Chiral cuprous coordination polymer circular polarization luminescent material and synthesis method thereof
By assembling zero-dimensional copper sub-coefficients into high-dimensional chiral copper sub-coefficients into a three-dimensional mesh-like structure, a circularly polarized luminescent material was formed, solving the problems of stability and luminescence asymmetry in zero-dimensional complexes and achieving the synthesis of highly stable and low-cost circularly polarized luminescent materials.
Patent Information
- Application Number
- CN202310563458.7
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2023-05-18
- Publication Date
- 2026-02-03
AI Technical Summary
Existing zero-dimensional chiral cuprous complexes have random molecular arrangements in solution, resulting in low luminescence asymmetry factor and quantum yield, as well as insufficient stability, which cannot meet the requirements of solid-state devices.
Zero-dimensional cuprous coordination units were assembled into high-dimensional chiral cuprous coordination polymers. Cinconidine or cinconidine was used as chiral bidentate ligands to form a three-dimensional mesh-like circularly polarized luminescent material. The compound [(Cu4I4)(Cin)2]n was synthesized by preparing a specific solution and reacting it under oil bath conditions.
It improves the stability and thermal stability of the material, enhances the structural stability of the luminescent material, and uses inexpensive raw materials with mild reaction conditions.
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Figure CN121449909A_ABST
Abstract
Description
TECHNICAL FIELD
[0001] The present application relates to the technical field of luminescent materials, in particular to a chiral cuprous coordination polymer circularly polarized luminescent material and a synthesis method thereof.
BACKGROUND
[0002] Circularly polarized luminescence (CPL) material refers to a chiral luminescent substance capable of emitting left-handed and right-handed unequal circularly polarized light. Compared with the method of converting non-polarized light into circularly polarized light through a polarizer and a 1 / 4 wave plate, directly emitting circularly polarized light by using a CPL material has the advantages of less energy loss, high adjustability, flexible size, accurate reflection of excited state structure information, etc., which is conducive to realizing a circularly polarized light system with low energy consumption, high integration and miniaturization, and has important application value in the fields of 3D imaging display, information storage, optical communication, chiral probe, molecular switch and medical detection.
[0003] Most of the current research on circularly polarized luminescence based on chiral cuprous complexes is zero-dimensional chiral cuprous complexes. Although they have the advantages of good solubility and easy detection, they often have problems of low luminescence asymmetry factor (g lum ) and quantum yield due to random molecular arrangement and large free vibration in solution state, and have short boards in stability, storage and transportation, which are not conducive to practical application and cannot meet the requirements of some solid devices.
SUMMARY
[0004] One of the technical problems to be solved by the present application is to provide a chiral cuprous coordination polymer circularly polarized luminescent material, which assembles zero-dimensional cuprous coordination units into high-dimensional chiral cuprous coordination polymers, can construct a more stable structure, and enhances the stability of the material.
[0005] The present application is to solve one of the above technical problems:
[0006] A chiral cuprous coordination polymer circularly polarized luminescent material, the chemical formula of the circularly polarized luminescent material is: [(Cu4I4)(Cin)2] n , the molecular formula is C 38 H 44 Cu4I4N4O2;
[0007] When Cin is cinchonine, the chemical formula of the circularly polarized luminescent material is [(Cu4I4)(Cinchonine)2] n ; when Cin is cinchonidine, the chemical formula of the circularly polarized luminescent material is [(Cu4I4)(Cinchonidine)2] n .
[0008] The circularly polarized luminescent material compound is crystallized in an orthorhombic space group P212121, and a crystal structure asymmetric unit is composed of a cubane-type Cu4I4 cluster and two Cin ligands: four Cu + ions and one N atom on one Cin ligand form a tetrahedral coordination, that is, the Cu4I4 cluster is a 4-connected node, and the Cin ligand is a 2-connected node, to form a three-dimensional grid structure; the three-dimensional grid structure has 21 helical chirality in the a, b and c axial directions. -
[0009] Further, the crystal structure data of the circularly polarized luminescent material compound is as follows: α / β / γ = 90°, Z = 4.
[0010] The second technical problem to be solved by the present application is to provide a synthesis method of a chiral cuproate coordination polymer circularly polarized luminescent material, which assembles zero-dimensional cuproate coordination units into high-dimensional chiral cuproate coordination polymers, constructs a more stable structure, enhances the stability of the material, and has low raw material prices and mild reaction conditions.
[0011] The present application solves the second technical problem as follows:
[0012] A synthesis method of a chiral cuproate coordination polymer circularly polarized luminescent material, the method steps are as follows:
[0013] An acetonitrile solution A of cuprous iodide CuI, a deionized water solution B of cinchonine, an acetone solution C of cinchonidine, and a saturated potassium iodide deionized water solution D are configured; then the ABD or ACD solution is mixed in a certain proportion, stirred at 60-100 DEG C in an oil bath for 2-12 hours, and then cooled, filtered and dried to obtain a corresponding coordination polymer solid powder material.
[0014] Further, in the solution A, the concentration of the CuI acetonitrile solution is 0.01-0.1 mol / L;
[0015] In the solution B, the concentration of the cinchonine deionized water solution is 0.005-0.02 mol / L;
[0016] In the solution C, the concentration of the cinchonidine acetone solution is 0.005-0.02 mol / L;
[0017] In the solution D, the concentration of the potassium iodide deionized water solution is saturated, which is 1400-1600 g / L.
[0018] The present application has the following advantages:
[0019] This invention uses cinconine and cinconidine as chiral bidentate ligands to connect zero-dimensional Cu4I4 cuprous clusters to form a three-dimensional mesh-like coordination polymer, thereby synthesizing a chiral cuprous coordination polymer circularly polarized luminescent material with high thermal stability, low raw material cost, and mild reaction conditions. [Attached Image Description]
[0020] The present invention will be further described below with reference to the accompanying drawings and embodiments.
[0021] Figure 1 This is a structural diagram of sample 1# asymmetric unit in an embodiment of the present invention.
[0022] Figure 2 This is a three-dimensional mesh stacking structure diagram of sample 1# in an embodiment of the present invention, wherein the cincorine ligand is simplified as 2-connecting lines.
[0023] Figure 3 This is a thermogravimetric analysis diagram of sample 1# in an embodiment of the present invention.
[0024] Figure 4 This is a comparison diagram of the theoretical diagram obtained by fitting single-crystal data in an embodiment of the present invention and the X-ray powder diffraction diagram.
[0025] Figure 5 The following is the excitation and emission spectrum of sample 1# in an embodiment of the present invention.
[0026] Figure 6 The emission spectrum of sample 1# in this embodiment of the invention is shown at a temperature of 80-400K.
[0027] Figure 7 This is a circularly polarized emission curve of sample 1# in an embodiment of the present invention.
[0028] Figure 8 This is a circularly polarized emission curve of sample 2# in an embodiment of the present invention.
Detailed Implementation Methods
[0029] This invention relates to a chiral copper sub-coordinated polymer circularly polarized luminescent material, the chemical formula of which is: [(Cu4I4)(Cin)2] n The molecular formula is C 38 H 44 Cu4I4N4O2;
[0030] When Cin is cininchonine, the chemical formula of the circularly polarized luminescent material is [(Cu4I4)(Cinchonine)2]. n When Cin is cinconidine, the chemical formula of the circularly polarized luminescent material is [(Cu4I4)(Cinchonidine)2].n ;
[0031] The circularly polarized luminescent material compound crystallizes in an orthorhombic crystal system, space group P212121. The asymmetric unit of the crystal structure consists of a cubane-type Cu4I4 cluster and two Cin ligands: the four Cu ligands in the cubane-type Cu4I4 cluster... + The ions reacted with three adjacent I atoms respectively. - An ion and an N atom on a Cin ligand form a tetrahedral coordination, i.e., the Cu4I4 cluster acts as a 4-connecting node and the Cin ligand acts as a 2-connecting node, forming a three-dimensional mesh structure; the three-dimensional mesh structure has 21 helical chirality in the a, b, and c axis directions.
[0032] The crystal structure data of the circularly polarized luminescent material compound are as follows: α / β / γ = 90° Z = 4.
[0033] This invention also relates to a method for synthesizing the above-mentioned chiral copper sub-coordinate polymer circularly polarized luminescent material, the method comprising the following steps:
[0034] Prepare an acetonitrile solution A of CuI iodide, a deionized aqueous solution B of cinconidine, an acetone solution C of cinconidine, and a saturated deionized aqueous solution D of potassium iodide; then mix solutions ABD or ACD in a certain proportion and react them in an oil bath at 60℃~100℃ for 2~12 hours. After cooling, filtering, and drying, obtain the corresponding coordination polymer solid powder material.
[0035] In solution A, the concentration of CuI acetonitrile solution is 0.01–0.1 mol / L;
[0036] In solution B, the concentration of cinkonin deionized water is 0.005–0.02 mol / L;
[0037] In solution C, the concentration of cinconidine acetone solution is 0.005–0.02 mol / L;
[0038] In the solution D, the concentration of potassium iodide deionized aqueous solution is saturated, ranging from 1400 to 1600 g / L.
[0039] The following will be combined with the appendix Figures 1-8 The technical solution of the present invention will be clearly and completely described in detail with specific embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention. Where specific conditions are not specified in the embodiments, conventional conditions or conditions recommended by the manufacturer shall apply. Reagents or instruments used, unless otherwise specified, are all commercially available conventional products.
[0040] Examples
[0041] 1. Chemical formula: [(Cu4I4)(Cin)2] n .
[0042] Cin is cinchonine, sample 1#, the chemical formula is [(Cu4I4)(Cinchonine)2] n , molecular formula C 38 H 44 Cu4I4N4O2 (molecular weight is 1350.53);
[0043] Cin is cinchonidine, sample 2#, the chemical formula is [(Cu4I4)(Cinchonidine)2] n , molecular formula C 38 H 44 Cu4I4N4O2 (molecular weight is 1350.53).
[0044] Sample 1# and sample 2# are enantiomers, the molecular formula is the same, but the chirality is different, respectively, dextrorotation and levorotation.
[0045] 2. Synthesis example:
[0046] The synthesis method of sample 1#: 95mg (0.5mmol) of iodine potassium, 75mg (0.25mmol) of cinchonine, 14.5g of potassium iodide were dissolved in 10mL of acetonitrile, 30mL of deionized water, 10mL of deionized water respectively, mixed and sealed, stirred in 85℃ oil bath for 4 hours, obtained light yellow solid powder, sample 1#, the yield is about 75%.
[0047] The synthesis method of sample 2#: 95mg (0.5mmol) of iodine potassium, 75mg (0.25mmol) of cinchonine, 14.5g of potassium iodide were dissolved in 10mL of acetonitrile, 30mL of deionized water, 10mL of deionized water respectively, mixed and sealed, stirred in 90℃ oil bath for 10 hours, obtained light yellow solid powder, sample 2#, the yield is about 70%.
[0048] 3. Crystal structure:
[0049] The compounds are crystallized in orthorhombic crystal system P212121 space group, the unit cell parameters of sample 1# and sample 2# are basically the same, the unit cell parameters of sample 1# are shown in table 1.
[0050] Table 1 crystal structure data of sample 1#
[0051]
[0052] The asymmetric unit of sample 1# crystal structure consists of cubane-type Cu4I4cluster and two quinonoid ligands, as shown in Figure 1 The four Cu + ions in the cubane-type Cu4I4cluster form tetrahedral coordination with three adjacent I - ions and one N atom on quinonoid ligand, in which Cu1and Cu2are coordinated with N atoms on quinoline ring of two quinonoid ligands, and Cu3and Cu4are coordinated with N atoms on quinuclidine ring of other two quinonoid ligands, thus each cubane-type Cu4I4cluster connects 4 quinonoid ligands, and each quinonoid ligand connects 2 cubane-type Cu4I4clusters. That is, Cu4I4cluster as 4-connected node and quinonoid ligand as 2-connected, forming a three-dimensional grid structure, as shown in Figure 2 The three-dimensional grid structure has 21 helical chirality in a, b, c axial direction.
[0053] The structure of sample 2# is basically the same as that of sample 1#, and the quinonoid ligand is replaced by quinonoid ligand, and the 21 helix direction in the structure is opposite to that of sample 1#.
[0054] 4. Thermogravimetric analysis:
[0055] The thermogravimetric analysis results of sample 1# and sample 2# under nitrogen atmosphere are similar, showing that the skeleton structure can be stable to 215℃. The thermogravimetric diagram of sample 1# is shown in Figure 3 .
[0056] 5. Powder analysis:
[0057] The theoretical diagram obtained by fitting the single crystal data of sample 1# and sample 2# is very good, as shown in Figure 4 , which shows that the purity is very high.
[0058] 6. Fluorescence performance test
[0059] The fluorescence test results of sample 1# at room temperature are shown in Figure 5 . Under the excitation of 390nm excitation light, there is a wide peak, which is superimposed by multiple emission peaks, and the maximum peak is 565nm, and the CIE coordinates are (0.42, 0.52), which is yellow fluorescence.
[0060] The variable temperature fluorescence test results of sample 1# are shown in Figure 6 . At 80K low temperature, there are three obvious peaks, respectively at wavelength of 525nm, 575nm and 630nm, and the CIE coordinates are (0.46, 0.53), which is orange yellow fluorescence, which is obviously different from the room temperature luminescence color and emission peak, and has the property of temperature-induced fluorescence color change.
[0061] 7. Circularly polarized luminescence property test
[0062] Sample 1# and sample 2# have relative yellow circularly polarized luminescence. Figure 7 and Figure 8 As shown in the figure, the left-handed circularly polarized luminescence of sample 1# is greater than the right-handed circularly polarized light, and the g value is maximum 0.002; the right-handed circularly polarized luminescence of sample 2# is greater than the left-handed circularly polarized light, and the g value is maximum -0.002.
[0063] In conclusion, the application uses cinchonine and cinchonidine as chiral bidentate ligand, connects zero-dimensional Cu4I4 cuprous cluster to form three-dimensional grid-shaped coordination polymer, and synthesizes a chiral cuprous coordination polymer circularly polarized luminescence material, which has high thermal stability, and the raw material price is low and the reaction condition is mild.
[0064] Although the specific embodiments of the application are described above, those skilled in the art should understand that the specific examples described are only illustrative, and are not intended to limit the scope of the application, and equivalent modifications and changes made by those skilled in the art in accordance with the spirit of the application should be covered within the scope of the claims of the application.
Claims
1. A chiral copper sub-coordinated polymer circularly polarized luminescent material, characterized in that: The chemical formula of the circularly polarized luminescent material is: [(Cu4I4)(Cin)2] n The molecular formula is C 38 H 44 Cu4I4N4O2; When Cin is cininchonine, the chemical formula of the circularly polarized luminescent material is [(Cu4I4)(Cinchonine)2]. n When Cin is cinconidine, the chemical formula of the circularly polarized luminescent material is [(Cu4I4)(Cinchonidine)2]. n ; The circularly polarized luminescent material compound crystallizes in an orthorhombic crystal system, space group P212121. The asymmetric unit of the crystal structure consists of a cubane-type Cu4I4 cluster and two Cin ligands: the four Cu ligands in the cubane-type Cu4I4 cluster... + The ions reacted with three adjacent I atoms respectively. - An ion and an N atom on a Cin ligand form a tetrahedral coordination, i.e., the Cu4I4 cluster acts as a 4-connecting node and the Cin ligand acts as a 2-connecting node, forming a three-dimensional mesh structure; the three-dimensional mesh structure has 21 helical chirality in the a, b, and c axis directions.
2. The chiral copper sub-coefficient polymer circularly polarized luminescent material according to claim 1, characterized in that: The crystal structure data of the circularly polarized luminescent material compound are as follows: Z = 4.
3. A method for synthesizing a chiral copper sub-coordinated polymer circularly polarized luminescent material, characterized in that: The circularly polarized luminescent material synthesized by the method is the chiral copper sub-coefficient polymer circularly polarized luminescent material as described in claim 1 or 2; the method steps are as follows: Prepare an acetonitrile solution A of CuI iodide, a deionized aqueous solution B of cinconidine, an acetone solution C of cinconidine, and a saturated deionized aqueous solution D of potassium iodide; then mix solutions ABD or ACD in a certain proportion and react them in an oil bath at 60℃~100℃ for 2~12 hours. After cooling, filtering, and drying, obtain the corresponding coordination polymer solid powder material.
4. The method for synthesizing a chiral copper sub-coordinated polymer circularly polarized luminescent material according to claim 3, characterized in that: In solution A, the concentration of CuI acetonitrile solution is 0.01–0.1 mol / L; In solution B, the concentration of cinkonin deionized water is 0.005–0.02 mol / L; In solution C, the concentration of cinconidine acetone solution is 0.005–0.02 mol / L; In the solution D, the concentration of potassium iodide deionized aqueous solution is saturated, ranging from 1400 to 1600 g / L.