An ionic ruthenium metal complex, a preparation method thereof and an application thereof

Abstract

The present invention relates to an ionic ruthenium metal complex, a preparation method thereof and an application thereof, belonging to the technical field of ruthenium metal complexes, and solves the problems of long and complex preparation process and high cost in the prior art. The ionic ruthenium metal complex is composed of an octahedral ruthenium complex cation and an anion with a chiral structure. The chiral circularly polarized electroluminescence of the ionic ruthenium metal complex is realized, and the preparation method is simple and the cost is low.

Description

Technical Field

[0001] The present invention relates to the technical field of metal ruthenium complexes, and in particular to an ionic metal ruthenium complex, a preparation method thereof and uses thereof. Background Art

[0002] Circularly polarized electroluminescence (CPEL) is a process in which a chiral luminescent material emits polarized light under electroexcitation. This method of directly generating polarized light without an optical lens has potential applications in fields such as anti-glare displays, energy-saving displays, future three-dimensional displays, optical encryption and anti-counterfeiting. Transition metal complexes have been widely used as emissive materials for green and red OLEDs in academia and industry due to their potential to efficiently capture singlet and triplet excitons generated by electricity.

[0003] Ionic octahedral transition metal complexes, such as [Ru(bpy)3] 2+ , have two chiral configurations, Δ and Λ, and have a wide range of applications in fields such as chiral sensing, recognition, and assembly. However, those prepared by traditional methods are often racemates in which the two configurations are mixed in equal proportions, and it is necessary to use expensive chiral high-performance liquid chromatography for resolution or introduce chiral auxiliary ligands in combination with chiral resolution to obtain the corresponding diastereoisomers. This preparation process is lengthy, complex and costly. Summary of the Invention

[0004] In view of the above analysis, embodiments of the present invention aim to provide an ionic metal ruthenium complex, a preparation method thereof and uses thereof, so as to solve the problem that the existing preparation process for obtaining a metal complex with diastereoisomers is lengthy, complex and costly.

[0005] On the one hand, embodiments of the present invention provide an ionic metal ruthenium complex, which is composed of an octahedral ruthenium complex cation and an anion with a chiral structure.

[0006] Based on a further improvement of the ionic metal ruthenium complex, the anion with a chiral structure is 1,1'-binaphthyl-2,2'-oxy-phosphate, tartrate or camphorsulfonate; preferably camphorsulfonate;

[0007] Among them, the camphorsulfonate has left-handed (-) or right-handed (+).

[0008] Based on a further improvement of the ionic metal ruthenium complex, the anion of the camphorsulfonate with a chiral structure and the octahedral ruthenium complex cation are combined through an ionic bond to form an ionic metal ruthenium complex.

[0009] Based on a further improvement of the ionic metal ruthenium complex, the ionic metal ruthenium complex has the structure shown in Formula I:

[0010]

[0011] Among them, in formula I, * represents the chirality of the camphorsulfonate ion, and the camphorsulfonate ion is left-handed (-) or right-handed (+);

[0012] The N^N ligand is a bipyridine or phenanthroline and its derivative ligand;

[0013] R is H, a C1-C12 alkyl group or a benzene ring.

[0014] Based on further improvement of the ionic metal ruthenium complex, the ionic metal ruthenium complex has a structure of formula II, formula III or formula IV:

[0015]

[0016] Among them, the ionic metal ruthenium complex with the structure of formula II uses octahedral tris(2,2'-bipyridine) ruthenium complex as the cation and left-handed or right-handed camphorsulfonate ion as the anion;

[0017] In formula II, * represents the chirality of the camphorsulfonate ion, and the camphorsulfonate ion is left-handed (-) or right-handed (+);

[0018] Or

[0019]

[0020] Among them, the ionic metal ruthenium complex with the structure of formula III uses octahedral tris(1,10-phenanthroline) ruthenium complex as the cation and left-handed or right-handed camphorsulfonate ion as the anion;

[0021] In formula III, * represents the chirality of the camphorsulfonate ion, and the camphorsulfonate ion is left-handed (-) or right-handed (+);

[0022] Or

[0023]

[0024] Among them, the ionic metal ruthenium complex with the structure of formula IV uses tris(4,7-diphenyl-1,10-phenanthroline) ruthenium complex as the cation and left-handed or right-handed camphorsulfonate ion as the anion;

[0025] In formula IV, * represents the chirality of the camphorsulfonate ion, and the camphorsulfonate ion is left-handed (-) or right-handed (+).

[0026] A method for preparing the above-mentioned ionic ruthenium metal complex, comprising: using a complex with chloride ion as the anion and tris(bipyridine)ruthenium, tris(phenanthroline)ruthenium and their derivatives as the cation as reactant (1), and a compound with silver ion as the cation and an anion with a chiral structure as reactant (2), dissolving reactants (1) and (2) in an organic solvent, and performing an ion exchange reaction to obtain the ionic ruthenium metal complex.

[0027] Based on a further improvement of the above method, the ion exchange reaction product is recrystallized and purified to obtain the ionic ruthenium metal complex; preferably, before recrystallization and purification, it includes filtering the solution after the ion exchange reaction to remove the silver chloride precipitate impurities generated by the reaction. After filtering the solution after the ion exchange reaction, the filtrate is concentrated and recrystallized to obtain the ionic ruthenium metal complex; more preferably, during the ion exchange reaction, the solution is heated.

[0028] Wherein, the molar ratio of the organic solvent to reactant (1) and reactant (2) is 500-2000:1:2-3.

[0029] The application of the above-mentioned ionic ruthenium metal complex or the ionic ruthenium metal complex prepared by the above method includes: the ionic ruthenium metal complex is applied to circularly polarized luminescent materials, circularly polarized luminescent layers, and circularly polarized luminescent devices.

[0030] Based on a further improvement of the application of the above ionic ruthenium metal complex, using the ionic ruthenium metal complex as a luminescent material to prepare a luminescent layer in CP-OLED; or using the ionic ruthenium metal complex to prepare an active layer in a chiral photodetector; or using the ionic ruthenium metal complex as a circularly polarized luminescent material to prepare a luminescent layer in a circularly polarized luminescent electrochemical cell; or using the ionic ruthenium metal complex to mix with a chiral ionic liquid to prepare a luminescent layer of a circularly polarized luminescent electrochemical cell.

[0031] Wherein, the chiral ionic liquid is 1-butyl-3-methylimidazolium camphorsulfonate;

[0032] The molar ratio of the chiral ionic liquid to the ionic ruthenium metal complex is 0.25-2.

[0033] Based on a further improvement of the application of the above ionic ruthenium metal complex, the circularly polarized luminescent electrochemical cell is composed of a transparent substrate, a PEDOT:PSS layer, a circularly polarized luminescent layer and a metal electrode;

[0034] Using the ionic ruthenium metal complex or a mixture thereof with a chiral ionic liquid as a solute to prepare a solution with a certain concentration, spin-coating the solution on a smooth layer, and after annealing treatment, obtaining the circularly polarized luminescent layer.

[0035] Based on further improvements to the applications of the above-mentioned ionic ruthenium metal complexes, using the ionic ruthenium metal complex as the solute, dissolving this solute in an organic solvent with high or low polarity to obtain a solution with a certain concentration; preferably, the organic solvent is one or more of methanol, dimethylformamide, acetonitrile, tetrahydrofuran, dioxane, ethanol, dichloromethane, and chlorobenzene.

[0036] Compared with the prior art, the present invention can achieve at least one of the following beneficial effects:

[0037] 1. The present invention introduces a chiral anion onto the octahedral ruthenium complex to change the configuration of the ruthenium metal complex. Without the need to resolve the octahedral ruthenium complex or introduce a chiral auxiliary ligand for chiral resolution treatment, by endowing the ruthenium metal complex with chirality through the chiral-structured anion, chiral circularly polarized electroluminescence of the ruthenium metal complex can be achieved. The preparation is simple and significantly reduces costs.

[0038] 2. The present invention introduces a left-handed or right-handed camphorsulfonate group onto the octahedral ruthenium complex. By endowing the ionic ruthenium metal complex with chirality through the camphorate group, there is no need to resolve the structure of the octahedral ruthenium complex, nor is it necessary to introduce an auxiliary ligand onto the octahedral ruthenium complex and combine chiral resolution to endow the target with chirality. Chiral circularly polarized electroluminescence of the ionic ruthenium metal complex can be achieved. The preparation method is simple and the cost is low.

[0039] 3. The present invention provides a new substance for chiral circularly polarized electroluminescence. This substance is composed of an octahedral ruthenium complex and a left-handed or right-handed camphorate group, and is prepared by an ion exchange reaction between silver camphorsulfonate and the octahedral ruthenium complex in a solvent. Without the need for a catalyst, the reaction can occur under heating or non-heating conditions. The preparation method is simple, and this new substance can be obtained. Moreover, this new substance can be used as a circularly polarized luminescent material to achieve chiral solid-state circularly polarized electroluminescence, and the luminescence asymmetry factor (g EL ) of the circularly polarized luminescent electrochemical cell prepared using this material can reach or even exceed the level of the prior art.

[0040] 4. The ionic ruthenium metal complex provided by the present invention can be dissolved in solvents with different polarities. It can be fully dissolved in solvents with high polarity such as methanol and solvents with low polarity such as chlorobenzene. When the ionic ruthenium metal complex is used as a circularly polarized luminescent material, it has good solubility in both strongly polar and weakly polar solvents, which is beneficial for device processing. In addition, there are many types of solvents to choose from. When preparing the circularly polarized luminescent layer, it is possible to overcome the adverse effects that may occur between layers, and low-cost solvents can be selected to reduce costs. Moreover, the ionic ruthenium metal complex of the present invention has good solubility, which is beneficial for spin coating into a film and is beneficial for device processing.

[0041] 5. Using the ionic ruthenium metal complex of the present invention as a circularly polarized luminescent material to prepare a circularly polarized luminescent layer, it has good surface film-forming properties, which is beneficial to device processing.

[0042] 6. Using the ionic ruthenium metal complex of the present invention as a circularly polarized luminescent material, it has good thermal, electrical and chemical stabilities, providing strong impetus for the application of electroluminescent devices.

[0043] 7. Compared with traditional classical chiral complexes, the chiral ionic ruthenium metal complex luminescent material prepared in the present invention has a simple preparation method and low cost. The spin-coated thin film shows circularly polarized photoluminescence, and as a chiral luminescent material, it shows good circularly polarized electroluminescence performance in a light-emitting electrochemical cell, and can be widely applied in fields such as circularly polarized luminescent electrical devices.

[0044] 8. Introducing a left-handed or right-handed camphorsulfonic acid root anion onto the octahedral ruthenium complex, and through the chiral transfer of the chiral anion in the solid state to the achiral cationic complex, it can enable the material to generate photoluminescence and electroluminescence circular polarization. At present, the development of circularly polarized photoluminescence is relatively fast, but the development of circularly polarized electroluminescent materials lags seriously. Ultimately, the actual application still mainly focuses on circularly polarized electroluminescent devices. Therefore, the present invention lays a foundation for the development of materials with both photoluminescence and electroluminescence circular polarization.

[0045] 9. The chiral camphorsulfonic acid root ion introduced into the chiral ionic ruthenium metal complex luminescent material has a large spatial volume, effectively preventing the quenching between cationic excitons, enabling the device to still maintain good electroluminescent performance at a high driving voltage, and showing a small efficiency roll-off.

[0046] 10. Introducing a chiral ionic liquid containing the same camphorsulfonic acid root ion as the metal complex into the luminescent layer of the circularly polarized light-emitting electrochemical cell can improve the efficiency of the circularly polarized light-emitting electrochemical cell device.

[0047] In the present invention, the above-mentioned technical solutions can also be combined with each other to achieve more preferred combination schemes. Other features and advantages of the present invention will be described in the subsequent specification, and some advantages can be made obvious from the specification or understood by implementing the present invention. The objectives and other advantages of the present invention can be realized and obtained from the content specifically pointed out in the specification and the drawings. BRIEF DESCRIPTION OF THE DRAWINGS

[0048] The drawings are only for the purpose of showing specific embodiments and are not considered as limiting the present invention. Throughout the drawings, the same reference signs represent the same components.

[0049] Figure 1Electrochemical cyclic voltammogram of the ionic ruthenium metal complex with the structure of formula II-1 in the present invention;

[0050] Figure 2 Circular dichroism absorption spectrum (CD) of the spin-coated and annealed films of the ionic ruthenium metal complexes with the structures of formula II-1 and formula II-2 in the present invention;

[0051] Figure 3 Photoluminescence circularly polarized luminescence spectrum of the spin-coated films of the ionic ruthenium metal complexes with the structures of formula II-1 and formula II-2 in the present invention;

[0052] Figure 4 AFM image of the film spin-coated on a silicon wafer substrate of the ionic ruthenium metal complex with the structure of formula II-1 in the present invention;

[0053] Figure 5 Electroluminescence spectrum of the light-emitting electrochemical cell prepared based on the ionic ruthenium metal complex with the structure of formula II-1 in the present invention under different pulse voltages;

[0054] Figure 6 Circularly polarized electroluminescence spectrum of the light-emitting electrochemical cell prepared based on the ionic ruthenium metal complexes with the structures of formula II-1 and formula II-2 in the present invention;

[0055] Figure 7 External quantum efficiency (EQE)-luminance curve of the light-emitting electrochemical cell prepared based on the ionic ruthenium metal complex with the structure of formula II-1 in the present invention;

[0056] Figure 8 Schematic diagram of the device structure of the circularly polarized light-emitting electrochemical cell in the present invention. Detailed implementation manners

[0057] The following combines the drawings to specifically describe the preferred embodiments of the present invention. Among them, the drawings form a part of this application and are used together with the embodiments of the present invention to explain the principle of the present invention, and are not used to limit the scope of the present invention.

[0058] Compared with inorganic semiconductors, organic light-emitting diodes (OLEDs) have economic and manufacturing advantages and have recently received increasing attention. Compared with the organic small molecules and polymers that have been widely used in OLEDs, the synthesis and purification of ionic octahedral transition metal complexes are relatively easy, and their symmetric t 6 2g configuration enhances the electrical stability, has a high photoluminescence (PL) quantum efficiency, a medium-long excited state lifetime, and chemical stability, and has therefore attracted great attention in the field of optoelectronic devices in recent years.

[0059] Among these complexes, Ru(bpy)32+ has been the most widely studied. It has good phosphorescent emission efficiency in solution. Ru(bpy)3 2+ also exhibits stable and reversible reduction / oxidation behavior based on metals and ligands, so it has been widely used as a material for solution electrochemiluminescence (ECL) cells, and a quantum efficiency of up to 25% has been achieved so far. In solutions containing Ru(bpy)3 2+ and most other luminescent transition metal complexes, the luminescence is phosphorescence from spin-forbidden triplet excited states, and according to spin statistics, its formation efficiency is three times that of singlet states.

[0060] In addition, 1 Ru(bpy)3 2+* 's spin-allowed singlet excited state will quickly deactivate through spin-orbit coupling, generating the lowest-energy triplet excited state. These PL and ECL properties provide strong motivation for the application of solid-state OLEDs.

[0061] In addition, when [Ru(bpy)3](PF6)2 is used, the accumulation / consumption of negative counterions (such as PF6 － ) near the anode / cathode is beneficial to the injection of holes and electrons and is independent of the work function of the electrode; while Ru(bpy)3 2+ can be used as both an effective hole / electron transporter and a lumophore, so a single-layer electroluminescent device, a light-emitting electrochemical cell (LEC), can be fabricated using it.

[0062] Circularly polarized electroluminescence (CPEL) is the process in which chiral luminescent materials emit polarized light under electroexcitation. This method of directly generating polarized light without optical lenses has potential application value in fields such as anti-glare displays, energy-saving displays, future three-dimensional displays, and optical encryption and anti-counterfeiting.

[0063] Transition metal complexes have been widely used as emission materials for green and red OLEDs in academia and industry due to their potential to fully capture electrically generated singlet and triplet excitons. Ionic octahedral transition metal complexes, such as [Ru(bpy)3] 2+ , have two chiral configurations, Δ and Λ, and have extensive applications in fields such as chiral sensing, recognition, and assembly.

[0064] However, what is often prepared by traditional methods is a racemate with an equal ratio of the two configurations, and it is necessary to obtain the corresponding diastereoisomers by means of expensive chiral high-performance liquid chromatography separation or by introducing chiral auxiliary ligands in combination with chiral separation. This preparation process is long, complex, and costly.

[0065] Therefore, it is highly necessary to develop a simple and efficient method for preparing chiral metal ruthenium complex luminescent materials, and it is expected to apply the prepared materials to the preparation of circularly polarized luminescence electrochemical cells (CP-LECs) and achieve efficient circularly polarized electroluminescence (CPEL).

[0066] To solve the above problems, the present invention provides an ionic metal ruthenium complex, which is composed of an octahedral ruthenium complex cation and an anion with a chiral structure.

[0067] Compared with the prior art, the present invention introduces a chiral anion onto the octahedral ruthenium complex to change the configuration of the metal ruthenium complex. Without the need to resolve the octahedral ruthenium complex or introduce a chiral auxiliary ligand for chiral resolution treatment, the chiral metal ruthenium complex can be achieved by endowing the metal ruthenium complex with chirality through an anion with a chiral structure. The preparation is simple and the cost is significantly reduced.

[0068] Among them, the anion with a chiral structure can be 1,1'-binaphthyl-2,2'-oxy-phosphate, tartrate or camphorsulfonate.

[0069] In a possible embodiment, the anion with a chiral structure is a chiral camphorsulfonate anion, and the chiral camphorsulfonate anion and the octahedral ruthenium complex cation are combined through an ionic bond to form an ionic metal ruthenium complex.

[0070] Furthermore, the camphorsulfonate is left-handed (-) or right-handed (+).

[0071] Furthermore, the structural formula of the ionic metal ruthenium complex is shown in Formula I,

[0072]

[0073] Among them, in Formula I, * represents the chirality of the camphorsulfonate, and the camphorsulfonate is left-handed (-) or right-handed (+);

[0074] The N^N ligand is a bipyridine or a phenanthroline and its derivative ligand;

[0075] R is H, a C1-C12 alkyl group or a benzene ring.

[0076] Exemplarily, a complex of octahedral tris(2,2'-bipyridine)ruthenium, tris(1,10-phenanthroline)ruthenium or tris(4,7-diphenyl-1,10-phenanthroline)ruthenium is used as the chromophore cation, and the chromophore cation and the camphorsulfonate anion form an ionic metal ruthenium complex.

[0077] Exemplarily, R is H or a benzene ring.

[0078] Specifically, a complex with chloride ion as the anion and tris(bipyridine)ruthenium, tris(o-phenanthroline)ruthenium and their derivatives as the cation is used as reactant (1), and silver camphorsulfonate with a chiral structure in the anion is used as reactant (2). Reactants (1) and (2) are dissolved in an organic solvent, and an ion exchange reaction is carried out to obtain an ionic metal ruthenium complex with the structure of Formula I.

[0079] In a possible embodiment, the ionic metal ruthenium complex has the structure of Formula II:

[0080]

[0081] Among them, the ionic metal ruthenium complex with the structure of Formula II has an octahedral tris(2,2'-bipyridine)ruthenium complex as the cation and a levorotatory or dextrorotatory camphorsulfonate as the anion.

[0082] In a possible embodiment, the ionic metal ruthenium complex has the structure of Formula III:

[0083]

[0084] Among them, the ionic metal ruthenium complex with the structure of Formula III has an octahedral tris(1,10-phenanthroline)ruthenium complex as the cation and a levorotatory or dextrorotatory camphorsulfonate as the anion.

[0085] In a possible embodiment, the ionic metal ruthenium complex has the structure of Formula IV:

[0086]

[0087] Among them, the ionic metal ruthenium complex with the structure of Formula IV has tris(4,7-diphenyl-1,10-phenanthroline)ruthenium complex as the cation and a levorotatory or dextrorotatory camphorsulfonate as the anion.

[0088] In order to obtain the above ionic metal ruthenium complex, the present invention also provides a preparation method of the above ionic metal ruthenium complex, including:

[0089] Using a complex with chloride ion as the anion and tris(bipyridine)ruthenium, tris(o-phenanthroline)ruthenium and their derivatives as the cation as reactant (1), and a compound with silver ion as the cation and a chiral structure in the anion as reactant (2), dissolving reactants (1) and (2) in an organic solvent, and carrying out an ion exchange reaction to obtain the above ionic metal ruthenium complex.

[0090] Among them, the molar ratio of the organic solvent to reactant (1) and reactant (2) is 500-2000:1:2-3.

[0091] Exemplarily, the organic solvent may be methanol, dimethylformamide, ethanol or dioxane.

[0092] In a possible implementation, the reactant (2) is silver camphorsulfonate.

[0093] Among them, silver camphorsulfonate is levorotatory (-) or dextrorotatory (+) silver camphorsulfonate.

[0094] Furthermore, the ion-exchange reaction product is recrystallized and purified to obtain an ionic metal ruthenium complex.

[0095] Among them, before recrystallization and purification, it includes filtering the solution after the ion-exchange reaction to remove the silver chloride precipitate impurities generated by the reaction.

[0096] Among them, after filtering the solution after the ion-exchange reaction, the filtrate is concentrated and recrystallized to obtain an ionic metal ruthenium complex.

[0097] Among them, the reagents used in the recrystallization process may be dichloromethane, tetrahydrofuran or diethyl ether.

[0098] In order to improve the ion-exchange reaction efficiency, the solution is heated during the reaction.

[0099] Among them, the heating temperature is lower than the boiling point temperature value of the organic solvent, generally 40°C to 100°C, in order to avoid the silver mirror reaction of the generated silver chloride precipitate. At the same time, it protects the chirality of the camphorsulfonate group, prevents racemization, and low temperature consumes less energy, which is beneficial to reducing costs.

[0100] Among them, when no solid continues to precipitate, the reaction terminates, and the reaction time is generally 0.5 - 2h.

[0101] Among them, the Cl ions in the reaction solution can be detected by thin layer chromatography (TLC). When there are no Cl ions in the solution, the reaction terminates.

[0102] In addition, the present invention also provides an application of the above ionic metal ruthenium complex, including the application of the above ionic metal ruthenium complex or the ionic metal ruthenium complex obtained by the above method in circularly polarized luminescent materials, circularly polarized luminescent layers, and circularly polarized luminescent devices.

[0103] Among them, the circularly polarized luminescent device includes CP-OLED, chiral photodetectors, circularly polarized luminescent electrochemical cells, etc.

[0104] In a possible implementation, the above ionic metal ruthenium complex is used as a luminescent material to prepare the luminescent layer in CP-OLED.

[0105] In a possible implementation, the above-mentioned ionic metal ruthenium complex is used to prepare an active layer in a chiral optoelectronic detector.

[0106] In a possible implementation, the above-mentioned ionic metal ruthenium complex is used as a circularly polarized luminescent material to prepare a luminescent layer in a circularly polarized luminescent electrochemical cell.

[0107] In a possible implementation, a luminescent layer of a circularly polarized luminescent electrochemical cell is prepared by mixing an ionic metal ruthenium complex with a chiral ionic liquid.

[0108] Among them, the chiral ionic liquid is 1-butyl-3-methylimidazolium camphorsulfonate to further improve the circularly polarized electroluminescence performance of the luminescent layer.

[0109] Among them, the circularly polarized luminescent electrochemical cell is composed of a transparent substrate, a PEDOT:PSS layer, a circularly polarized luminescent layer, and a metal electrode. When preparing the luminescent layer, the above-mentioned ionic metal ruthenium complex or the mixture of the ionic metal ruthenium complex and the chiral ionic liquid is coated on a smooth layer to prepare a circularly polarized luminescent layer.

[0110] Among them, since the circularly polarized luminescent layer is too thin and easily broken down, and too thick will cause serious exciton quenching, therefore, the circularly polarized luminescent layer needs to have a medium thickness. Exemplarily, the thickness of the circularly polarized luminescent layer is 30 - 100 nm.

[0111] Among them, the molar ratio of the chiral ionic liquid to the ionic metal ruthenium complex is 0.25 - 2.

[0112] Furthermore, a preparation method of a circularly polarized luminescent electrochemical cell based on a chiral luminescent material of an ionic metal ruthenium complex includes:

[0113] S1: Spin-coat a smooth layer on a transparent conductive substrate;

[0114] Among them, the transparent conductive substrate is ITO glass, and the thickness of the coating (ITO) is 120 nm - 250 nm.

[0115] Among them, the sheet resistance of the substrate is 15 Ω / sq, and the light transmittance is 88%.

[0116] Among them, the raw material of the spin-coated smooth layer can be PMMA or PEDOT:PSS, and the solvent can be water, ethanol, isopropanol, etc.

[0117] Among them, both PMMA and PEDOT:PSS have the ability of smoothing and hole transport.

[0118] Among them, the spin-coating speed is 1000 - 4000 rpm, and the spin-coating time can be 30 - 60 s.

[0119] Among them, after the spin coating of the smoothing layer is completed, the smoothing layer is annealed to dry the smoothing layer.

[0120] Exemplarily, the annealing temperature is 100-150 °C, and the annealing time can be 10-60 minutes.

[0121] Among them, the thickness of the smoothing layer is 30-80 nm.

[0122] S2: Spin-coat an ionic metal ruthenium complex or a mixture thereof with a chiral ionic liquid on the smoothing layer to prepare a light-emitting layer;

[0123] Among them, a solution with a certain concentration is prepared using an ionic metal ruthenium complex or a mixture thereof with a chiral ionic liquid as the solute, and the solution is spin-coated on the smoothing layer and annealed to obtain a circularly polarized light-emitting layer.

[0124] Exemplarily, the concentration of the solution is 15-40 mg / ml.

[0125] In a possible implementation manner, an ionic metal ruthenium complex is used as the main raw material of the light-emitting layer.

[0126] Among them, the obtained ionic metal ruthenium complex is in the form of a solid powder, which has good solubility and a wide range of polar compatibility. Therefore, the solvent can be selected from organic solvents with large or small polarity.

[0127] Exemplarily, the organic solvent is one or more of methanol, dimethylformamide, acetonitrile, tetrahydrofuran, dioxane, ethanol, dichloromethane, and chlorobenzene.

[0128] Among them, the ionic metal ruthenium complex or the ionic metal ruthenium complex obtained by the above preparation method has good solubility. When preparing each layer of the circularly polarized electrochemical cell, there are many choices for the solvent type of the light-emitting layer. When selecting the solvent, avoid using the same solvent as the light-emitting layer to avoid eluting the light-emitting layer and damaging the device structure.

[0129] In a possible implementation manner, a mixture of an ionic metal ruthenium complex and a chiral ionic liquid is used as the main raw material of the light-emitting layer.

[0130] Among them, the molar ratio of the chiral ionic transition metal ruthenium complex to the chiral ionic liquid is 1 / 0, 4 / 1, 2 / 1, 1 / 1.

[0131] Among them, the solvent can be acetonitrile, dimethylformamide (DMF), dimethyl sulfoxide (DMSO), etc., or a mixed solution in a certain proportion.

[0132] Among them, during spin coating, the rotation speed can be 1000-3000 rpm, and the spin coating time is 30-60 s.

[0133] Among them, the greater the concentration of the solution and the smaller the rotation speed, the greater the thickness of the light-emitting layer.

[0134] S3: Prepare a top electrode LiF / Al on the light-emitting layer by vacuum thermal evaporation.

[0135] In this way, after preparing the light-emitting layer on the smoothing layer, a circularly polarized light-emitting electrochemical cell is formed together with the transparent substrate and the metal electrode.

[0136] Compared with the prior art, the present invention introduces a chiral anion onto the octahedral ruthenium complex to change the configuration of the metal ruthenium complex. Without the need to resolve the octahedral ruthenium complex or introduce a chiral auxiliary ligand for chiral resolution treatment, the chiral metal ruthenium complex can be achieved by endowing the metal ruthenium complex with chirality through the chiral anion with a chiral structure. The preparation is simple and the cost is significantly reduced.

[0137] The present invention introduces a left-handed or right-handed camphorsulfonate group onto the octahedral ruthenium complex. By endowing the ionic metal ruthenium complex with chirality through the camphorate group, there is no need to resolve the structure of the octahedral ruthenium complex, nor to introduce an auxiliary ligand onto the octahedral ruthenium complex and combine chiral resolution to endow the target with chirality. The chiral circularly polarized electroluminescence of the ionic metal ruthenium complex can be achieved. The preparation method is simple and the cost is low.

[0138] The present invention provides a new substance for chiral circularly polarized electroluminescence. This substance is composed of an octahedral ruthenium complex and a left-handed or right-handed camphorate group, and is prepared by an ion exchange reaction between silver camphorsulfonate and an octahedral ruthenium complex in a solvent. Without the need for a catalyst, the reaction can occur under heating or non-heating conditions. The preparation method is simple, and the new substance can be obtained. Moreover, this new substance can be used as a circularly polarized light-emitting material to achieve chiral solid-state circularly polarized electroluminescence, and the luminescence asymmetry factor (g EL ) of the circularly polarized light-emitting electrochemical cell prepared using this material can reach or even exceed the level of the prior art.

[0139] The ionic metal ruthenium complex provided by the present invention can be dissolved in solvents with different polarities, such as methanol with high polarity and chlorobenzene with low polarity, and can be fully dissolved. When the ionic metal ruthenium complex is used as a circularly polarized light-emitting material, it has good solubility in both strongly polar and weakly polar solvents, which is beneficial for device processing, and there are many types of solvents to choose from. When preparing the circularly polarized light-emitting layer, it can overcome the adverse effects that may occur between layers, and low-cost solvents can be selected to reduce costs; in addition, the ionic metal ruthenium complex of the present invention has good solubility, which is beneficial for spin coating into a film and is beneficial for device processing.

[0140] Using the ionic metal ruthenium complex of the present invention as a circularly polarized light-emitting material to prepare a circularly polarized light-emitting layer has good film-forming properties on the surface and is beneficial for device processing.

[0141] Using the ionic ruthenium complex of the present invention as a circularly polarized luminescent material, it has good thermal, electrical and chemical stability, providing strong impetus for the application of electroluminescent devices.

[0142] Compared with traditional classical chiral complexes, the chiral ionic ruthenium complex luminescent material prepared in the present invention has a simple preparation method, low cost. The spin-coated film shows circularly polarized photoluminescence, and as a chiral luminescent material, it shows good circularly polarized electroluminescence performance in a light-emitting electrochemical cell, and can be widely applied in fields such as circularly polarized luminescent electrical devices.

[0143] Introducing a left-handed or right-handed camphorsulfonic acid root anion onto an octahedral ruthenium complex, and through chiral transfer of the chiral anion in the solid state to the achiral cationic complex, it can enable the material to generate photoluminescence and electroluminescence with circular polarization. At present, the development of circularly polarized photoluminescence is relatively fast, but the development of circularly polarized electroluminescent materials lags severely. Ultimately, it is still mainly the circularly polarized electroluminescent devices that move towards practical applications. Therefore, the present invention lays a foundation for the development of materials with both photoluminescence and electroluminescence with circular polarization.

[0144] The introduced chiral camphorsulfonic acid root ion in the chiral ionic ruthenium complex luminescent material has a large spatial volume, effectively preventing quenching between cationic excitons, enabling the device to still maintain good electroluminescent performance at a high driving voltage, showing a small efficiency roll-off.

[0145] Introducing a chiral ionic liquid containing the same camphorsulfonic acid root ion as the metal complex into the light-emitting layer of the circularly polarized luminescent electrochemical cell can improve the efficiency of the circularly polarized luminescent electrochemical cell device.

[0146] Example 1

[0147] An ionic ruthenium complex, which has a structure of Formula II.

[0148] Its synthetic route is as follows:

[0149]

[0150] Among them, the anion of silver (+)-camphorsulfonate or (-)-camphorsulfonate is used to endow the cation of tris(2,2'-bipyridine)ruthenium chloride with a chiral configuration.

[0151] (1) Using silver (+)-camphorsulfonate and tris(2,2'-bipyridine)ruthenium chloride to prepare an ionic ruthenium complex luminescent material shown in Formula II-1 as follows:

[0152]

[0153] (2) Prepare an ionic ruthenium metal complex luminescent material shown in Formula II-2 by using silver (-)-camphorsulfonate and tris(2,2'-bipyridine) ruthenium(II) chloride:

[0154]

[0155] Example 2

[0156] An ionic ruthenium metal complex having a structure of Formula III.

[0157] Its synthetic route is as follows:

[0158]

[0159] Among them, the anions of silver (+)- or (-)-camphorsulfonate are used to endow the cations of tris(1,10-phenanthroline) ruthenium(II) chloride with chiral configurations.

[0160] (1) Prepare an ionic ruthenium metal complex luminescent material shown in Formula III-1 by using silver (+)-camphorsulfonate and tris(1,10-phenanthroline) ruthenium(II) chloride:

[0161]

[0162] (2) Prepare an ionic ruthenium metal complex luminescent material shown in Formula III-2 by using silver (-)-camphorsulfonate and tris(1,10-phenanthroline) ruthenium(II) chloride:

[0163]

[0164] Example 3

[0165] An ionic ruthenium metal complex having a structure of Formula IV.

[0166] Its synthetic route is as follows:

[0167]

[0168] Among them, the anions of silver (+)- or (-)-camphorsulfonate are used to endow the cations of tris(4,7-diphenyl-1,10-phenanthroline) ruthenium(II) chloride with chiral configurations.

[0169] (1) Prepare an ionic ruthenium metal complex luminescent material shown in Formula IV-1 by using silver (+)-camphorsulfonate and tris(4,7-diphenyl-1,10-phenanthroline) ruthenium(II) chloride:

[0170]

[0171] (2) Prepare an ionic metal ruthenium complex shown in Formula IV-2 below by using silver L-(−)-camphorsulfonate and tris(4,7-diphenyl-1,10-phenanthroline) ruthenium(III) chloride:

[0172]

[0173] Example 4

[0174] A method for preparing an ionic metal ruthenium complex having the structure of Formula II-1 above, comprising:

[0175] Dissolve 64 mg of tris(2,2'-bipyridine) ruthenium(III) chloride and 70 mg of D-(+)-camphorsulfonic acid silver in 20 mL of methanol, and heat under reflux for 1 hour under nitrogen protection; after cooling to room temperature, filter to remove the resulting silver chloride precipitate; concentrate the filtrate, and recrystallize with dichloromethane / tetrahydrofuran to obtain 94 mg of red needle crystals of Formula II-1, with a yield of 91%. 1 H NMR (400 MHz, CD3CN): δ 8.58 (d, J = 8.2 Hz, 6H), 8.06 (t, J = 7.9 Hz, 6H), 7.73 (d, J = 5.5 Hz, 6H), 7.40 (dd, J = 7.5, 5.9 Hz, 6H), 3.02 (d, J = 14.6 Hz, 2H), 2.80–2.70 (m, 2H), 2.53 (d, J = 14.6 Hz, 2H), 2.31–2.26 (m, 2H), 1.99 - 1.91 (m, 4H), 1.81 (d, J = 18.1 Hz, 2H), 1.50–1.42 (m, 2H), 1.35 - 1.28 (m, 2H), 1.08 (s, 6H), 0.79 (s, 6H).

[0176] Among them, nitrogen can be replaced by an inert gas, that is, heating under reflux can be carried out under inert gas protection.

[0177] Among them, the heating temperature is 70 °C.

[0178] Among them, before recrystallizing with dichloromethane / tetrahydrofuran, the filtrate is concentrated to dryness.

[0179] Among them, when the filtrate is concentrated to 1 / 2 of the original volume, the filtrate is cooled to room temperature, filtered, and the filtered filtrate is continuously concentrated.

[0180] Among them, the solution is concentrated by means of reduced-pressure rotary evaporation, and the temperature of reduced-pressure rotary evaporation is 35 - 45 °C.

[0181] Among them, during the recrystallization process, the mixing ratio of dichloromethane / tetrahydrofuran added is 1:2 to 1:5, and the addition amount is up to the volume of the solution before concentration. Stir to fully dissolve the solid precipitated by concentration, and then at room temperature, filter the dissolved solution to obtain a filtrate, and perform recrystallization treatment on the filtrate to obtain an ionic metal ruthenium complex with the structure of Formula II-1.

[0182] Among them, the ion exchange reaction is carried out using a two-necked or single-necked round-bottom flask equipped with a reflux condenser under nitrogen or inert gas.

[0183] Example 5

[0184] A preparation method of an ionic metal ruthenium complex having the above structure of Formula II-2, comprising:

[0185] Dissolve 64 mg of tris(2,2'-bipyridine) ruthenium chloride and 70 mg of silver L-(−)-camphorsulfonate in 20 mL of methanol, and heat under reflux for 1 hour under nitrogen protection; after cooling to room temperature, filter to remove the precipitated silver chloride; concentrate the filtrate, and recrystallize with dichloromethane / tetrahydrofuran to obtain 97 mg of red needle crystals of Formula II-2, with a yield of 94%. 1 H NMR (400 MHz, CD3CN): δ 8.58 (d, J = 8.2 Hz, 6H), 8.06 (t, J = 7.9 Hz, 6H), 7.73 (d, J = 5.5 Hz, 6H), 7.40 (dd, J = 7.5, 5.9 Hz, 6H), 3.02 (d, J = 14.6 Hz, 2H), 2.80–2.70 (m, 2H), 2.53 (d, J = 14.6 Hz, 2H), 2.31–2.26 (m, 2H), 1.99 - 1.91 (m, 4H), 1.81 (d, J = 18.1 Hz, 2H), 1.50–1.42 (m, 2H), 1.35 - 1.28 (m, 2H), 1.08 (s, 6H), 0.79 (s, 6H).

[0186] Among them, nitrogen can be replaced by an inert gas, that is, heating under reflux can be carried out under the protection of an inert gas.

[0187] Among them, the heating temperature is 70 °C.

[0188] Among them, before recrystallization with dichloromethane / tetrahydrofuran, the filtrate is concentrated to dryness.

[0189] Among them, when the filtrate is concentrated to 1 / 2 of the original volume, the filtrate is cooled to room temperature, filtered, and the filtered filtrate is continuously concentrated.

[0190] Among them, the solution is concentrated by means of reduced-pressure rotary evaporation, and the temperature of reduced-pressure rotary evaporation is 35 - 45 °C.

[0191] Among them, during the recrystallization process, the mixing ratio of dichloromethane / tetrahydrofuran added is 1:2 to 1:5, and the addition amount is up to the volume of the solution before concentration. Stir to fully dissolve the solid precipitated by concentration, then at room temperature, filter the dissolved solution to obtain a filtrate, and perform recrystallization treatment on the filtrate to obtain an ionic ruthenium metal complex having the structure of Formula II-2.

[0192] Among them, the ion exchange reaction is carried out using a two-necked or single-necked round-bottom flask equipped with a reflux condenser under nitrogen or an inert gas.

[0193] Example 6

[0194] A preparation method of an ionic ruthenium metal complex having the above structure of Formula III-1, comprising:

[0195] Dissolve 71 mg of ruthenium(III) chloride tris(1,10-phenanthroline) and 68 mg of silver (+)-camphorsulfonate in 10 mL of methanol, and heat under reflux for 1 hour under nitrogen protection; after cooling to room temperature, filter to remove the precipitated silver chloride; concentrate the filtrate, and perform diffusion recrystallization with acetonitrile / ether to obtain 92 mg of red rod-shaped crystals of Formula III-1, with a yield of 83%. 1 H NMR (400 MHz, CD3CN): δ 8.65 (dd, J = 8.2, 0.7 Hz, 6H), 8.30 (s, 6H), 8.07 (d, J = 4.5 Hz, 6H), 7.67 (dd, J = 8.2, 5.3 Hz, 6H), 3.09 (d, J = 14.7 Hz, 2H), 2.77–2.67 (m, 2H), 2.63 (d, J = 14.7 Hz, 2H), 2.32–2.23 (m, 2H), 2.01 (t, J = 4.1 Hz, 2H), 1.98–1.95 (m, 2H), 1.83 (d, J = 18.1 Hz, 2H), 1.53–1.45 (m, 2H), 1.37–1.30 (m, 2H), 1.08 (s, 6H), 0.79 (s, 6H).

[0196] Among them, nitrogen can be replaced by an inert gas, that is, heating under reflux can be carried out under the protection of an inert gas.

[0197] Among them, the heating temperature is 70 °C.

[0198] Among them, before performing diffusion recrystallization with acetonitrile / ether, the filtrate is concentrated to dryness.

[0199] Among them, when the filtrate is concentrated to 1 / 2 of the original volume, the filtrate is cooled to room temperature, filtered, and the filtered filtrate is continuously concentrated.

[0200] Among them, the solution is concentrated by reduced-pressure rotary evaporation, and the temperature of the reduced-pressure rotary evaporation is 35-45 °C.

[0201] Among them, during the diffusion recrystallization process, the mixing ratio of acetonitrile / ether added is 3:1-1:1, and the addition method is: dissolving the solid obtained by concentration in acetonitrile, and ether enters in the form of vapor diffusion to reduce the crystallization rate of the product, so as to improve the morphology of the solid during the recrystallization process and obtain a target substance with better purity, that is, an ionic metal ruthenium complex having the structure of Formula III-1.

[0202] Among them, after adding acetonitrile to the concentrated solid, stir to fully dissolve the concentrated solid, then filter the dissolved solution at room temperature to obtain a filtrate, and perform recrystallization treatment on the filtrate to obtain an ionic metal ruthenium complex having the structure of Formula III-1.

[0203] Among them, the ion exchange reaction is carried out in a two-necked or single-necked round-bottom flask equipped with a reflux condenser under nitrogen or an inert gas.

[0204] Example 7

[0205] A preparation method of an ionic metal ruthenium complex having the above-mentioned structure of Formula III-2 includes:

[0206] Dissolve 71 mg of tris(1,10-phenanthroline) ruthenium chloride and 68 mg of silver L-(−)-camphorsulfonate in 10 mL of methanol, and heat under reflux for 1 hour under nitrogen protection; after cooling to room temperature, filter to remove the generated silver chloride precipitate; concentrate the filtrate, and perform diffusion recrystallization with acetonitrile / ether to obtain 94 mg of red rod-shaped crystals of Formula III-2, with a yield of 85%. 1 H NMR (400 MHz, CD3CN): δ 1 HNMR (400 MHz, CD3CN): δ 8.67 (dd, J = 8.4, 0.9 Hz, 6H), 8.32 (s, 6H), 8.09 (d, J = 4.5 Hz, 6H), 7.68 (dd, J = 8.4, 5.3 Hz, 6H), 3.10 (d, J = 14.9 Hz, 2H), 2.78–2.67 (m, 2H), 2.64 (d, J = 14.5 Hz, 2H), 2.33–2.20 (m, 2H), 2.03 (t, J = 4.2 Hz, 2H), 1.97–1.95 (m, 2H), 1.84 (d, J = 18.1 Hz, 2H), 1.54–1.46 (m, 2H), 1.39–1.31 (m, 2H), 1.09 (s, 6H), 0.81 (s, 6H).

[0207] Among them, nitrogen can be replaced by an inert gas, that is, heating under reflux can be carried out under the protection of an inert gas.

[0208] Among them, the heating temperature is 70 °C.

[0209] Among them, before diffusion recrystallization with acetonitrile / ether, the filtrate is concentrated to dryness.

[0210] Among them, when the filtrate is concentrated to 1 / 2 of the original volume, the filtrate is cooled to room temperature, filtered, and the filtered filtrate is continuously concentrated.

[0211] Among them, the solution is concentrated by means of reduced-pressure rotary evaporation, and the temperature of reduced-pressure rotary evaporation is 35-45 °C.

[0212] Among them, during the diffusion recrystallization process, the mixing ratio of the added acetonitrile / ether is 3:1 to 1:1, and the addition method is: the solvent enters the device in the form of vapor diffusion to contact with the acetonitrile solution, reducing the speed of solid precipitation, so as to improve the morphology of the solid during recrystallization, and obtain the target substance with better purity, that is, the ionic ruthenium metal complex with the structure of formula III-2.

[0213] Among them, after acetonitrile is added to the concentrated solid, stirring is carried out to fully dissolve the concentrated solid, and then the dissolved solution is filtered at room temperature to obtain a filtrate, and the filtrate is subjected to recrystallization treatment to obtain an ionic ruthenium metal complex with the structure of formula III-2.

[0214] Among them, the ion exchange reaction is carried out using a two-necked or single-necked round-bottom flask equipped with a reflux condenser under nitrogen or inert gas.

[0215] Example 8

[0216] A preparation method of an ionic ruthenium metal complex with the structure of formula IV-1, comprising:

[0217] Dissolve 117 mg of tris(1,10-phenanthroline) ruthenium chloride and 70 mg of silver D-(+)-camphorsulfonate in 20 mL of acetonitrile, heat under reflux for 1 hour under nitrogen protection; after cooling to room temperature, filter to remove the generated silver chloride precipitate; concentrate the filtrate, and perform diffusion recrystallization with acetonitrile / ether to obtain 138 mg of red rod-shaped crystals of formula IV-1, with a yield of 88%. 11H NMR (400 MHz, CD3CN): δ 8.32 (d, J = 5.4 Hz, 6H), 8.24 (s, 6H), 7.71–7.61 (m, 36H), 2.99 (d, J = 15.1 Hz, 2H), 2.78 (ddd, J = 16.4, 12.5, 3.0 Hz, 2H), 2.51 (d, J = 14.4 Hz, 2H), 2.27 (d, J = 17.6 Hz, 2H), 2.19 - 2.14 (m, 2H), 1.82 (d, J = 18.2 Hz, 4H), 1.49 - 1.42 (m, 2H), 1.37 - 1.30 (m, 2H), 1.11 (s, 6H), 0.81 (s, 6H).

[0218] Among them, nitrogen can be replaced by an inert gas, that is, heating under reflux can be carried out under the protection of an inert gas.

[0219] Among them, the heating temperature is 85 °C.

[0220] Among them, before diffusion recrystallization with acetonitrile / ether, the filtrate is concentrated to dryness.

[0221] Among them, when the filtrate is concentrated to 1 / 2 of the original volume, the filtrate is cooled to room temperature, filtered, and the filtered filtrate is continuously concentrated.

[0222] Among them, the solution is concentrated by rotary evaporation under reduced pressure, and the temperature of rotary evaporation under reduced pressure is 35 - 45 °C.

[0223] Among them, during the diffusion recrystallization process, the mixing ratio of acetonitrile / ether added is 1:1 - 1:2, and the addition method is: the solvent enters the concentration device in the form of vapor diffusion to contact with the acetonitrile solution, reducing the speed of solid precipitation, so as to improve the morphology of the solid during recrystallization to obtain a target substance with better purity, that is, an ionic metal ruthenium complex with the structure of formula IV-1.

[0224] Among them, after acetonitrile is added to the concentrated solid, stirring is carried out to fully dissolve the concentrated solid, and then the dissolved solution is filtered at room temperature to obtain a filtrate, and the filtrate is recrystallized to obtain an ionic metal ruthenium complex with the structure of formula IV-1.

[0225] Among them, the ion exchange reaction is carried out in a two-necked or single-necked round-bottom flask equipped with a reflux condenser under nitrogen or an inert gas.

[0226] Example 9

[0227] A preparation method of an ionic metal ruthenium complex with the structure of formula IV-2, comprising:

[0228] 117 mg of ruthenium(III) chloride tris(1,10-phenanthroline) and 70 mg of silver (+)-camphorsulfonate were dissolved in 20 mL of acetonitrile and heated under reflux for 1 h under nitrogen protection; after cooling to room temperature, the precipitated silver chloride was removed by filtration; the filtrate was concentrated and recrystallized by acetonitrile / ether diffusion to give 136 mg of red rod-shaped crystals of formula IV-2 in 87% yield. 1 H NMR (400 MHz, CD3CN): δ 8.33 (d, J = 5.5 Hz, 6H), 8.25 (s, 6H), 7.76–7.55 (m, 36H), 2.99 (d, J = 14.6 Hz, 2H), 2.79 (t, J = 12.6 Hz, 2H), 2.52 (d, J = 14.6 Hz, 2H), 2.31 - 2.17 (m, 2H), 2.15–2.08 (m, 2H), 2.01 - 1.97 (m, 2H), 1.83 (d, J = 18.1 Hz, 2H), 1.50 - 1.44 (m, 2H), 1.37 - 1.30 (m, 2H), 1.12 (s, 6H), 0.82 (s, 6H).

[0229] Among them, nitrogen can be replaced by an inert gas, that is, heating under reflux can be carried out under the protection of an inert gas.

[0230] Among them, the heating temperature is 85 °C.

[0231] Among them, before recrystallization by acetonitrile / ether diffusion, the filtrate was concentrated to dryness.

[0232] Among them, when the filtrate was concentrated to 1 / 2 of the original volume, the filtrate was cooled to room temperature, filtered, and the filtered filtrate was continuously concentrated.

[0233] Among them, the solution was concentrated by rotary evaporation under reduced pressure, and the temperature of rotary evaporation under reduced pressure was 35 - 45 °C.

[0234] Among them, during the diffusion recrystallization process, the mixing ratio of acetonitrile / ether added was 1:1 - 1:2, and the addition method was: the solvent was introduced into the concentration device by steam diffusion to contact with the concentrated solution, reducing the rate of solid precipitation to improve the morphology of the solid during recrystallization to obtain a target substance with better purity, that is, an ionic metal ruthenium complex with the structure of formula IV-2.

[0235] Among them, after acetonitrile was added to the concentrated solid, stirring was carried out to fully dissolve the concentrated solid, and then the dissolved solution was filtered at room temperature to obtain a filtrate, and the filtrate was recrystallized to obtain an ionic metal ruthenium complex with the structure of formula IV-2.

[0236] Among them, the ion exchange reaction was carried out in a two-necked or single-necked round-bottom flask equipped with a reflux condenser under nitrogen or an inert gas.

[0237] Example 10

[0238] Application of an ionic ruthenium metal complex having the structure of Formula II-1, Formula II-2, Formula III-1, Formula III-2, Formula IV-1 or Formula IV-2 in a CP-OLED, including using the above ionic ruthenium metal complex as a luminescent material to prepare a luminescent layer in a CP-OLED.

[0239] Example 11

[0240] Application of an ionic ruthenium metal complex having the structure of Formula II-1, Formula II-2, Formula III-1, Formula III-2, Formula IV-1 or Formula IV-2 in a chiral optoelectronic detector, including using the above ionic ruthenium metal complex to prepare an active layer in a chiral optoelectronic detector.

[0241] Example 12

[0242] Application of an ionic ruthenium metal complex having the structure of Formula II-1, Formula II-2, Formula III-1, Formula III-2, Formula IV-1 or Formula IV-2 in a circularly polarized luminescent material, including:

[0243] An ionic ruthenium metal complex having the structure of Formula II-1, Formula II-2, Formula III-1, Formula III-2, Formula IV-1 or Formula IV-2 can be applied to a circularly polarized luminescent material

[0244] Example 13

[0245] Application of an ionic ruthenium metal complex having the structure of Formula II-1, Formula II-2, Formula III-1, Formula III-2, Formula IV-1 or Formula IV-2 in a circularly polarized luminescent layer, including using the above ionic ruthenium metal complex as a circularly polarized luminescent material to prepare a circularly polarized luminescent layer.

[0246] Example 14

[0247] Application of an ionic ruthenium metal complex having the structure of Formula II-1, Formula II-2, Formula III-1, Formula III-2, Formula IV-1 or Formula IV-2 in a circularly polarized luminescent electrochemical cell, including using the ionic ruthenium metal complex to mix with a chiral ionic liquid to prepare a luminescent layer of a circularly polarized luminescent electrochemical cell.

[0248] Wherein, the chiral ionic liquid is 1-butyl-3-methylimidazolium camphorsulfonate, and the camphorsulfonate is left-handed (-) or right-handed (+).

[0249] Wherein, the chiral structure of the ionic liquid corresponds to the chirality of the ionic ruthenium metal complex.

[0250] Specifically, a circularly polarized luminescent layer is prepared by mixing an ionic ruthenium metal complex having the structure of Formula II-1, Formula III-1 or Formula IV-1 with (+)-1-butyl-3-methylimidazolium camphorsulfonate having a right-handed chirality and coating the mixture on a smooth layer.

[0251] A circularly polarized luminescent layer is prepared by mixing an ionic ruthenium metal complex having the structure of Formula II-2, Formula III-2 or Formula IV-2 with (—)-1-butyl-3-methylimidazolium camphorsulfonate having a left-handed chirality and coating the mixture on a smooth layer.

[0252] Among them, the circularly polarized luminescent electrochemical cell is composed of a transparent substrate, a PEDOT:PSS layer, a circularly polarized luminescent layer and a metal electrode. When preparing the luminescent layer, an ionic ruthenium metal complex is mixed with a chiral ionic liquid and coated on a smooth layer to prepare a circularly polarized luminescent layer.

[0253] Among them, the molar ratio of the chiral ionic liquid to the ionic ruthenium metal complex is 2:1.

[0254] Among them, before mixing the ionic ruthenium metal complex with the chiral ionic liquid and coating it on the smooth layer, dimethylformamide (DMF) is added to the mixture of the ionic ruthenium metal complex and the chiral ionic liquid and stirred until it becomes uniformly transparent, based on achieving a spin-coating state.

[0255] Among them, the thickness of the circularly polarized luminescent layer is 40-50 nm.

[0256] Specifically, a method for preparing a circularly polarized luminescent electrochemical cell based on a chiral luminescent material of an ionic ruthenium metal complex includes:

[0257] S1: Spin-coating a smooth layer on a transparent conductive substrate;

[0258] Among them, the transparent conductive substrate is ITO glass, and the thickness of the coating (ITO) is 150 nm.

[0259] Among them, the sheet resistance of the substrate is 15 Ω / sq, and the transmittance is 88%.

[0260] Among them, the raw material of the spin-coated smooth layer is PEDOT:PSS, and the solvent is water.

[0261] Among them, the spin-coating speed is 4000 rpm, and the spin-coating time is 30 s.

[0262] Among them, after the spin-coating of the smooth layer is completed, the smooth layer is annealed to dry the smooth layer.

[0263] Exemplarily, the annealing temperature is 150 °C, and the annealing time can be 30 minutes.

[0264] Among them, the thickness of the smooth layer is 40-50 nm.

[0265] S2: Spin-coat a luminescent layer on the smoothing layer, which is a mixture of an ionic ruthenium metal complex and a chiral ionic liquid;

[0266] Among them, the solution concentration is 30 mg / mL, and the solvent is DMF, acetonitrile, DMSO, acetonitrile / DMF or acetonitrile / DMSO.

[0267] Among them, the mixing ratio of acetonitrile / DMF is 4 / 1 to 1 / 1, and the mixing ratio of acetonitrile / DMSO is 4 / 1 to 1 / 1.

[0268] Among them, during spin-coating, the rotation speed is 2000 rpm and the spin-coating time is 30 s.

[0269] S3: Prepare the top electrode LiF / Al on the luminescent layer by vacuum thermal evaporation.

[0270] In this way, after preparing the luminescent layer on the smoothing layer, a circularly polarized luminescent electrochemical cell is formed together with the transparent substrate and the metal electrode.

[0271] Example 15

[0272] The application of an ionic ruthenium metal complex having the structure of Formula II-1, Formula II-2, Formula III-1, Formula III-2, Formula IV-1 or Formula IV-2 in a circularly polarized luminescent electrochemical cell, including using the ionic ruthenium metal complex as a circularly polarized luminescent material to prepare the luminescent layer in the circularly polarized luminescent electrochemical cell.

[0273] Among them, as Figure 8 shown, the circularly polarized luminescent electrochemical cell is composed of a transparent substrate, a PEDOT:PSS layer, a circularly polarized luminescent layer and a metal electrode. When preparing the luminescent layer, the above-mentioned ionic ruthenium metal complex is coated on the smoothing layer to prepare the circularly polarized luminescent layer.

[0274] Among them, before coating the ionic ruthenium metal complex on the smoothing layer, acetonitrile is added to the ionic ruthenium metal complex and stirred until it becomes transparent, so as to achieve the spin-coating state.

[0275] Among them, the thickness of the circularly polarized luminescent layer is 40-50 nm.

[0276] Specifically, the preparation method of the circularly polarized luminescent electrochemical cell based on the chiral luminescent material of the ionic ruthenium metal complex is different from that of Example 14 in that:

[0277] S2: Spin-coat the ionic ruthenium metal complex on the smoothing layer to prepare the luminescent layer;

[0278] Among them, a solution with a certain concentration is prepared with the ionic ruthenium metal complex as the solute, and the solution is spin-coated on the smoothing layer and annealed to obtain the luminescent layer.

[0279] Among them, the concentration of the solution is 30 mg / ml, and the solvent is acetonitrile.

[0280] Analysis of the properties of ionic ruthenium metal complexes with the structures of Formula II-1, Formula II-2, Formula III-1, Formula III-2, Formula IV-1 or Formula IV-2 and the corresponding parameters during the preparation process:

[0281] 1. Analysis of the thermal and electrochemical stability of ionic ruthenium metal complexes:

[0282] 1) The electrochemical stability is related to the nature of the cations of the ionic ruthenium metal complexes. It can be illustrated by the CV curve and belongs to the existing well-known content.

[0283] Taking the ionic ruthenium metal complex with the structure of Formula II-1 as an example for elaboration, as Figure 1 shown, the figure shows that II-1 has a pair of reversible oxidation peaks and three pairs of reversible reduction peaks, indicating that this type of complex material has good electrochemical stability.

[0284] It can be shown that the introduction of chiral anions has no effect on its electrochemical properties, and it still maintains the electrochemical properties similar to those of ruthenium complexes combined with other achiral anions (PF6 － , BF4 － ).

[0285] The ionic ruthenium metal complexes with other structures are similar to Formula II-1. That is, for the ionic ruthenium metal complexes with the structures of Formula II-2, Formula III-1, Formula III-2, Formula IV-1 or Formula IV-2, the introduction of chiral anions has no effect on their electrochemical properties.

[0286] 2) After preparing the light-emitting layer of the circularly polarized luminescence electrochemical cell and detecting the light-emitting layer before and after annealing, it is found that the light-emitting layer before and after annealing maintains the same chiral absorption spectrum (CD) pattern, indicating that during the annealing process, that is, the structure and chirality of the ionic ruthenium metal complexes will not be destroyed.

[0287] Taking the ionic ruthenium metal complex with the structure of Formula II-2 as an example, as Figure 2 shown, the CD curve close to mirror symmetry remains consistent with that before annealing, and the chirality of the camphorsulfonate anion is successfully transferred to the cations in the thin film at the ground state, indicating that the high-temperature annealing process does not destroy the molecular structure and chiral information of the material, has good thermal stability, and is beneficial to device processing.

[0288] The ionic ruthenium metal complexes with other structures are similar to Formula II-2. That is, for the ionic ruthenium metal complexes with the structures of Formula II-1, Formula III-1, Formula III-2, Formula IV-1 or Formula IV-2, they also have good thermal stability and are beneficial to device processing.

[0289] 2. Analysis of the circularly polarized photoluminescence properties of ionic ruthenium metal complexes as circularly polarized materials:

[0290] Taking ionic ruthenium metal complexes with the structures of Formula II-1 and Formula II-2 as examples, in Figure 3 The mirror-symmetric circularly polarized emission curves indicate that the chirality of the anions in the complex can also be successfully transferred to the achiral cationic chromophore in the excited state. According to the chirality of the camphorsulfonate group, the thin film exhibits mirror-image circularly polarized photoluminescence characteristics, and the luminescence asymmetry factor g PL is 10 -4 .

[0291] It can be seen that the ionic ruthenium metal complexes with the structures of Formula II-1 and Formula II-2 have the property of circularly polarized photoluminescence.

[0292] The ionic ruthenium metal complexes with other structures are similar to those of Formula II-1 and Formula II-2. That is, for the ionic ruthenium metal complexes with the structures of Formula III-1, Formula III-2, Formula IV-1 or Formula IV-2, they also have the property of circularly polarized photoluminescence.

[0293] 3. Analysis of the film-forming property on the surface of the circularly polarized luminescent layer prepared with ionic ruthenium metal complexes as circularly polarized materials:

[0294] Taking the ionic ruthenium metal complex with the structure of Formula II-1 as an example, in Figure 4 it shows that the surface of the thin film coated with the complex is flat and smooth, and the roughness is very small, indicating that this type of material has good film-forming property.

[0295] The ionic ruthenium metal complexes with other structures are similar to that of Formula II-1. That is, for the ionic ruthenium metal complexes with the structures of Formula II-2, Formula III-1, Formula III-2, Formula IV-1 or Formula IV-2, they also have good film-forming property.

[0296] 4. Analysis of the electroluminescence properties of ionic ruthenium metal complexes:

[0297] Taking the ionic ruthenium metal complex with the structure of Formula II-1 as an example, in Figure 5 it shows red luminescence with a maximum emission peak of 640 nm, which is consistent with the photoluminescence spectrum of the luminescent layer thin film, indicating the phosphorescence emission of the ionic ruthenium metal complex. The electroluminescence spectra under different pulsed voltage drives and the dependence of the spectral peak intensity on the voltage change show that the red luminescence intensity of the device increases non-linearly with the voltage before 10 V, and the brightness decreases significantly after 10.2 V. At this time, the device has reached the limit voltage and current that it can withstand. It shows that this type of material has good electroluminescence performance when applied to electrical devices.

[0298] Ionic ruthenium metal complexes with other structures are similar to Formula II-1. That is, for ionic ruthenium metal complexes having the structures of Formula II-2, Formula III-1, Formula III-2, Formula IV-1 or Formula IV-2, they also have good electroluminescent properties.

[0299] 5. Analysis of the circularly polarized electroluminescent properties of ionic ruthenium metal complexes:

[0300] Taking ionic ruthenium metal complexes having the structures of Formula II-1 and Formula II-2 as examples, in Figure 6 According to the chirality of the camphorsulfonate anion, the light-emitting electrochemical cells based on the ionic ruthenium metal complexes of Formula II-1 and Formula II-2 exhibited mirror-symmetric circularly polarized electroluminescence spectra, indicating that under the driving voltage, the chirality of the anion was successfully transferred to the cationic complex chromophore, achieving effective circularly polarized emission. The luminescence dissymmetry factor (|g EL |) was 1.7×10 -3 .

[0301] It can be seen that ionic ruthenium metal complexes having the structures of Formula II-1 and Formula II-2 have circularly polarized electroluminescent properties.

[0302] Ionic ruthenium metal complexes with other structures are similar to Formula II-1 and Formula II-2. That is, for ionic ruthenium metal complexes having the structures of Formula III-1, Formula III-2, Formula IV-1 or Formula IV-2, they also have circularly polarized electroluminescent properties.

[0303] Currently, the g PL of metal ruthenium complexes is generally in the range of 10 -4 ~10 -3 , and there is no report on the circularly polarized electroluminescence of this type of complexes. The ionic ruthenium metal complexes provided by the present invention can achieve circularly polarized electroluminescence with g EL being 10 -3 .

[0304] 6. Efficiency analysis of circularly polarized light-emitting devices prepared using ionic ruthenium metal complexes:

[0305] The current-voltage (I-V) characteristics of the devices were measured using a semiconductor parameter analyzer (Keithley 2400 source meter); the luminance was recorded in real time using a luminance meter (Photo Research, PR 735); the light driving voltage characteristic curve and the external quantum efficiency-current density characteristic curve were measured using a computer-controlled source measurement unit and a spectroradiometer.

[0306] Among them, the current efficiency refers to the ratio of the luminescence luminance of the device to the injected current, and the calculation method of EQE is the ratio of the number of emitted photons to the number of injected electrons.

[0307] Taking the ionic metal ruthenium complex having the structure of formula II-1 as an example, the above method is used to test the performance characterization spectra of the light-emitting electrochemical cell prepared based on the ionic metal ruthenium complex of formula II-1 without adding ionic liquid and after adding ionic liquid. Figure 7 As shown, the maximum brightness of the luminescent electrochemical cell prepared based on the ionic metal ruthenium complex of formula II-1 is 370 cd / m 2 , the current efficiency is 0.44cd / A, and the maximum external quantum efficiency (EQE max ) is 0.73%; a chiral 1-butyl-3-methylimidazolium camphorsulfonate ionic liquid is introduced into the light-emitting layer, and the ionic metal ruthenium complex of formula II-1 is uniformly mixed and dissolved in acetonitrile according to a specific molar ratio, and a light-emitting electrochemical cell is prepared by the same device process as above, so that the electroluminescent performance of the light-emitting electrochemical cell is significantly improved, and the maximum brightness is 724cd / m 2 , current efficiency is 1.12cd / A, maximum external quantum efficiency (EQE max ) is 1.27%, indicating that the introduction of ionic liquid improves the electroluminescence performance of the electrochemical cell by 1.7 times.

[0308] It can be seen that the electrical device prepared by the ionic metal ruthenium complex having the structure of formula II-1 has good stability and electroluminescent efficiency.

[0309] Ionic ruthenium complexes with other structures are similar to Formula II-1, that is, ionic ruthenium complexes with structures of Formula II-2, Formula III-1, Formula III-2, Formula IV-1 or Formula IV-2 also have good stability and electroluminescent efficiency.

[0310] 7. Solubility analysis of ionic ruthenium complexes:

[0311] 1) Analysis object: ionic metal ruthenium complex having the structure of formula II-1, formula II-2, formula III-1, formula III-2, formula IV-1 or formula IV-2.

[0312] 2) Solvent types: methanol, dimethylformamide, acetonitrile, tetrahydrofuran, dioxane, ethanol, dichloromethane, chlorobenzene.

[0313] 3) Detection method: For an ionic metal ruthenium complex of a certain structure, take 8 portions, each with 1 mg, and place them in 5 ml of methanol, dimethylformamide, acetonitrile, tetrahydrofuran, dioxane, ethanol, dichloromethane, and chlorobenzene respectively, and stir. It can be observed that the solid can be quickly dissolved and become clear when added to the solvent.

[0314] The same test was performed on all configurations of ionic metal ruthenium complexes, and all of them were able to quickly dissolve and become clear after the solid was added to the solvent.

[0315] It can be seen that the ionic ruthenium metal complexes with the structures of Formula II-1, Formula II-2, Formula III-1, Formula III-2, Formula IV-1 or Formula IV-2 have good solubility and can be dissolved in solvents with large or small polarity. The range of solvent polarity selection is wide. When preparing multi-layer devices, a solvent in which the upper layer will not dissolve can be selected, so that the device structure will not be damaged, which is conducive to device processing. For example, in the OLED multi-layer device structure, there will be an impact between layers, and a stripping phenomenon may occur between multi-layers of the same solvent, that is, the device layers of the same solvent may adsorb the solute, resulting in elution. The ionic ruthenium metal complexes of the present invention can overcome the adverse effects that may occur between layers.

[0316] In addition, good solubility promotes film-forming properties, and spin-coating to form a film to make a device requires good film-forming properties. The ionic ruthenium metal complexes of the present invention have good solubility, which is conducive to spin-coating and film-forming, and is conducive to device processing.

[0317] 9. Analysis of the target product yields in Examples 4-9:

[0318] Using the preparation methods of Examples 4-9 to prepare ionic ruthenium metal complexes with the structures of Formula II-1, Formula II-2, Formula III-1, Formula III-2, Formula IV-1 or Formula IV-2, the yields of the obtained products are 91%, 94%, 83%, 85%, 88%, and 87% respectively, which can basically reach the existing equivalent level, belong to the normal range, and have the prospect of industrial marketization.

[0319] 10. Determination method of reaction time:

[0320] The Cl ions in the reaction solution are detected by thin-layer chromatography, including:

[0321] Using saturated potassium nitrate aqueous solution as the developing agent; detecting Cl ions through a TLC plate to judge whether the reaction is completed.

[0322] Among them, the mass concentration of the saturated potassium nitrate aqueous solution is ≥24%.

[0323] Among them, if there are no Cl ions, the reaction terminates.

[0324] Among them, the complex with anions as chloride ions is easy to carry out ion exchange and moves relatively fast, while the complex with anions as camphorsulfonate ions is not easy to carry out ion exchange and has extremely strong adsorption and is not easy to move.

[0325] Among them, after the reaction is completed, the number of cations and anions can be determined by nuclear magnetic resonance characterization, and then it can be judged whether the reaction is complete. Among them, when the reaction is complete, the ratio of cations to anions is 2:1.

[0326] Those skilled in the art can understand that all or part of the processes of implementing the methods of the above embodiments can be completed by instructing relevant hardware through a computer program, and the program can be stored in a computer-readable storage medium. Among them, the computer-readable storage medium is a disk, an optical disc, a read-only memory or a random access memory, etc.

[0327] As described above, the above are only the preferred specific embodiments of the present invention, but the protection scope of the present invention is not limited thereto. Any changes or substitutions that can be easily thought of by those skilled in the art within the technical scope disclosed by the present invention should be covered by the protection scope of the present invention.

Claims

1. An ionic ruthenium metal complex, characterized in that, The ionic metal ruthenium complex has the structure shown in Formula I: Wherein, in Formula I, * represents the chirality of the camphorsulfonate group, and the camphorsulfonate group is left-handed (-) or right-handed (+); The N^N ligand is a bipyridine or a phenanthroline and its derivative ligand; R is H or a benzene ring.

2. The ionic ruthenium metal complex according to claim 1, wherein The ionic metal ruthenium complex has the structure of Formula II, Formula III or Formula IV: Among them, the ionic metal ruthenium complex with the structure of Formula II uses octahedral tris(2,2'-bipyridine)ruthenium complex as the cation and left-handed or right-handed camphorsulfonate as the anion; In Formula II, * represents the chirality of the camphorsulfonate group, and the camphorsulfonate group is left-handed (-) or right-handed (+); Or Among them, the ionic metal ruthenium complex with the structure of Formula III uses octahedral tris(1,10-phenanthroline)ruthenium complex as the cation and left-handed or right-handed camphorsulfonate as the anion; In Formula III, * represents the chirality of the camphorsulfonate group, and the camphorsulfonate group is left-handed (-) or right-handed (+); Or Among them, the ionic metal ruthenium complex with the structure of Formula IV uses tris(4,7-diphenyl-1,10-phenanthroline)ruthenium complex as the cation and left-handed or right-handed camphorsulfonate as the anion; In Formula IV, * represents the chirality of the camphorsulfonate group, and the camphorsulfonate group is left-handed (-) or right-handed (+).

3. A method for preparing the ionic ruthenium metal complex according to any one of claims 1-2, characterized in that: Taking the complex with chloride ion as the anion and tris(bipyridine)ruthenium, tris(phenanthroline)ruthenium and their derivatives as the cation as Reactant (1), and the compound with silver ion as the cation and the anion having a chiral structure as Reactant (2), dissolving Reactant (1) and (2) in an organic solvent, and performing an ion exchange reaction to obtain the ionic metal ruthenium complex.

4. The method according to claim 3, characterized in that: Recrystallize and purify the ion exchange reaction product to obtain the ionic metal ruthenium complex; wherein, the molar ratio of the organic solvent to Reactant (1) and Reactant (2) is 500-2000:1:2-3.

5. The method according to claim 4, characterized in that: Before the recrystallization purification, it includes filtering the solution after the ion exchange reaction to remove the silver chloride precipitation impurities generated by the reaction. After filtering the solution after the ion exchange reaction, concentrate the filtrate and recrystallize to obtain the ionic metal ruthenium complex.

6. The method according to claim 3, characterized in that: During the ion exchange reaction, heat the solution.

7. Use of the ionic ruthenium metal complex according to any one of claims 1-2 or the ionic ruthenium metal complex prepared by the method according to any one of claims 3-6, characterized in that: The ionic metal ruthenium complex is applied to circularly polarized luminescent materials, circularly polarized luminescent layers, and circularly polarized luminescent devices.

8. Use of the ionic ruthenium metal complex according to claim 7, characterized in that: Using the ionic metal ruthenium complex as a luminescent material to prepare the luminescent layer in CP-OLED; or using the ionic metal ruthenium complex to prepare the active layer in a chiral photodetector; or using the ionic metal ruthenium complex as a circularly polarized luminescent material to prepare the luminescent layer in a circularly polarized luminescent electrochemical cell; or using the ionic metal ruthenium complex to mix with a chiral ionic liquid to prepare the luminescent layer of a circularly polarized luminescent electrochemical cell; Among them, the chiral ionic liquid is 1-butyl-3-methylimidazolium camphorsulfonate; The molar ratio of the chiral ionic liquid to the ionic metal ruthenium complex is 0.25-2.

9. Use of the ionic ruthenium metal complex according to claim 8, characterized in that: The circularly polarized luminescent electrochemical cell is composed of a transparent substrate, a PEDOT:PSS layer, a circularly polarized luminescent layer and a metal electrode; A solution with a certain concentration is prepared by using the ionic metal ruthenium complex or a mixture thereof with a chiral ionic liquid as a solute. The solution is spin-coated on a smooth layer and, after annealing treatment, the circularly polarized luminescent layer is obtained.

10. Use of the ionic ruthenium metal complex according to claim 9, characterized in that: Using the ionic metal ruthenium complex as a solute, the solute is dissolved in an organic solvent with high or low polarity to obtain a solution with a certain concentration.

11. Use of the ionic metal ruthenium complex according to claim 10, characterized in that: The organic solvent is one or more of methanol, dimethylformamide, acetonitrile, tetrahydrofuran, dioxane, ethanol, dichloromethane, and chlorobenzene.

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