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CN-122011020-A - Photo-activated adjustable circular polarized afterglow chiral zinc complex material and preparation method and application thereof

CN122011020ACN 122011020 ACN122011020 ACN 122011020ACN-122011020-A

Abstract

The invention discloses a photo-activated adjustable circular polarized afterglow chiral zinc complex material and a preparation method and application thereof, and belongs to the field of circular polarized afterglow materials. The chiral zinc complex material is prepared by self-assembling zinc iodide and S- (-) -1,1 '-binaphthyl-2, 2' -diphenyl phosphine ligand at room temperature and adopting an interface diffusion method, has a molecular formula of S-Zn (BINAP) I 2 , realizes rapid and simple mass synthesis, has good solubility and stability, provides technical support for further application of the material, and provides a basis for the subsequent preparation of a film material. The prepared polymethyl methacrylate film doped with the chiral zinc complex material and the polymethyl methacrylate film doped with the chiral zinc complex material and rubrene show multicolor circular polarized afterglow after being irradiated by ultraviolet light, and have important application values in the safety fields of dynamic multiple anti-counterfeiting, advanced information encryption and the like.

Inventors

  • SONG LI
  • HONG JIAQI
  • ZHANG WANQING

Assignees

  • 浙江理工大学

Dates

Publication Date
20260512
Application Date
20260123

Claims (6)

  1. 1. The optically activated chiral zinc complex material with the adjustable circular polarization afterglow is characterized by being an orthorhombic system, chiral space groups are P212121, a face value is 0.006 (2), unit cell parameters are a= 12.0870 (7) a, b= 17.0220 (9) a, c= 18.4957 (10) a, alpha=90 degrees, beta=90 degrees, gamma=90 degrees, V= 3805.4 (4), Z=4, dc= 1.644g/cm 3 , the zinc complex material is a square crystal, the crystal color of the zinc complex material is colorless, the molecular formula of the zinc complex material is S-Zn (BINAP) I 2 , S-BINAP is S- (-) -1,1 '-binaphthyl-2, 2' -diphenyl phosphine, and the molecular structural formula of the zinc complex material is as follows: Wherein Zn is a zinc atom, P is a phosphorus atom, I is an iodine atom, ph 2 is a diphenyl group, the zinc atom adopts a distorted tetrahedral geometry, and the zinc atom is coordinated with two iodine atoms and also coordinated with two phosphorus atoms of the S-BINAP.
  2. 2. A method for preparing a single core of the chiral zinc complex material of claim 1, comprising the steps of: (1) 0.1mmol of zinc iodide was dissolved in tetrahydrofuran; (2) Dissolving 0.1mmolS-BINA in dichloromethane; (3) Mixing the two solutions obtained in the step (1) and the step (2) to obtain yellow clear solution, and stirring the yellow clear solution to uniformly mix the solutions; (4) Spin-evaporating the uniformly mixed yellow clear solution obtained in the step (3) on a rotary evaporator to obtain yellow powder; (5) The yellow powder obtained by rotary evaporation was added to 3mL of methylene chloride and transferred to a test tube, and 6mL of petroleum ether was further added thereto, followed by diffusion for 2 days by a diffusion method to obtain colorless bulk crystals.
  3. 3. A rapid bulk synthesis method of chiral zinc complex material according to claim 1, comprising the steps of: (1) 0.1mmol of zinc iodide was dissolved in tetrahydrofuran; (2) Dissolving 0.1mmolS-BINA in dichloromethane; (3) Mixing the two solutions obtained in the step (1) and the step (2) to obtain yellow clear solution, and stirring the yellow clear solution to uniformly mix the solutions; (4) And (3) spin-evaporating the uniformly mixed yellow clear solution obtained in the step (3) on a rotary evaporator to obtain yellow powder.
  4. 4. A method for preparing a polymethyl methacrylate film doped with the chiral zinc complex material of claim 1, comprising the steps of: (1) 0.004g of zinc complex material S-Zn (BINAP) I 2 crystal or powder and 0.0096g of polymethyl methacrylate are weighed and dissolved in 1mL of dichloromethane together, and stirred to be completely dissolved, so as to obtain colorless clear solution; (2) And (3) dripping the colorless clear solution which is completely dissolved on a quartz plate, and drying to obtain the film.
  5. 5. A method for preparing a polymethyl methacrylate film doped with the chiral zinc complex material of claim 1 and rubrene, comprising the steps of: (1) 0.004g of zinc complex material S-Zn (BINAP) I 2 crystal or powder, 0.0096g of polymethyl methacrylate and 0.001g of rubrene are weighed and dissolved in 1mL of dichloromethane together, and stirring is carried out to completely dissolve the materials, thus obtaining orange clear solution; (2) And (3) dripping the completely dissolved orange clear solution on a quartz plate, and drying to obtain the film.
  6. 6. Use of a chiral zinc complex material according to claim 1 in dynamic multiple anti-counterfeiting and advanced information encryption.

Description

Photo-activated adjustable circular polarized afterglow chiral zinc complex material and preparation method and application thereof Technical Field The invention relates to the technical field of luminescent materials, in particular to the technical field of optically activated circular polarized afterglow materials, and particularly relates to the technical field of dynamic multiple anti-counterfeiting and advanced information encryption application, in particular to an optically activated chiral zinc complex material with adjustable circular polarized afterglow, and a preparation method and application thereof. Background The anti-counterfeiting technology has very important significance for maintaining modern economic order, protecting independent intellectual property rights and striking counterfeit and inferior products. Along with the continuous progress of counterfeiting technology, the demand for anti-counterfeiting materials is also expanded from initial visual identification to multiple and difficult-to-copy performances. The traditional single-band fluorescent material, physical watermark and other anti-counterfeiting means have difficulty in meeting the safety requirements of high-end products, securities, important certificates and other aspects due to the characteristics of single information carrier, easy counterfeiting and the like. In order to improve the anti-counterfeiting reliability, scientists propose a novel anti-counterfeiting method by using a long-afterglow luminescent material. The material still keeps luminous after being excited, has a time resolution function, can be detected in a dark environment, and achieves a preliminary double anti-counterfeiting effect. Most long afterglow materials (represented by sulfides) still have a static character in their afterglow signal and are largely unpolarized and easily reproduced. The application of the circular polarization luminescent material in the chiral optical field is a novel anti-counterfeiting technology. The circular polarized light has the property of both left-handed and right-handed, and the detection of the circular polarized light needs special optical devices, so that the simulation is very difficult to manufacture. By utilizing the characteristics of long afterglow and circular polarized luminescence, a novel optical signal with the characteristics of ultra-long service life and chirality is developed, and is considered as an important research direction for the development of a new generation of anti-counterfeiting technology. Currently, circularly polarized afterglow is obtained by introducing chiral phosphorescent molecules and synthetic chiral coordination polymers into a rigid matrix. However, the research direction still faces some key bottleneck problems, and the method is still to break through, namely the efficient regulation and conversion of the nano material to the signal at present. Most of the circularly polarized afterglow materials reported at present belong to a normally bright or single excited state, however, few researches on such materials are carried out at present. On the basis, the synthesized chiral phosphorescence signal can change, and triggering and repeated erasing can not be carried out according to the requirement. This feature restricts its application in information encryption, dynamic display, and other high-level security applications. An ideal cryptographic material should be able to react to external stimuli to achieve hiding and visualization, and light as a simple and controllable stimulus with high spatial and temporal resolution should solve this problem well. The development of the material with circular polarization afterglow can completely embed the encrypted information into the material, and can be excited only by certain stimulus, thereby presenting circular polarization afterglow and greatly improving the confidentiality and confidentiality of the information. Second, the optical properties of the materials lack compatibility. Wherein, the asymmetric factors of the luminous color, the afterglow time and the circularly polarized luminescence are key factors influencing the anti-counterfeiting code information quantity. However, in the current material system, the parameters are usually fixed step by step, and it is difficult to continuously control the parameters on a single material platform in a large range and high precision. The rigidity characteristic makes it difficult to carry out personalized design according to different application scenes, so that universality is restricted. Therefore, the design of a synergistic system capable of realizing simple regulation and control of the properties through molecular design or external environment is a key for constructing a large-scale coding combined high-flux anti-counterfeiting system. Third, it relates to viability and cost in practical use. At present, many circularly polarized afterglow materials with excellent performan