versus the input pumping intensity at 800 nm［27］

Fig.4 （A） The molecular structure of octupolar molecules 3 and 14；（B） UV-Vis absorption and two-photon absorption （TPA） emission spectra of compounds 3 （C42H33N）（C） and 14 （C138H168N4） under the excitation of an 800 nm femtosecond laser. Insets of （B， C） are images of TPA fluorescent emission for two molecules with the same concentration［35］

Fig.5 （A） The molecular structure of octupolar molecule Mito-3arm；（B） Z-stack confocal microscopy images of organoids stained with Mito-3arm were recorded at different imaging depths using one-photon （488 nm） or two-photon （840 nm） excitation；（C） One-photon （488 nm） or two-photon （840 nm） excitation， along with corresponding fluorescence intensity distribution maps， constructed by ImageJ；（D） Two-photon confocal microscopy images of organoids stained with Mito-3arm were obtained at 30 and 120 min［37］

Fig.6 （A） Analysis of the change of fluorescence intensity of molecule 144 with the H2O fraction， inset： the molecular structure of octupolar molecule 144；（B） Fluorescence emission spectra of molecule 144 in different solvents with an excitation wavelength of 365 nm；（C） Fluorescence emission spectra of molecule 144 in DMSO/H2O with different ratios with an excitation wavelength of 365 nm；（D） Two-photon fluorescence imaging of HeLa cancer cells stained with BSA/144 excited at 820 nm with different incubation times［42］

Fig.7 （A） The molecular structure of octupolar molecule F and F2；（B） Two-photon absorption spectra of chromophores F and F2 in THF；（C） Preparation of fluorophore-based periodic mesoporous organosilica nanoparticles （F PMO NPs）， including silylation process of fluorophore F and integration of resulting F—Si precursor in the sol-gel synthesis of E 4S F PMO NPs；（D） Two-photon fluorescence imaging of synthesized fluorophore-PMO NPs［44］

Fig.8 （A） The octupolar molecular structure of 2DCP1 and the two-photon action cross section of 2DCP1 under an excitation wavelength of 780~1080 nm；（B） The octupolar molecular structure of 2DCP2 and the two-photon action cross section of 2DCP2 under an excitation wavelength of 780~1080 nm；（C） Confocal laser scanning microscope images of 4T1 cells treated with 2DCP1 NPs excited by one- and two-photon excitation （scale bar： 50 μm）［46］

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Research Progress in Design， Synthesis and Properties of Organic Octupolar Two-Photon Excited Fluorescence Materials

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