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CN-121974941-A - Triarylboron-modified aza [7] spiroalkene derivative with two-photon absorption and two-state circular polarization luminescence characteristics

CN121974941ACN 121974941 ACN121974941 ACN 121974941ACN-121974941-A

Abstract

Triarylboron-modified aza [7] spiroalkene derivatives with two-photon absorption and two-state circular polarization luminescence characteristics. The invention belongs to the technical field of organic photoelectric functional materials, and provides an aza [7] spiroalkene derivative with two-state circularly polarized luminescence and two-photon absorption properties. The fluorescent quantum efficiency of the pure carbon [7] spiroalkene is obviously improved, and the double-state CPL in a single organic molecule is realized and the strong TPA characteristic is realized.

Inventors

  • ZHAO CUIHUA
  • WANG RUNZE

Assignees

  • 山东大学

Dates

Publication Date
20260505
Application Date
20260203

Claims (10)

  1. 1. The triarylboron modified aza [7] spiroalkene derivative with two-photon absorption and two-state circular polarization luminescence characteristics is characterized in that the structural formula is one of the following formulas: 。
  2. 2. The process for the preparation of aza [7] spiroalkene derivatives according to claim 1, characterized in that the following synthetic route (1) or (2) is adopted: ; route (1) is adopted, comprising: Under inert atmosphere, oBr-A7H, pdCl 2 (dppf)、B 2 Pin 2 and KOAc are uniformly mixed, then 1, 4-dioxane is added, and the temperature is increased for reaction to obtain oBpin-A7H; Sequentially adding a re-evaporated and dried toluene solution, ethanol and water into a mixed system of oBpin-A7H, 4-Br-FBPh and Pd (PPh 3 ) 4 and K 2 CO 3 ), and heating to react to obtain oFBPh-A7H; Or, taking route (2), comprising: Dissolving A7H in chloroform, and adding N-bromosuccinimide to react to obtain oDiBr-A7H; Mixing oDiBr-A7H, pdCl 2 (dppf)、B 2 Pin 2 , KOAc and 1, 4-dioxane uniformly, and reacting oBiBpin-A7H; under the protection of inert atmosphere, sequentially adding dry and degassed toluene, ethanol and water into a mixture of oBiBpin-A7H, 4-Br-FBPh and Pd (PPh 3 ) 4 and K 2 CO 3 ), and heating to react to obtain oBiFBPh-A7H.
  3. 3. The method for producing an aza [7] helicene derivative according to claim 2, wherein the molar ratio of oBr-A7H, pdCl 2 (dppf)、B 2 Pin 2 to KOAc is 1.83-2:0.13-0.15:2.56-2.6:5.49-5.6.
  4. 4. The process for the preparation of aza [7] helicene derivatives according to claim 2, wherein the molar ratio of oBpin-A7H, 4-Br-FBPh, pd (PPh 3 ) 4 and K 2 CO 3 ) is 0.34-0.36:0.41-0.42:0.01-0.012:1.02-1.05.
  5. 5. The method for preparing aza [7] spiroalkene derivatives according to claim 2, wherein the molar ratio of A7H to N-bromosuccinimide is 1:2-2.1.
  6. 6. The method for preparing aza [7] helicene derivative according to claim 2, wherein the molar ratio of iBr-A7H, pdCl 2 (dppf)、B 2 Pin 2 and KOAc is 3.20-3.25:0.45-0.46:8.96-8.98:19.20-19.25.
  7. 7. The process for preparing aza [7] helicene derivatives according to claim 2, wherein the molar ratio of oBiBpin-A7H, 4-Br-FBPh, pd (PPh 3 ) 4 and K 2 CO 3 ) is 0.28-0.30:0.67-0.68:0.02-0.03:1.68-1.69.
  8. 8. The method for preparing an aza [7] helicene derivative according to claim 2, wherein the method for synthesizing 4-Br-FBPh comprises: Uniformly mixing a methyl tertiary butyl ether solution of 2, 6-bis (trifluoromethyl) bromobenzene and an n-hexane solution of n-butyllithium, reacting, adding (4-bromophenyl) potassium trifluoroborate into the mixture after the reaction is finished, and heating to react to obtain 4-Br-FBPh; Or the molar ratio of the 2, 6-bis (trifluoromethyl) bromobenzene to the n-butyllithium to the potassium (4-bromophenyl) trifluoroborate is 6.85-6.88:8.91-8.92:3.43-3.45.
  9. 9. The use of an aza [7] spiroalkene derivative according to claim 1 or an aza [7] spiroalkene derivative prepared by the method according to any one of claims 2 to 8 in the fields of 3D display, photoelectric information storage and processing, and biological probes.
  10. 10. The use of an aza [7] spiroalkene derivative according to claim 1 or an aza [7] spiroalkene derivative prepared by the method according to any one of claims 2 to 8 in the fields of two-photon excitation and two-state CPL fluorescence imaging.

Description

Triarylboron-modified aza [7] spiroalkene derivative with two-photon absorption and two-state circular polarization luminescence characteristics Technical Field The invention belongs to the technical field of organic photoelectric functional materials, and particularly relates to an aza [7] spiroalkene derivative with two-photon absorption and two-state circular polarization luminescence properties. Background The disclosure of this background section is only intended to increase the understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art already known to those of ordinary skill in the art. Organic small molecule materials with Circular Polarized Luminescence (CPL) characteristics are receiving great attention due to the wide application of the organic small molecule materials in 3D display, information storage, high-security encryption, biological imaging and other front-edge technologies. The overall performance of CPL can be assessed by the CPL brightness (B CPL=ε×ΦF× |glum/2) parameter. In addition to pursuing high CPL brightness, achieving materials with significant CPL signals (i.e., bimodal CPL) in both solution and aggregate states is also an important topic currently in need of solution. The bimodal CPL can solve the contradiction between the aggregation fluorescence quenching (ACQ) and the Aggregation Induced Emission (AIE) effect, thereby ensuring that the organic micromolecular material obtains stable CPL property which is not interfered by concentration. On the other hand, in order to further expand the application range of molecules containing CPL characteristics, the combination of two-photon absorption (TPA) characteristics and CPL small organic molecule systems has important significance. The molecule with the two-photon absorption characteristic has the unique advantages of high three-dimensional spatial resolution, small photodamage, large tissue penetration depth and the like. Recently, the inventors have obtained an aza [7] spiroalkene emitter derivative oBPh-NH-A7H with a strong charge transfer state (CT) using a triarylboron unit that is strongly electron-withdrawing and sterically hindered, which molecule exhibits CPL brightness (B CPL) in solution as high as 69.1M -¹ cm- 1, with a Φ F of 0.61. However, this donor (D) -acceptor (a) -type molecule shows little two-photon absorption properties. Thus, it has been extremely challenging to implement either the bi-state CPL or CPL-TPA integration alone, while achieving both at the same time is more difficult. Disclosure of Invention In order to solve the problems, the invention provides a triarylboron-modified aza [7] spiroalkene derivative, and the two compounds show circular polarized luminescence with high fluorescence quantum yield in solution, PMMA doped film and pure film. In addition, they have two-photon absorption characteristics, which are the first examples of simultaneously realizing two-state circularly polarized luminescence and two-photon absorption performance. In order to achieve the above purpose, the present invention adopts the following technical scheme: In a first aspect of the invention, there is provided a triarylboron-modified aza [7] spiroalkene derivative having both two-photon absorption and two-state circularly polarized luminescence properties, having a structural formula selected from one of the following formulae: 。 In a second aspect of the present invention, there is provided a process for preparing the aza [7] spiroalkene derivatives described above, using the following synthetic route (1) or (2): ; route (1) is adopted, comprising: Under inert atmosphere, oBr-A7H, pdCl 2(dppf)、B2Pin2 and KOAc are uniformly mixed, then 1, 4-dioxane is added, and the temperature is increased for reaction to obtain oBpin-A7H; Sequentially adding a re-evaporated and dried toluene solution, ethanol and water into a mixed system of oBpin-A7H, 4-Br-FBPh and Pd (PPh 3)4 and K 2CO3), and heating to react to obtain oFBPh-A7H; Or, taking route (2), comprising: Dissolving A7H in chloroform, and adding N-bromosuccinimide to react to obtain oDiBr-A7H; Mixing oDiBr-A7H, pdCl 2(dppf)、B2Pin2, KOAc and 1, 4-dioxane uniformly, and reacting oBiBpin-A7H; under the protection of inert atmosphere, sequentially adding dry and degassed toluene, ethanol and water into a mixture of oBiBpin-A7H, 4-Br-FBPh and Pd (PPh 3)4 and K 2CO3), and heating to react to obtain oBiFBPh-A7H. The third aspect of the invention provides the application of the aza [7] spiroalkene derivative or the aza [7] spiroalkene derivative prepared by the method in the fields of 3D display, photoelectric information storage and processing and biological probes. The fourth aspect of the invention provides the application of the aza [7] spiroalkene derivative or the aza [7] spiroalkene derivative prepared by the method in the fields of two-photon excitation a