Synthesis and application of a concentration-solvent-dependent platinum complex luminescent material

Abstract

The present invention is applicable to the fields of stimulus-responsive light-variable materials, catalysis, fluorescence sensing, biomolecule labeling, information processing and storage, and anti-counterfeiting technology, and provides the synthesis and application of a concentration-solvent-dependent platinum complex luminescent material. The preparation process of the present method is simple and easy to purify. The obtained ionic metal Pt(II) complex phosphorescent material with concentration- and solvent-dependent luminescence changes is stimuli-responsive to solvent and concentration.

Description

Technical Field

[0001] The present invention belongs to the fields of stimulus-responsive light-variable materials, catalysis, fluorescence sensing, biomolecule labeling, information processing and storage, and anti-counterfeiting technology, and in particular relates to the synthesis and application of a concentration-solvent-dependent platinum complex luminescent material. Background Art

[0002] Based on d 8 The metal organic complexes constructed by the transition metal Pt(II) of the first group, benefit from the unique tetragonal planar structure. Under certain conditions, non-covalent metal-metal interactions can be formed between the metal central atoms, accompanied by rich luminescent properties. The supramolecular self-assembly behavior of metal organic Pt(II) complexes is mainly driven by non-covalent weak interactions, including hydrogen bonds, Stacking, electrostatic effects, hydrophobic interactions, and metals The resulting supramolecular self-assembled materials have shown rich application value in OLEDs, catalysis, fluorescence sensing, biomolecule labeling, etc. These reversible and flexible non-covalent weak interactions play a vital role in regulating the luminescence properties and self-assembly behavior of the target complexes, and show unique responsiveness to external stimuli, broadening the development space for the development of stimuli-responsive materials.

[0003] Although various types of Pt(II) complexes have been studied and reported, the research on targeted functionalization design and excited state regulation based on molecular structure, especially the regulation of the self-assembly behavior and luminescence properties of complexes under multiple interactions, is still somewhat insufficient. Therefore, starting from the structural design of the complex molecules, phosphorescent functional units are constructed, and the self-assembly behavior and photophysical properties of Pt(II) complexes driven by multiple weak interactions are deeply explored. In particular, the self-assembly behavior and photophysical properties of functional complex molecules are further regulated under stimulus-responsive conditions. This provides more theoretical basis and design ideas for the more rational design of the structure of supramolecular self-assembly materials, and provides important reference significance in coordinating non-covalent interactions to construct complex systems with rich optical and stimulus-responsive properties. Summary of the Invention

[0004] The present invention provides the synthesis and application of a concentration-solvent-dependent platinum complex luminescent material, which is used in the fields of stimulus-responsive light-variable materials, catalysis, fluorescence sensing, biomolecule labeling, information processing and storage, and anti-counterfeiting.

[0005] The present invention is achieved by providing a concentration solvent-dependent platinum complex luminescent material, comprising: a luminescent material having a molecular structure formula, wherein the molecular structure formula is as shown in formula (1):

[0006] General formula (1):

[0007]

[0008] Wherein, R1 is at least one of H, CF3, and C(CH3)3; R2 is at least one of H, CH3, and C(CH3)3; X is OTf - 、ClO4 - 、BF4 - 、NO3 - At least one of .

[0009] Preferably, the luminescent material adjusts the luminescent color by changing the concentration and solvent.

[0010] A synthesis of a concentration solvent-dependent platinum complex luminescent material comprises the following steps:

[0011] (1) 2-(tri-tert-butyltin)pyridine derivatives and 3,5-dibromo derivatives are refluxed and stirred in toluene with a catalyst of bis(triphenylphosphine)palladium dichloride and potassium carbonate overnight to obtain 1,3-dipyridylbenzene derivatives;

[0012] (2) 1,3-Bipyridinylbenzene derivatives were refluxed with K2PtCl4 in acetic acid for three days to obtain 1,3-Bipyridinylbenzene platinum chloride derivatives.

[0013] Preferably, the method further comprises dissolving a 1,3-dipyridinylbenzeneplatinum chloride derivative in a mixed solution of dichloromethane and acetonitrile, adding silver salt, and stirring for two days to obtain the target molecule.

[0014] Preferably, the preparation method of the luminescent material is: weighing a certain mass of target molecules, dissolving them in acetonitrile, and preparing solutions of different concentrations.

[0015] Preferably, the method for preparing the luminescent material further comprises: adding an appropriate amount of acetonitrile mother liquor to water to obtain mixed solutions of acetonitrile and water in different ratios. When the concentration is changed and water (a poor solvent) is added, the concentration and solvent change the interaction between the molecules of the ionic metal Pt(II) complex, causing changes in the appearance color and luminescent color.

[0016] Preferably, a platinum complex is also included, and the ultraviolet-visible absorption spectrum and emission spectrum of the platinum complex are measured using an ultraviolet spectrophotometer and a fluorescence photometer.

[0017] Preferably, the relationship between the luminescence change and concentration change of the platinum complex is measured using an ultraviolet spectrophotometer and a fluorescence photometer.

[0018] Preferably, the relationship between the luminescence change of the platinum complex and the change of the solvent ratio is measured using an ultraviolet spectrophotometer and a fluorescence photometer.

[0019] A concentration-solvent-dependent platinum complex luminescent material is synthesized and applied in the fields of stimulus-responsive luminescent materials, chemical and biological detection, biological imaging, anti-counterfeiting, etc.

[0020] Compared with the prior art, the embodiments of the present application have the following beneficial effects:

[0021] The method has a simple preparation process and is easy to purify. The obtained ionic metal Pt (II) complex phosphorescent material with concentration- and solvent-dependent luminescence changes has a stimulus response to the solvent and concentration. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] Figure 1 This is the H NMR spectrum of compound C3 in deuterated CDCl3;

[0023] Figure 2 This is the H NMR spectrum of compound C4 in deuterated CDCl3;

[0024] Figure 3 Compound C5 in deuterated DMSO- d 6 H NMR spectrum in;

[0025] Figure 4 is the concentration-dependent UV-visible absorption spectrum of compound C5;

[0026] Figure 5 These are images of samples of compound C5 at different concentrations under visible light;

[0027] Figure 6 It is the absorption value change curve of samples with different concentrations at 500nm;

[0028] Figure 7 is the concentration-dependent luminescence spectrum of compound C5;

[0029] Figure 8 These are images of samples of compound C5 at different concentrations under UV light;

[0030] Figure 9 is the concentration-dependent CIE coordinate diagram of compound C5;

[0031] Figure 10 is the UV-visible absorption spectrum of compound C5 containing different proportions of water;

[0032] Figure 11 Images of compound C5 in acetonitrile and 90% acetonitrile-water under visible light;

[0033] Figure 12This is the luminescence spectrum of compound C5 with different proportions of water;

[0034] Figure 13 These are the images of compound C5 in water at different ratios under UV light;

[0035] Figure 14 CIE coordinate diagram of compound C5 with different proportions of water; DETAILED DESCRIPTION

[0036] Unless otherwise defined, all technical and scientific terms used herein have the same meanings as commonly understood by those skilled in the art to which this application belongs. The terms used in the specification of the application are only for the purpose of describing specific embodiments and are not intended to limit this application. The terms "including" and "having" and any variations thereof in the specification and claims of this application and the above-mentioned drawings are intended to cover non-exclusive inclusions. The terms "first", "second", etc. in the specification and claims of this application or the above-mentioned drawings are used to distinguish different objects, not to describe a specific order.

[0037] References herein to "embodiments" mean that a particular feature, structure, or characteristic described in connection with the embodiments may be included in at least one embodiment of the present application. The appearance of this phrase in various places in the specification does not necessarily refer to the same embodiment, nor does it constitute an independent or alternative embodiment that is mutually exclusive of other embodiments. It is understood, both explicitly and implicitly, by those skilled in the art that the embodiments described herein may be combined with other embodiments.

[0038] The embodiment of the present invention provides a synthesis and application of a concentration-solvent-dependent platinum complex luminescent material, the molecular formula of which is shown in formula (1):

[0039] General formula (1):

[0040]

[0041] Wherein, R1 is at least one of H, CF3, and C(CH3)3; R2 is at least one of H, CH3, and C(CH3)3; X is OTf - 、ClO4 - 、BF4 - 、NO3 - At least one of .

[0042] A method for the synthesis and application of a concentration- and solvent-dependent platinum complex luminescent material [General Formula (1)]:

[0043] (1) 2-(tri-tert-butyltin)pyridine derivatives and 3,5-dibromo derivatives are refluxed and stirred in toluene with a catalyst of bis(triphenylphosphine)palladium dichloride and potassium carbonate overnight to obtain 1,3-dipyridylbenzene derivatives;

[0044] (2) Reflux and stir the 1,3-dipyridinylbenzene derivative with K2PtCl4 in acetic acid for three days to obtain the 1,3-dipyridinylbenzene platinum chloride derivative;

[0045] (3) Dissolve the 1,3-dipyridinylbenzeneplatinum chloride derivative in a mixed solution of dichloromethane and acetonitrile, add silver salt and stir for two days to obtain the target molecule.

[0046] The synthesis and application of concentration- and solvent-dependent platinum complex luminescent materials involve weighing a certain mass of the target molecule and dissolving it in acetonitrile to prepare solutions of varying concentrations. Separately, appropriate amounts of the acetonitrile mother liquor are added to water to create acetonitrile-water mixed solutions of varying ratios. The concentration and solvent changes, along with the addition of water as a poor solvent, alter the interactions between the ionic Pt(II) complex molecules, causing changes in both the apparent color and the luminescent color.

[0047] The method has a simple preparation process and is easy to purify. The obtained ionic metal Pt (II) complex phosphorescent material with concentration- and solvent-dependent luminescence changes has a stimulus-responsive property to the solvent and concentration.

[0048] 1. Synthesis of concentration and solvent-dependent platinum complexes:

[0049] (1) Synthesis of compound C3

[0050]

[0051] A 100 mL, three-necked Shrek flask was charged with degassed toluene (50 mL), C1 (1.33 g, 3.62 mmol), C2 (500 mg, 1.65 mmol), Pd(PPh3)2Cl2 (116 mg, 0.17 mmol), and K2CO3 (1.14 mg, 8.25 mmol). The mixture was stirred at reflux overnight. After the reaction, ethyl acetate (100 mL) was added and the mixture was washed twice with deionized water. The organic layer was collected, dried over anhydrous MgSO4, and the organic solvent was evaporated under reduced pressure to obtain the crude product. Purification by column chromatography (eluent: CH2Cl2-petroleum ether, 1:10, v / v) afforded a white solid (418 mg) in 85% yield. 1 H NMR (400 MHz, CDCl3, 298 K, relative to Me4Si) δ = 8.83 (s, 1H), 8.75 (d, J= 4.8 Hz, 2H), 8.34 (s, 1H), 7.89 (d, J =7.4 Hz, 2H), 7.83 (t, J = 7.6 Hz, 2H), 7.32 (m, t, J = 7.4 Hz, 2H). NMR spectra are shown in Figure 1 .

[0052] (2) Synthesis of compound C4

[0053]

[0054] To a 100 mL three-necked Shrek flask, K2PtCl4 (378 mg, 0.91 mmol), C3 (300 mg, 1.01 mmol), and degassed glacial acetic acid (20 mL) were added and heated under reflux for 3 days. After the reaction, the mixture was cooled to room temperature, filtered, and washed with deionized water to obtain the desired yellow solid (0.35 g) in a 65% yield.

[0055] 1 H NMR (400 MHz, CDCl3, 298 K, relative to Me4Si) δ = 9.39 (d, J = 5.6Hz, 2H), 8.11 – 7.97 (t, J = 9.5 Hz, 2H), 7.78 (d, J = 9.7 Hz, 2H), 7.67 (s,2H), 7.39 (t, J = 7.4 Hz, 2H). NMR spectra are shown in Figure 2 .

[0056] (3) Synthesis of Compound C-6

[0057]

[0058] A mixed solution of C4 (200 mg, 0.38 mmol) and dichloromethane-acetonitrile (10 mL / 10 mL) was added to a 50 mL round-bottom flask and stirred at room temperature for 4 h. The mixture was filtered, the organic solvent was dried, and the target orange solid (187 mg) was obtained by recrystallization with a yield of 72%. 1 H NMR (400 MHz, DMSO- d 6 , 298 K, relative to Me4Si): δ = 8.69 (d, J=5.2 Hz, 2H), 8.43 (d, J = 7.6 Hz, 2H), 8.32 (t, J = 7.6 Hz, 2H), 8.17 (s,2H), 7.67 (t, J = 6.5 Hz, 2H), 2.07 (s, 3H). Figure 3 .

[0059] 2. Synthesis and application of concentration and solvent-dependent platinum complex luminescent materials:

[0060] A certain mass of the target molecule is weighed and dissolved in acetonitrile to prepare solutions of varying concentrations. Separately, appropriate amounts of the acetonitrile mother liquor are added to water to create mixed solutions of varying acetonitrile-water ratios. The concentration and solvent changes in the interaction between the ionic Pt(II) complex molecules, leading to changes in both the apparent color and the luminescent color.

[0061] 3. Study on the properties of ionic metal Pt(II) complex phosphorescent materials with concentration and solvent-dependent luminescence changes:

[0062] from Figure 4 It can be seen from the figure that as the concentration of the target complex molecules in the acetonitrile solution gradually increases, the color of the solution changes from colorless to yellow ( Figure 5 ), the deviation from the linear relationship between absorption and concentration indicates that the molecule is in the MMLCT state ( Figure 6 ), and the luminescence of the solution gradually changes from green to orange ( Figure 7 and Figure 8 ), CIE ( Figure 9 ) The coordinate diagram can clearly show the change process of the luminescent color. With the addition of poor solvent water, the appearance color changes from colorless to light yellow ( Figure 10 and Figure 11 ), the luminescence of the solution gradually changes from green to red ( Figure 12 and Figure 13 ), CIE ( Figure 14 ) The coordinate diagram shows the trend of the color change of the luminescence. The yellow and red luminescence comes from the intermolecular 3 The MMLCT excited state is the result of the combined effects of π-π stacking, Pt-Pt interaction and electrostatic interaction between molecules.

[0063] It should be noted that for the aforementioned embodiments, for simplicity of description, they are all expressed as a series of action combinations. However, those skilled in the art should be aware that the present invention is not limited by the order of the actions described, because according to the present invention, certain steps may be performed in other orders or simultaneously. Secondly, those skilled in the art should also be aware that the embodiments described in this specification are all preferred embodiments, and the actions and modules involved are not necessarily required by the present invention.

[0064] In the several embodiments provided in this application, it should be understood that the disclosed devices can be implemented in other ways. For example, the device embodiments described above are merely illustrative, such as the division of the above-mentioned units. In actual implementation, there may be other division methods, such as multiple units or components can be combined or integrated into another system, or some features can be ignored or not executed. Another point is that the coupling or communication connection between each other shown or discussed can be through some interfaces, and the indirect coupling or communication connection between devices or units can be in the form of telecommunications or other forms.

[0065] The units described above as separate components may or may not be physically separate, and the components shown as units may or may not be physical units, that is, they may be located in one place or distributed across multiple network units. Some or all of these units may be selected according to actual needs to achieve the purpose of the solution of this embodiment.

[0066] The above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit the scope of protection of the invention. Obviously, the embodiments described are only some embodiments of the present invention, rather than all embodiments. Based on these embodiments, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of the present invention. Although the present invention has been described in detail with reference to the above embodiments, ordinary technicians in this field can still combine, add, delete or make other adjustments to the features in the various embodiments of the present invention according to the circumstances without conflict, without making creative work, so as to obtain different other technical solutions that do not deviate from the concept of the present invention in essence, and these technical solutions also fall within the scope of protection of the present invention.

Claims

1. A concentration solvent-dependent platinum complex luminescent material, characterized in that: include: The luminescent material comprises a molecular structure having a general formula, and the molecular structure has a general formula as shown in formula (1): General formula (1): Wherein, R1 is CF3; R2 is at least one of H, CH3, and C(CH3)3; and X is at least one of OTf-, ClO4-, BF4-, and NO3-.

2. The synthesis of a concentration solvent-dependent platinum complex luminescent material according to claim 1, characterized in that: The following steps are involved: (1) 2-(tri-tert-butyltin)pyridine derivatives and 3,5-dibromo derivatives are refluxed and stirred in toluene with a catalyst of bis(triphenylphosphine)palladium dichloride and potassium carbonate overnight to obtain 1,3-dipyridylbenzene derivatives; (2) 1,3-Bipyridinylbenzene derivatives were refluxed with K2PtCl4 in acetic acid for three days to obtain 1,3-Bipyridinylbenzene platinum chloride derivatives.

3. The synthesis of a concentration-solvent-dependent platinum complex luminescent material according to claim 2, characterized in that: The method also includes dissolving a 1,3-dipyridinylbenzeneplatinum chloride derivative in a mixed solution of dichloromethane and acetonitrile, adding silver salt and stirring for two days to obtain a target molecule.

4. The synthesis of a concentration-solvent-dependent platinum complex luminescent material according to claim 3, characterized in that: The preparation method of the luminescent material is as follows: a certain mass of target molecules is weighed, dissolved in acetonitrile, and prepared into solutions of different concentrations.

5. The synthesis of a concentration solvent-dependent platinum complex luminescent material according to claim 4, characterized in that: The preparation method of the luminescent material further includes: taking an appropriate amount of acetonitrile mother liquor and adding it to water to obtain a mixed solution of acetonitrile and water in different proportions; when the concentration is changed and a poor solvent water is added, the concentration and solvent change the interaction between the ionic metal Pt (II) complex molecules, causing changes in the appearance color and the luminescent color.

6. The use of a concentration solvent-dependent platinum complex luminescent material according to claim 1, characterized in that: Applied to stimulus-responsive luminescent materials and anti-counterfeiting fields.

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