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CN-122010980-A - Near infrared two-region material with high fluorescence quantum yield and preparation method and application thereof

CN122010980ACN 122010980 ACN122010980 ACN 122010980ACN-122010980-A

Abstract

The invention belongs to the field of organic photoelectric functional materials, and particularly relates to a near infrared two-region material with high fluorescence quantum yield, and a preparation method and application thereof. The high fluorescence quantum yield near infrared two-region material prepared by the invention has good solubility, has strong light absorption capacity and strong near infrared fluorescence emission capacity in infrared and near infrared regions, and has potential for application in the biomedical field.

Inventors

  • TANG BENZHONG
  • ZHANG JIANQUAN
  • XIE HUILIN
  • ZHAN YONGLIANG
  • Xin Peikun

Assignees

  • 香港中文大学（深圳）

Dates

Publication Date
20260512
Application Date
20260203

Claims (10)

  1. 1. A near infrared two-region material with high fluorescence quantum yield is a compound shown as a formula (I), or a stereoisomer, a geometric isomer or a pharmaceutically acceptable salt of the compound shown as the formula (I); (I); Ring A is 、 、 、 Or (b) ; Each ring B is independently selected from the following groups: 、 、 Or (b) ; Each Ar is independently selected from the following groups: 、 、 、 、 、 、 Or (b) ; R 1 、R 2 、R 3 、R 4 is independently selected from the group consisting of C 1-30 alkyl, C 1-30 alkoxy, C 1-30 alkylthio, and C 1-30 alkylsilyl, which C 1-30 alkyl, C 1-30 alkoxy, C 1-30 alkylthio, and C 1-30 alkylsilyl are independently optionally substituted with substituents selected from F, cl, br, and I; R 5 ~ R 33 is independently selected from H, D, F, cl, br, I, OH, NH 2 、CN、NO 2 , benzene, thiophene, C 1-30 alkyl, C 1-30 alkoxy, C 1-30 alkylthio, and C 1-30 alkylsilyl, which C 1-30 alkyl, C 1-30 alkoxy, C 1-30 alkylthio, and C 1-30 alkylsilyl may independently be optionally substituted with substituents selected from F, cl, br, and I.
  2. 2. The near infrared two-region material of claim 1, wherein R 1 、R 2 、R 3 、R 4 is each independently C 4-10 alkyl, C 4-10 alkoxy, C 4-10 alkylthio, C 4-10 alkylsilyl, said C 4-10 alkyl, C 4-10 alkoxy, C 4-10 alkylthio and C 4-10 alkylsilyl being independently optionally substituted with substituents selected from F, cl, br and I.
  3. 3. The near infrared two-region material of claim 2, wherein R 1 、R 2 、R 3 、R 4 is each independently C 4 linear alkyl, C 5 linear alkyl, C 6 linear alkyl, C 7 linear alkyl, C 8 linear alkyl, C 9 linear alkyl, C 10 linear alkyl.
  4. 4. The near infrared two-region material of claim 3, wherein R 1 、R 3 is linear C 4 H 9 ;R 2 、R 4 and linear C 6 H 13 .
  5. 5. The near infrared two-region material of claim 1, wherein R 5 ~ R 33 is each independently selected from H, D, F, cl, br, I, OH, NH 2 、CN、NO 2 , benzene, thiophene, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl 、-CHF 2 、-CF 3 、-CHFCH 2 F、-CF 2 CHF 2 、-CH 2 CF 3 、-CH 2 CF 2 CHF 2 、 methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, -OCHF 2 、-OCF 3 、-OCHFCH 2 F、-OCF 2 CHF 2 、-OCH 2 CF 3 , or-OCH 2 CF 2 CHF 2 .
  6. 6. The high fluorescence quantum yield near infrared two-region material of claim 1, which is a compound having one of the following structures or a stereoisomer, geometric isomer, or pharmaceutically acceptable salt of a compound having one of the following structures: 。
  7. 7. The method for preparing the near infrared two-region material with high fluorescence quantum yield according to any one of claims 1 to 6, comprising the following steps: step1, obtaining a compound 2 from the compound 1 through Suzuki coupling reaction; step 2, obtaining a compound 3 from the compound 2 through Stille reaction; Step 3, compound 3 is subjected to Stille coupling reaction to obtain compound 4; step 4, compound 4 is subjected to condensation ring closure and nucleophilic substitution reaction to obtain compound 5; step 5, the compound 5 is subjected to Vilsmeier-Haack reaction to obtain a compound formula 6; step 6, obtaining a compound shown in a formula (I) by a Knoevenagel reaction of the compound 6; The reaction route is as follows: 。
  8. 8. A photodecomposition nanoparticle comprising the high fluorescence quantum yield near infrared two-region material of any one of claims 1-7, and a matrix for encapsulating the material.
  9. 9. The photodisruption nanoparticle of claim 8, wherein the matrix is one or both of DSPE-PEG2000-L arginine or DSPE-PEG 2000-FA.
  10. 10. Use of the high fluorescence quantum yield infrared two-region material of any one of claims 1-7, the photodecomposition nanoparticle of claim 8 or 9 for the preparation of a near infrared two-region fluorescence imaging reagent, a tumor photothermal therapeutic reagent or a tumor photodecomposition integrated reagent.

Description

Near infrared two-region material with high fluorescence quantum yield and preparation method and application thereof Technical Field The invention belongs to the field of organic photoelectric functional materials, and particularly relates to a near infrared two-region material with high fluorescence quantum yield, and a preparation method and application thereof. Background Cancer is a serious disease threatening human health, and traditional treatment methods (surgical excision, radiotherapy and chemotherapy) have various limitations such as systemic toxic and side effects, drug resistance, diagnosis and treatment separation. Fluorescent imaging has become an indispensable key technology in modern biomedical diagnosis and image-guided surgery by virtue of its excellent spatial-temporal resolution, ultra-high sensitivity and real-time dynamic imaging capability. Especially, the fluorescence imaging working in the near infrared window benefits from the penetration depth of the near infrared band, can greatly reduce the autofluorescence of biological tissues and reduce tissue absorption and scattering, so that the realization of better signal to noise ratio (SBR) in the imaging of living deep tissues attracts wide attention of global students. In various near infrared materials, organic near infrared fluorescent molecules have more outstanding clinical transformation potential than inorganic materials due to adjustable energy band gap, easy chemical modification, clear structure and good biocompatibility. In recent years, with the development of aromatic condensed ring Y series non-fullerene acceptor materials, the characteristic of strong light absorption capacity in infrared and near infrared bands is attracting the wide attention of researchers. The Y series non-fullerene acceptor material is a near infrared luminescent material constructed by an A-D-A unit (acceptor-donor-acceptor), but due to the planar structure, fluorescence quenching usually occurs in an aggregation state due to strong pi-pi interaction, namely, aggregation Causes Quenching (ACQ), so that PLQY is low in the aggregation state, and the application of the PLQY in fluorescence imaging is limited. The proposal of the aggregation-induced emission (AIE) concept provides an important idea for overcoming the ACQ problem. Based on this, researchers have designed a series of near-infrared AIE luminophores (AIEgens) by introducing twisted, rotatable AIE units into the strong D-a scaffold, whose non-planar structure is effective to inhibit intermolecular pi-pi interactions, thus maintaining higher fluorescence in the aggregated state. However, the light absorption capacity of most near infrared AIEgens is not ideal. Therefore, it is still a technical difficulty how to use the strong light absorption capability of the Y-series non-fullerene materials in the infrared and near infrared bands to enable the aggregation state to maintain high fluorescence in the near infrared region. Disclosure of Invention Aiming at the problems existing in the prior art, the invention provides a near infrared two-region material with high fluorescence quantum yield, and a preparation method and application thereof. The unit with aggregation-induced emission (AIE) characteristic is introduced on the side chain of Y series non-fullerene acceptor thiophene, and the high fluorescence quantum yield near infrared two-region luminescent material is prepared by utilizing mechanisms such as enhancing molecular steric hindrance, improving stacking mode and the like, and can successfully realize mouse vascular imaging and mouse breast cancer treatment after the amphiphilic polymers DSPE-PEG2000-FA and DSPE-PEG 2000-L-arginine are wrapped into nano particles. In one aspect, the invention provides a near infrared two-region material with high fluorescence quantum yield, which is a compound shown as a formula (I), or a stereoisomer, a geometric isomer or a pharmaceutically acceptable salt of the compound shown as the formula (I); (I); Wherein ring A is 、、、Or (b); Each ring B is independently selected from the following groups: 、、 Or (b) ; Each Ar is independently selected from the following groups: 、、、、、、 Or (b) ; R 1、R2、R3、R4 is independently selected from the group consisting of C 1-30 alkyl, C 1-30 alkoxy, C 1-30 alkylthio, and C 1-30 alkylsilyl, which C 1-30 alkyl, C 1-30 alkoxy, C 1-30 alkylthio, and C 1-30 alkylsilyl may independently be optionally substituted with a substituent selected from the group consisting of F, cl, br, and I. R 5 ~ R33 is independently selected from H, D, F, cl, br, I, OH, NH 2、CN、NO2, benzene, thiophene, C 1-30 alkyl, C 1-30 alkoxy, C 1-30 alkylthio, and C 1-30 alkylsilyl, which C 1-30 alkyl, C 1-30 alkoxy, C 1-30 alkylthio, and C 1-30 alkylsilyl may independently be optionally substituted with substituents selected from F, cl, br, and I. In some embodiments, R 1、R2、R3、R4 is each independently C 4-10 alkyl, C 4-10 alkoxy, C 4-10 alkylthio, C 4-10 s