Ionic cuprous complex with thermally activated delayed fluorescence properties, preparation method, and application thereof
By developing cuprous complexes, the problems of overlapping spectral photos of fluorescence signal and high cost of precious metal materials are solved, and efficient and low-cost fluorescence life imaging technology in information recording, storage and protection are achieved.
Patent Information
- Application Number
- CN202210917692.0
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Filing Date
- 2022-08-01
- Publication Date
- 2025-08-12
- Estimated Expiration
- 2042-08-01
AI Technical Summary
In the existing fluorescence lifetime imaging technology, the spectral overlap between the fluorescence signals is severe and difficult to distinguish, and the precious metal phosphorescent materials are costly, which limits their application in information protection.
An ionic cuprous complex centered on cuprous ions was developed. By selecting suitable ligands to regulate their luminescence life, the one-pot method was used to synthesize cuprous complexes with thermal activation delayed fluorescence properties for information recording, storage and protection.
It realizes adjusting the luminous life without changing the luminous color, improving the security and reliability of information recording, storage and protection, and reducing material costs.
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Figure CN115109080B_ABST
Abstract
Description
Technical Field
[0001] The invention relates to a cuprous complex luminescent material and application thereof in recording, storing and protecting information, belonging to the field of information recording, storing and protecting. Background Art
[0002] The recording, storage and protection of information are becoming increasingly important in modern life. Traditional anti-counterfeiting technologies such as barcodes, QR codes, watermarks, and laser holograms have been developed and utilized. However, these technologies are easy to copy and have low security. Stimulus-responsive fluorescent materials that emit different luminescence colors or intensities under external stimuli (such as temperature, light, humidity, mechanical pressure, pH, voltage, etc.) have opened up new avenues for the development of optical information protection. However, there is often varying degrees of spectral overlap between different fluorescent signals of this technology, making it difficult to distinguish which fluorescent signal is which. Fluorescence lifetime imaging technology, which uses the different fluorescence lifetimes of luminescent materials as detection signals, has opened up a new dimension for improving the ability to record, store and protect optical information. This technology can eliminate the influence of different fluorescence spectra, excitation light sources, optical filters and signal detectors without increasing the complexity of the information recording, storage and protection procedures.
[0003] To realize the utilization of fluorescence lifetime imaging technology, the development of luminescent materials with long emission lifetimes is urgently needed. Phosphorescent noble metal transition metal and lanthanide complexes are widely used in the field of optical information protection due to their advantages such as long emission lifetimes, large Stokes shifts, narrow emission spectra, good photostability, and minimal background interference. However, these materials contain expensive metals, which greatly limits their application in optical information protection.
[0004] Ionic cuprous complexes centered on the abundant and inexpensive cuprous ion can achieve phosphorescence or thermally activated delayed fluorescence with long luminescence lifetimes due to their weak spin-orbit coupling, opening up potential applications in information encryption. The luminescence of such complexes typically originates from the charge transfer state from the metal to the ligand. By varying the electrostatic interaction between the cationic coordination unit and the counterion, the luminescence lifetime of ionic cuprous complexes can be modulated, leading to applications in data storage and security (Adv. Optical Mater. 2018, 1801065). However, there are relatively few ionic cuprous complexes suitable for fluorescence lifetime imaging, and developing new strategies to modulate their luminescence lifetimes is crucial.
[0005] Compared to counterions, ligands themselves, due to their direct coordination with the central cuprous ion, have a significant influence on the luminescence properties of the complex. If the appropriate ligand is selected, the luminescence lifetime can be adjusted without changing the emission color. Summary of the Invention
[0006] The present invention provides an ionic cuprous complex with thermally activated delayed fluorescence properties, as well as the use of the complex as a luminescent material in recording, storing and protecting information and a preparation method thereof.
[0007] The technical solutions of the present invention are as follows:
[0008] A cuprous complex with thermally activated delayed fluorescence performance, wherein the cuprous complex with thermally activated delayed fluorescence performance is tetrakis(3,5-bis(trifluoromethyl)phenyl)boric acid-[bis(2-diphenylphosphinophenyl)ether]-[1,10-phenanthroline]copper(I), with the structural formula shown in 1a; tetrakis(3,5-bis(trifluoromethyl)phenyl)boric acid-[4,5-bisdiphenylphosphino-9,9-dimethylxanthene]-[1,10-phenanthroline]copper(I), with the structural formula shown in 1b; tetrakis(3,5-bis(trifluoromethyl)phenyl)boric acid-[bis(2-diphenylphosphinophenyl)ether]-[4,7- diphenyl-1,10-phenanthroline] copper (I), the structural formula is shown in 2a; tetrakis (3,5-bis (trifluoromethyl) phenyl) borate-[4,5-bis (diphenylphosphine) -9,9-dimethylxanthene] - [4,7-diphenyl-1,10-phenanthroline] copper (I), the structural formula is shown in 2b,
[0009]
[0010] The preparation method of tetrakis(3,5-bis(trifluoromethyl)phenyl)boric acid-[bis(2-diphenylphosphinophenyl)ether]-[1,10-phenanthroline]copper(I) comprises the following steps: dissolving tetraacetonitrile copper(I) hexafluorophosphate and bis(2-diphenylphosphinophenyl)ether in dichloromethane under anhydrous and oxygen-free conditions, stirring at room temperature for 1 to 3 hours under argon protection; then adding the dichloromethane solution of 1,10-phenanthroline to the above solution, and continuing stirring at room temperature for 2 to 4 hours under argon protection; then adding the methanol solution of sodium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate to the above solution, and stirring at room temperature for 2 to 4 hours under argon protection; Stirring is continued at room temperature for 0.5 to 1.5 hours, and the molar ratio of tetraacetonitrile copper (I) hexafluorophosphate: bis(2-diphenylphosphinophenyl) ether: 1,10-phenanthroline: sodium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate is (0.5 to 1.5): (0.5 to 2): (0.5 to 2): (0.5 to 1.5); after the reaction is completed, the mixture is filtered, and the solvent is slowly evaporated from the filtrate to obtain light yellow transparent crystals, namely, tetrakis(3,5-bis(trifluoromethyl)phenyl)borate-[bis(2-diphenylphosphinophenyl) ether]-[1,10-phenanthroline] copper (I).
[0011] The preparation method of tetrakis(3,5-bis(trifluoromethyl)phenyl)boric acid-[4,5-bisdiphenylphosphine-9,9-dimethylxanthene]-[1,10-phenanthroline]copper(I) comprises the following steps: dissolving tetraacetonitrile copper(I) hexafluorophosphate and 4,5-bisdiphenylphosphine-9,9-dimethylxanthene in dichloromethane under anhydrous and oxygen-free conditions, and stirring at room temperature for 1 to 3 hours under argon protection; then adding a dichloromethane solution of 1,10-phenanthroline to the above solution, and continuing stirring at room temperature for 2 to 4 hours under argon protection; then adding a methanol solution of sodium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate to the above solution, and continuing stirring at room temperature for 0.5 to 1.5 hours under argon protection; wherein the tetraacetonitrile copper(I) hexafluorophosphate: 4,5-bisdiphenylphosphine-9,9-dimethylxanthene are added to the above solution, and continuing stirring at room temperature for 0.5 to 1.5 hours under argon protection. The molar ratio of bis(diphenylphosphino-9,9-dimethylxanthene): 1,10-phenanthroline: sodium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate is (0.5-1.5): (0.5-2): (0.5-2): (0.5-1.5); after the reaction is completed, the filtrate is filtered, and the solvent is slowly evaporated to obtain light yellow transparent crystals, which are tetrakis(3,5-bis(trifluoromethyl)phenyl)borate-[4,5-bis(diphenylphosphino-9,9-dimethylxanthene]-[1,10-phenanthroline] copper (I).
[0012] The preparation method of tetrakis(3,5-bis(trifluoromethyl)phenyl)boric acid-[bis(2-diphenylphosphinophenyl)ether]-[4,7-diphenyl-1,10-phenanthroline]copper(I) comprises the following steps: dissolving tetrakis(3,5-bis(trifluoromethyl)phenyl)boric acid-[bis(2-diphenylphosphinophenyl)ether)-[4,7-diphenyl-1,10-phenanthroline]copper(I) in dichloromethane under anhydrous and oxygen-free conditions, and stirring at room temperature for 1 to 3 hours under argon protection; then adding a dichloromethane solution of 4,7-diphenyl-1,10-phenanthroline to the above solution, and continuing stirring at room temperature for 2 to 4 hours under argon protection; then adding a methanol solution of sodium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate to the above solution, and continuing stirring at room temperature for 0.5 to 1.5 hours under argon protection; and The molar ratio of bis(2-diphenylphosphinophenyl) ether: 4,7-diphenyl-1,10-phenanthroline: sodium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate is (0.5-1.5):(0.5-2):(0.5-2):(0.5-1.5); after the reaction is completed, the mixture is filtered and the solvent is slowly evaporated from the filtrate to obtain light yellow transparent crystals, namely tetrakis(3,5-bis(trifluoromethyl)phenyl)borate-[bis(2-diphenylphosphinophenyl) ether]-[4,7-diphenyl-1,10-phenanthroline]copper(I).
[0013] The preparation method of tetrakis(3,5-bis(trifluoromethyl)phenyl)boronic acid-[4,5-bis(diphenylphosphine-9,9-dimethylxanthene]-[4,7-diphenyl-1,10-phenanthroline]copper(I) comprises the following steps: dissolving tetraacetonitrile copper(I) hexafluorophosphate and 4,5-bis(diphenylphosphine-9,9-dimethylxanthene) in dichloromethane under anhydrous and oxygen-free conditions, stirring at room temperature for 1 to 3 hours under argon protection; then adding a dichloromethane solution of 4,7-diphenyl-1,10-phenanthroline to the above solution, and continuing stirring at room temperature for 2 to 4 hours under argon protection; then adding tetrakis(3,5-bis(trifluoromethyl)phenyl)boronic acid-[4,5-bis(diphenylphosphine-9,9-dimethylxanthene)-[4,7-diphenyl-1,10-phenanthroline]copper(I) A methanol solution of sodium (trifluoromethyl)phenyl)borate is added to the above solution, and stirring is continued at room temperature for 0.5 to 1.5 hours under argon protection. The molar ratio of tetraacetonitrile copper (I) hexafluorophosphate: 4,5-bis(diphenylphosphino-9,9-dimethylxanthene: 4,7-diphenyl-1,10-phenanthroline: tetrakis(3,5-bis(trifluoromethyl)phenyl)borate) sodium is (0.5 to 1.5): (0.5 to 2): (0.5 to 2): (0.5 to 1.5); after the reaction is completed, the filtrate is filtered, and the solvent is slowly evaporated from the filtrate to obtain light yellow transparent crystals, namely, tetrakis(3,5-bis(trifluoromethyl)phenyl)borate-[4,5-bis(diphenylphosphino-9,9-dimethylxanthene]-[4,7-diphenyl-1,10-phenanthroline] copper (I).
[0014] The above preparation method is a "one-pot method" and does not require the separation of intermediates; and the feed ratio of various raw materials is preferably: cuprous salt: bisphosphine ligand: phenanthroline ligand: borate = 1:1:1:1.
[0015] Application of ionic cuprous complexes with thermally activated delayed fluorescence in information recording, storage and protection.
[0016] use 1 The structures of these complexes were confirmed by H NMR, mass spectrometry, elemental analysis (C, H, N), and X-ray single crystal diffraction. Thermogravimetric, UV absorption, emission spectra, and luminescence lifetimes were also measured. Instruments used included a NETZSCH STA 449F3 thermogravimetric analyzer, a Rigaku AFC-10 / Saturn 724+CCD X-ray single crystal diffractometer, a Bruker DPX 400 NMR (400M) nuclear magnetic resonance spectrometer, a Waters Xevo G2-S QT mass spectrometer, an Elementar VarioEL III elemental analyzer, an Agilent Cary 60 UV-Vis spectrophotometer, a Hitachi F-7000 fluorescence spectrometer, and an Edinburgh FLS920 transient / steady-state fluorescence spectrophotometer.
[0017] Using complexes 1b, 2a, and 2b as luminescent dyes, their powders were used to write the Chinese character "本" (běn). Under the illumination of a fluorescent lamp and an ultraviolet lamp, only the pattern of the character "本" could be seen. By using fluorescence lifetime imaging technology, the hidden information contained in the strokes "一" (yī), "八" (bā), and "十" (shí) of this Chinese character could be clearly read out, indicating that such complexes have application value in information recording, storage, and protection. BRIEF DESCRIPTION OF THE DRAWINGS
[0018] Figure 1 It is the crystal structure diagram of complex 1a;
[0019] Figure 2 It is the crystal structure diagram of complex 1b;
[0020] Figure 3 It is the crystal structure diagram of complex 2a;
[0021] Figure 4 It is the crystal structure diagram of complex 2b;
[0022] Figure 5 It is the thermogravimetric curve diagram of complexes 1a, 1b, 2a, and 2b;
[0023] Figure 6 It is the ultraviolet absorption spectrum diagram of complexes 1a, 1b, 2a, and 2b in dichloromethane solution;
[0024] Figure 7 It is the fluorescence emission spectrum diagram of complexes 1a, 1b, 2a, and 2b solids at 10K and 300K;
[0025] Figure 8 It is the curve diagram of the fluorescence lifetime of complexes 1a, 1b, 2a, and 2b solids changing with temperature;
[0026] Figure 9 It is the application diagram of complexes 1b, 2a, and 2b in information recording, storage, and protection;
[0027] Figure 10 It is the MS diagram of complex 1a;
[0028] Figure 11 It is the MS diagram of complex 1b;
[0029] Figure 12 It is the MS diagram of complex 2a;
[0030] Figure 13 It is the MS diagram of complex 2b;
[0031] Figure 14 It is for complex 1a's 1 1H NMR diagram;
[0032] Figure 15For complex 1b 1 H NMR spectrum;
[0033] Figure 16 For complex 2a 1 H NMR spectrum;
[0034] Figure 17 For complex 2b 1 H NMR spectrum. DETAILED DESCRIPTION
[0035] The complex of the present invention can be synthesized according to the following formula:
[0036]
[0037] The above preparation operation is carried out in a round-bottom flask using a "one-pot" synthesis method without the need to isolate intermediates. The feed ratio of various raw materials is: cuprous salt: bisphosphine ligand: phenanthroline ligand: borate = 1:1:1:1. Finally, a pure complex product is obtained by a solvent volatilization method. The hydrogen nuclear magnetic resonance spectrum was measured on a Bruker DPX 400NMR (400M) nuclear magnetic resonance instrument; the ESI-MS mass spectrum was measured on a Waters Xevo G2-S QT mass spectrometer, and the elemental analysis of C, H, and N was measured on an Elementar Vario EL III elemental analyzer; the thermogravimetric analysis was determined on a NETZSCH STA 449F3 thermogravimetric analyzer; the single crystal structure was determined on a Rigaku AFC-10 / Saturn 724+CCD X-ray single crystal diffractometer; the UV absorption spectrum was measured on an Agilent Cary 60 UV-visible spectrophotometer; the fluorescence emission spectrum was measured on a Hitachi F-7000 fluorescence spectrophotometer; and the phosphorescence lifetime was measured on an Edinburgh FLS920 transient / steady-state fluorescence spectrophotometer.
[0038] Example 1
[0039] Synthesis of complex 1a:
[0040] Under anhydrous and oxygen-free conditions, 1.0 mmol of tetraacetonitrile copper (I) hexafluorophosphate and 1.0 mmol of bis(2-diphenylphosphinophenyl) ether were dissolved in 10 mL of dichloromethane and stirred at room temperature for 1 hour under argon protection; then a dichloromethane solution (5 mL) of 1.0 mmol of 1,10-phenanthroline was added to the above solution, and stirring was continued at room temperature for 2 hours under argon protection; then a methanol solution (5 mL) of 1.0 mmol of sodium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate was added to the above solution, and stirring was continued at room temperature for 0.5 hour under argon protection; after the reaction was completed, the solution was filtered with suction, and the solvent was slowly evaporated from the filtrate to obtain light yellow transparent crystals, namely tetrakis(3,5-bis(trifluoromethyl)phenyl)borate-[bis(2-diphenylphosphinophenyl) ether]-[1,10-phenanthroline] copper (I) (1a).
[0041] Example 2
[0042] Synthesis of complex 1b:
[0043] The preparation method of the ionic cuprous complex with thermally activated delayed fluorescence performance is characterized in that: under anhydrous and oxygen-free conditions, 1.0 mmol of tetraacetonitrile copper (I) hexafluorophosphate and 1.0 mmol of 4,5-bis(diphenylphosphine)-9,9-dimethylxanthene are dissolved in 10 mL of dichloromethane, and stirred at room temperature for 1 hour under argon protection; then 1.0 mmol of a dichloromethane solution (5 mL) of 1,10-phenanthroline is added to the above solution, and stirring is continued at room temperature for 2 hours under argon protection; then 1.0 mmol of a methanol solution (5 mL) of sodium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate is added to the above solution, and stirring is continued at room temperature for 0.5 hour under argon protection; after the reaction is completed, the solution is filtered with suction, and the solvent in the filtrate is slowly evaporated to obtain light yellow transparent crystals, namely tetrakis(3,5-bis(trifluoromethyl)phenyl)boronic acid-[4,5- [bis(diphenylphosphino-9,9-dimethylxanthene)]-[1,10-phenanthroline]copper(I) (1b).
[0044] Example 3
[0045] Synthesis of complex 2a:
[0046] The method for preparing an ionic cuprous complex having thermally activated delayed fluorescence properties is characterized in that: under anhydrous and oxygen-free conditions, 1.0 mmol of tetraacetonitrile copper (I) hexafluorophosphate and 1.0 mmol of bis(2-diphenylphosphinophenyl) ether are dissolved in 10 mL of dichloromethane, and stirred at room temperature for 1 to 3 hours under argon protection; then a dichloromethane solution (5 mL) of 1.0 mmol of 4,7-diphenyl-1,10-phenanthroline is added to the above solution, and stirring is continued at room temperature for 2 to 4 hours under argon protection; then a methanol solution (5 mL) of 1.0 mmol of sodium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate is added to the above solution, and stirring is continued at room temperature for 0.5 to 1.5 hours under argon protection; after the reaction is completed, the solution is filtered with suction, and the solvent in the filtrate is slowly evaporated to obtain light yellow transparent crystals, namely tetrakis(3,5-bis(trifluoromethyl)phenyl) Boric acid-[bis(2-diphenylphosphinophenyl)ether]-[4,7-diphenyl-1,10-phenanthroline]copper(I) (2a).
[0047] Example 4
[0048] Synthesis of complex 2b:
[0049] The method for preparing an ionic cuprous complex having thermally activated delayed fluorescence performance is characterized in that: under anhydrous and oxygen-free conditions, 1.0 mmol of tetraacetonitrile copper (I) hexafluorophosphate and 1.0 mmol of 4,5-bisdiphenylphosphine-9,9-dimethylxanthene are dissolved in 10 mL of dichloromethane, and stirred at room temperature for 1 to 3 hours under argon protection; then 1.0 mmol of a dichloromethane solution (5 mL) of 4,7-diphenyl-1,10-phenanthroline is added to the above solution, and stirring is continued at room temperature for 2 to 4 hours under argon protection; and then 1.0 mmol of A methanol solution (5 mL) of sodium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate was added to the above solution, and stirring was continued at room temperature for 0.5 to 1.5 hours under argon protection. After the reaction was completed, the filtrate was filtered and the solvent was slowly evaporated to obtain light yellow transparent crystals, namely tetrakis(3,5-bis(trifluoromethyl)phenyl)borate-[4,5-bis(diphenylphosphine-9,9-dimethylxanthene]-[4,7-diphenyl-1,10-phenanthroline]copper(I) (2b).
[0050] In the above embodiment, the ligand bis(2-diphenylphosphinophenyl)ether or 4,5-bisdiphenylphosphino-9,9-dimethylxanthene can be replaced by triphenylphosphine, and the chemical formula is as follows:
[0051]
[0052] Example 5
[0053] Synthesis of complex 1a:
[0054] Under anhydrous and oxygen-free conditions, 0.5 mmol of tetraacetonitrile copper (I) hexafluorophosphate and 0.5 mmol of bis(2-diphenylphosphinophenyl) ether were dissolved in 10 mL of dichloromethane and stirred at room temperature for 1 hour under argon protection; then 2.0 mmol of 1,10-phenanthroline in dichloromethane (5 mL) was added to the above solution, and stirring was continued at room temperature for 2 hours under argon protection; then 1.5 mmol of sodium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate in methanol (5 mL) was added to the above solution, and stirring was continued at room temperature for 0.5 hour under argon protection; after the reaction was completed, the solution was filtered with suction, and the solvent was slowly evaporated from the filtrate to obtain light yellow transparent crystals, namely tetrakis(3,5-bis(trifluoromethyl)phenyl)borate-[bis(2-diphenylphosphinophenyl) ether]-[1,10-phenanthroline] copper (I) (1a).
[0055] Example 6
[0056] Synthesis of complex 1b:
[0057] The method for preparing the ionic cuprous complex having thermally activated delayed fluorescence performance is characterized in that: under anhydrous and oxygen-free conditions, 1.5 mmol of tetraacetonitrile copper (I) hexafluorophosphate and 2.0 mmol of 4,5-bis(diphenylphosphine)-9,9-dimethylxanthene are dissolved in 20 mL of dichloromethane, and stirred at room temperature for 1 hour under argon protection; then 2.0 mmol of A dichloromethane solution (10 mL) of 1,10-phenanthroline was added to the above solution, and the mixture was stirred at room temperature for 2 hours under argon protection. Then, a methanol solution (10 mL) of 1.5 mmol of sodium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate was added to the above solution, and the mixture was stirred at room temperature for 0.5 hours under argon protection. After the reaction was completed, the mixture was filtered and the solvent was slowly evaporated from the filtrate to obtain light yellow transparent crystals, namely tetrakis(3,5-bis(trifluoromethyl)phenyl)borate-[4,5-bis(diphenylphosphine-9,9-dimethylxanthene]-[1,10-phenanthroline]copper(I) (1b).
[0058] Example 7
[0059] Synthesis of complex 2a:
[0060] The method for preparing an ionic cuprous complex having thermally activated delayed fluorescence performance is characterized in that: under anhydrous and oxygen-free conditions, 1.5 mmol of tetraacetonitrile copper (I) hexafluorophosphate and 2.0 mmol of bis(2-diphenylphosphinophenyl) ether are dissolved in 10 mL of dichloromethane, and stirred at room temperature for 1 to 3 hours under argon protection; then a dichloromethane solution (5 mL) of 0.5 mmol of 4,7-diphenyl-1,10-phenanthroline is added to the above solution, and stirring is continued at room temperature for 2 to 4 hours under argon protection; then a methanol solution (5 mL) of 0.5 mmol of sodium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate is added to the above solution, and stirring is continued at room temperature for 0.5 to 1.5 hours under argon protection; after the reaction is completed, the solution is filtered with suction, and the solvent in the filtrate is slowly evaporated to obtain light yellow transparent crystals, namely tetrakis(3,5-bis(trifluoromethyl)phenyl) Boric acid-[bis(2-diphenylphosphinophenyl)ether]-[4,7-diphenyl-1,10-phenanthroline]copper(I) (2a).
[0061] Example 8
[0062] Synthesis of complex 2b:
[0063] The method for preparing an ionic cuprous complex having thermally activated delayed fluorescence performance is characterized in that: under anhydrous and oxygen-free conditions, 1.0 mmol of tetraacetonitrile copper (I) hexafluorophosphate and 1.0 mmol of 4,5-bis(diphenylphosphine)-9,9-dimethylxanthene are dissolved in 10 mL of dichloromethane, and stirred at room temperature for 1 to 3 hours under argon protection; then 2.0 mmol of a dichloromethane solution (5 mL) of 4,7-diphenyl-1,10-phenanthroline is added to the above solution, and stirring is continued at room temperature for 2 to 4 hours under argon protection; then 1.5 mmol of A methanol solution (5 mL) of sodium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate was added to the above solution, and stirring was continued at room temperature for 0.5 to 1.5 hours under argon protection. After the reaction was completed, the filtrate was filtered and the solvent was slowly evaporated to obtain light yellow transparent crystals, namely tetrakis(3,5-bis(trifluoromethyl)phenyl)borate-[4,5-bis(diphenylphosphine-9,9-dimethylxanthene]-[4,7-diphenyl-1,10-phenanthroline]copper(I) (2b).
[0064] The complexes of Examples 1-4 are 1 H NMR, mass spectrometry, and elemental analysis confirmed that the structure was correct. The data are as follows:
[0065] Complex 1a, yield 86%:
[0066] 1H NMR (400MHz, DMSO-d6, δ): 8.89 (d, J = 4.7, 2H), 8.74 (d, J = 8.1, 2H), 8.21 (s, 2H), 7.86 (dt,J=8.1,3.9,2H),7.72(s,4H),7.62(s,9H),7.43(t,J=7.9,2H),7.30(t,J =7.4,4H),7.13(dt,J=32.8,7.4,13H),6.95(q,J=6.9,6.3,8H),6.67(s,2H).
[0067] ESI-MS[m / z]:781.16(M–BArF 24 ) + .
[0068] Elemental analysis results: Calculated value (%): C 58.39, H 2.94, N 1.70.
[0069] Found (%): C 58.46, H 2.93, N 1.72.
[0070] Complex 1b, yield 79%:
[0071] 1 H NMR (400MHz, DMSO-d6, δ): 8.74 (d, J = 8Hz, 2H), 8.59 (d, J = 4Hz, 2H), 8.20 (d, J = 4Hz, 2H) ,7.88–7.84(m,4H),7.72(s,4H),7.62(s,8H),7.29–7.24(m,6H),7.10(d,J=8Hz,8H), 6.91–6.87(m,8H),6.58(d,J=8Hz,2H),1.74(s,6H).
[0072] ESI-MS[m / z]:821.19(M–BArF 24 ) + .
[0073] Elemental analysis results: Calculated value (%): C 59.14, H 3.11, N 1.66.
[0074] Found (%): C 59.19, H 3.08, N 1.64.
[0075] Complex 2a, yield 81%:
[0076] 1H NMR (400MHz, DMSO-d6, δ): 8.95 (d, J = 4Hz, 2H), 8.00 (s, 2H), 8.82 (d, J = 8Hz, 2H), 7.70(s,4H),7.62(s,18H),7.43(t,J=8Hz,2H),7.33(dd,J=8,4Hz,4H),7.23–7.11(m,12H),7.06–7.01(m,8H),6.81–6.78(m,2H).
[0077] ESI-MS[m / z]:933.22(M–BArF 24 ) + .
[0078] Elemental analysis results: Calculated value (%): C 61.47, H 3.14, N 1.56.
[0079] Found (%): C 61.44, H 3.12, N 1.53.
[0080] Complex 2b, yield 88%:
[0081] 1 H NMR (400MHz, DMSO-d6, δ): 8.68 (d, J = 5.1, 2H), 7.95–7.80 (m, 6H), 7.72 (s, 4H), 7.62 (q,J=6.4,5.4,18H),7.30(t,J=7.6,6H),7.16(t,J=7.4,8H),7.00(q,J=6.3,8H),6.78(dd,J=8.2,4.2,2H),1.74(s,6H).
[0082] ESI-MS[m / z]:973.25(M–BArF 24 ) + .
[0083] Elemental analysis results: Calculated value (%): C 62.09, H 3.29, N 1.52.
[0084] Found (%): C 62.15, H 3.32, N 1.54.
[0085] Crystal structure, thermogravimetric analysis, UV absorption spectrum, emission spectrum and other characterizations of complexes 1a, 1b, 2a and 2b:
[0086] The single crystal structure of the complex tetrakis(3,5-bis(trifluoromethyl)phenyl)boronic acid-[bis(2-diphenylphosphinophenyl)ether]-[1,10-phenanthroline]copper(I) (1a) is shown in Figure 1 ;
[0087] The single crystal structure of the complex tetrakis(3,5-bis(trifluoromethyl)phenyl)boronic acid-[4,5-bis(diphenylphosphine)-9,9-dimethylxanthene]-[1,10-phenanthroline]copper(I) (1b) is shown in Figure 2 ;
[0088] The single crystal structure of the complex tetrakis(3,5-bis(trifluoromethyl)phenyl)boronic acid-[bis(2-diphenylphosphinophenyl)ether]-[4,7-diphenyl-1,10-phenanthroline]copper(I) (2a) is shown in Figure 3 ;
[0089] The single crystal structure of the complex tetrakis(3,5-bis(trifluoromethyl)phenyl)boronic acid-[4,5-bis(diphenylphosphine)-9,9-dimethylxanthene]-[4,7-diphenyl-1,10-phenanthroline]copper(I) (2b) is shown in Figure 4 ;
[0090] The thermal decomposition temperatures of complexes 1a, 1b, 2a, and 2b are 321, 337, 338, and 331°C, respectively. Figure 5 ;
[0091] Complexes 1a, 1b, 2a, and 2b were dissolved in dichloromethane (10 -5 M), and its absorption spectrum was measured on an Agilent Cary 60 UV-visible spectrophotometer (see Figure 6 ), and the positions of their absorption peaks are:
[0092] Tetrakis(3,5-bis(trifluoromethyl)phenyl)boronic acid-[bis(2-diphenylphosphinophenyl)ether]-[1,10-phenanthroline]copper(I) (1a): λ abs,max , nm 229, 269, 395;
[0093] Tetrakis(3,5-bis(trifluoromethyl)phenyl)boronic acid-[4,5-bis(diphenylphosphine)-9,9-dimethylxanthene]-[1,10-phenanthroline]copper(I) (1b):λ abs,max , nm 229, 269, 389;
[0094] Tetrakis(3,5-bis(trifluoromethyl)phenyl)boronic acid-[bis(2-diphenylphosphinophenyl)ether]-[4,7-diphenyl-1,10-phenanthroline]copper(I) (2a): λ abs,max , nm 229, 282, 399;
[0095] Tetrakis(3,5-bis(trifluoromethyl)phenyl)boronic acid-[4,5-bis(diphenylphosphine)-9,9-dimethylxanthene]-[4,7-diphenyl-1,10-phenanthroline]copper(I) (2b): λabs,max , nm 229, 281, 400;
[0096] The fluorescence emission spectra of complexes 1a, 1b, 2a, and 2b solids at 10 K and 300 K were measured on a Hitachi F-7000 fluorescence spectrometer (see Figure 7 ), and the positions of their fluorescence emission peaks are as follows:
[0097] Copper(I) bis(2-diphenylphosphinophenyl) ether-1,10-phenanthroline tetrakis(3,5-bis(trifluoromethyl)phenyl)borate (1a): λ em,max , nm 583 (300 K), 605 (10 K);
[0098] Copper(I) 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene-1,10-phenanthroline tetrakis(3,5-bis(trifluoromethyl)phenyl)borate (1b): λ em,max , nm 573 (300 K), 590 (10 K);
[0099] Copper(I) bis(2-diphenylphosphinophenyl) ether-4,7-diphenyl-1,10-phenanthroline tetrakis(3,5-bis(trifluoromethyl)phenyl)borate (2a): λ em,max , nm 579 (300 K), 603 (10 K);
[0100] Copper(I) 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene-4,7-diphenyl-1,10-phenanthroline tetrakis(3,5-bis(trifluoromethyl)phenyl)borate (2b): λ em,max , nm 576 (300 K), 603 (10 K);
[0101] To verify that the luminescence of the complexes comes from thermally activated delayed fluorescence, the temperature-dependent fluorescence lifetime curves of the complexes were measured using an Edinburgh FLS920 transient / steady-state fluorescence spectrophotometer, see Figure 8 ;
[0102] The application tests of complexes 1b, 2a, and 2b in information recording, storage, and protection are shown in Figure 9 . Take the powders of complexes 1b, 2a, and 2b to write the Chinese character "本". Under the illumination of a fluorescent lamp and an ultraviolet lamp, only the pattern of the character "本" can be shown. Using fluorescence lifetime imaging technology, the hidden information contained in the strokes "一", "八", and "十" of this Chinese character can be clearly read out.
Claims
1. An ionic cuprous complex having thermally activated delayed fluorescence, characterized in that: The ionic cuprous complex with thermally activated delayed fluorescence performance is tetrakis(3,5-bis(trifluoromethyl)phenyl)boric acid-[bis(2-diphenylphosphinophenyl)ether]-[1,10-phenanthroline]copper(I), with the structural formula shown in 1a; tetrakis(3,5-bis(trifluoromethyl)phenyl)boric acid-[4,5-bis(diphenylphosphino-9,9-dimethylxanthene]-[1,10-phenanthroline]copper(I), with the structural formula shown in 1b As shown; Tetrakis(3,5-bis(trifluoromethyl)phenyl)boronic acid-[bis(2-diphenylphosphinophenyl)ether]-[4,7-diphenyl-1,10-phenanthroline]copper(I), the structural formula is shown in 2a; Tetrakis(3,5-bis(trifluoromethyl)phenyl)boronic acid-[4,5-bis(diphenylphosphino-9,9-dimethylxanthene]-[4,7-diphenyl-1,10-phenanthroline]copper(I), the structural formula is shown in 2b, 2. The method for preparing an ionic cuprous complex having thermally activated delayed fluorescence according to claim 1, wherein: Under anhydrous and oxygen-free conditions, tetraacetonitrile copper (I) hexafluorophosphate and bis (2-diphenylphosphinophenyl) ether are dissolved in dichloromethane and stirred at room temperature for 1 to 3 hours under argon protection; then a dichloromethane solution of 1,10-phenanthroline is added to the above solution, and stirring is continued at room temperature for 2 to 4 hours under argon protection; then a methanol solution of sodium tetrakis (3,5-bis (trifluoromethyl) phenyl) borate is added to the above solution, and stirring is continued at room temperature for 0.5 to 1.5 hours under argon protection, and the tetraacetonitrile copper (I) hexafluorophosphate is added to the above solution. The molar ratio of tetrakis(3,5-bis(trifluoromethyl)phenyl)borate:bis(2-diphenylphosphinophenyl)ether:1,10-phenanthroline:sodium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate) is (0.5-1.5):(0.5-2):(0.5-2):(0.5-1.5); after the reaction is completed, the filtrate is filtered and the solvent is slowly evaporated to obtain light yellow transparent crystals, which are tetrakis(3,5-bis(trifluoromethyl)phenyl)borate-[bis(2-diphenylphosphinophenyl)ether]-[1,10-phenanthroline]copper(I).
3. The method for preparing an ionic cuprous complex having thermally activated delayed fluorescence according to claim 1, wherein: Under anhydrous and oxygen-free conditions, tetraacetonitrile copper (I) hexafluorophosphate and 4,5-bisdiphenylphosphine-9,9-dimethylxanthene are dissolved in dichloromethane and stirred at room temperature for 1 to 3 hours under argon protection; then a dichloromethane solution of 1,10-phenanthroline is added to the above solution, and stirring is continued at room temperature for 2 to 4 hours under argon protection; then a methanol solution of sodium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate is added to the above solution, and stirring is continued at room temperature for 0.5 to 1.5 hours under argon protection. The tetraacetonitrile copper (I) hexafluorophosphate: 4, The molar ratio of 5-bis(diphenylphosphino-9,9-dimethylxanthene): 1,10-phenanthroline: sodium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate is (0.5-1.5): (0.5-2): (0.5-2): (0.5-1.5); after the reaction is completed, the filtrate is filtered, and the solvent is slowly evaporated to obtain light yellow transparent crystals, which are tetrakis(3,5-bis(trifluoromethyl)phenyl)borate-[4,5-bis(diphenylphosphino-9,9-dimethylxanthene]-[1,10-phenanthroline] copper (I).
4. The method for preparing an ionic cuprous complex having thermally activated delayed fluorescence according to claim 1, wherein: Under anhydrous and oxygen-free conditions, copper (I) tetraacetonitrile hexafluorophosphate and bis(2-diphenylphosphinophenyl) ether are dissolved in dichloromethane and stirred at room temperature for 1 to 3 hours under argon protection; then a dichloromethane solution of 4,7-diphenyl-1,10-phenanthroline is added to the above solution, and stirring is continued at room temperature for 2 to 4 hours under argon protection; then a methanol solution of sodium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate is added to the above solution, and stirring is continued at room temperature for 0.5 to 1.5 hours under argon protection. The copper (I) tetraacetonitrile hexafluorophosphate: bis(2-diphenylphosphinophenyl) ether are added to the above solution, and stirring is continued at room temperature for 0.5 to 1.5 hours under argon protection. The molar ratio of tetrakis(3,5-bis(trifluoromethyl)phenyl)borate-[bis(2-diphenylphosphinophenyl)ether]-[4,7-diphenyl-1,10-phenanthroline]copper(I) was obtained after the reaction was completed. The mixture was filtered and the solvent was slowly evaporated from the filtrate to obtain light yellow transparent crystals. The crystals were tetrakis(3,5-bis(trifluoromethyl)phenyl)borate-[bis(2-diphenylphosphinophenyl)ether]-[4,7-diphenyl-1,10-phenanthroline]copper(I).
5. The method for preparing an ionic cuprous complex having thermally activated delayed fluorescence according to claim 1, wherein: Under anhydrous and oxygen-free conditions, tetraacetonitrile copper (I) hexafluorophosphate and 4,5-bisdiphenylphosphine-9,9-dimethylxanthene are dissolved in dichloromethane and stirred at room temperature for 1 to 3 hours under argon protection; then a dichloromethane solution of 4,7-diphenyl-1,10-phenanthroline is added to the above solution, and stirring is continued at room temperature for 2 to 4 hours under argon protection; then a methanol solution of sodium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate is added to the above solution, and stirring is continued at room temperature for 0.5 to 1.5 hours under argon protection. The molar ratio of phenylphosphine-9,9-dimethylxanthene: 4,7-diphenyl-1,10-phenanthroline: sodium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate is (0.5-1.5): (0.5-2): (0.5-2): (0.5-1.5); after the reaction is completed, the filtrate is filtered, and the solvent is slowly evaporated to obtain light yellow transparent crystals, which are tetrakis(3,5-bis(trifluoromethyl)phenyl)borate-[4,5-bisdiphenylphosphine-9,9-dimethylxanthene]-[4,7-diphenyl-1,10-phenanthroline]copper(I).
6. Use of the ionic cuprous complex having thermally activated delayed fluorescence properties according to claim 1 in recording, storing and protecting information.