Luminescent material, preparation method and application thereof

Abstract

The present invention provides a luminescent material, preparation method, and application thereof, belonging to the field of luminescent functional complexes. Ruthenium complexes contain a greater number of low-light-excited states and high-light-excited states, increasing the number of photons generated when the luminescent material transitions from the low-light-excited state to the ground state and vice versa. This reduces the peak of light intensity, increases the peak of light intensity, and increases the energy difference. Experimental results demonstrate that the energy difference of the luminescent material of the present invention exceeds 146 nm.

Description

Technical Field

[0001] The present invention relates to the field of luminescent functional complexes, and in particular to a luminescent material and a preparation method and application thereof. Background Art

[0002] Luminescent materials with dual emission are attractive for both fundamental photophysics research and practical applications such as sensing, bioimaging, and color-tunable emission devices. To date, numerous dual-emission materials have been reported, including organic small molecules and polymers, quantum dots, metal-organic frameworks, and transition metal complexes (TMCs). However, the energy difference between existing luminescent materials is small, which can cause the two emission peaks to overlap, hindering their differentiation and observation. Summary of the Invention

[0003] The object of the present invention is to provide a luminescent material and a preparation method and application thereof. The luminescent material of the present invention has good dual emission performance.

[0004] In order to achieve the above-mentioned object of the invention, the present invention provides the following technical solutions:

[0005] The present invention provides a luminescent material having the structural formula shown in Formula I:

[0006]

[0007] described The bidentate polypyridine ligand is a compound in which X includes an oxygen atom, a sulfur atom or an alkyl group, and R includes one of hydrogen, a methoxy group, a trifluoromethyl group and a benzo group.

[0008] Preferably, the bidentate polypyridine ligand includes 2,2′-bipyridine or 1,10-phenanthroline.

[0009] Preferably, it has any one of the structures shown in Formulas 1 to 18:

[0010]

[0011] The present invention also provides a method for preparing the luminescent material described in the above scheme, comprising the following steps:

[0012] A 2,5-bis(N-methyl-N′-(2-pyridyl)amino)pyrazine derivative, a polypyridyl dichloride ruthenium precursor complex and a polar solvent are mixed to carry out a chelation reaction to obtain a metal ruthenium complex;

[0013] Mixing the metal ruthenium complex with a hexafluorophosphate solution to perform an anion replacement reaction to obtain the luminescent material;

[0014] The 2,5-bis(N-methyl-N′-(2-pyridyl)amino)pyrazine derivative has the structural formula shown in Formula II:

[0015]

[0016] The polypyridyl ruthenium dichloride precursor complex has the structural formula shown in Formula III:

[0017]

[0018] Preferably, the molar ratio of the 2,5-bis(N-methyl-N′-(2-pyridyl)amino)pyrazine derivative to the polypyridyl ruthenium dichloride precursor complex is 1 to 1.2:1.

[0019] Preferably, the polar solvent includes ethylene glycol and / or N,N-dimethylformamide.

[0020] Preferably, the molar ratio of the metal ruthenium complex to the hexafluorophosphate is 1:1-10.

[0021] Preferably, the temperature of the chelating reaction is 150-300° C., and the time is 0.5-12 h.

[0022] Preferably, the mass ratio of the polypyridyl ruthenium dichloride precursor complex to the volume ratio of the polar solvent is 1:0.1-0.2 mg / mL.

[0023] The present invention also provides the use of the luminescent material described in the above scheme or the luminescent material obtained by the preparation method described in the above scheme in the preparation of ratio detection imaging materials and the construction of single-molecule white light materials.

[0024] The present invention provides a luminescent material, characterized by having a structural formula shown in Formula I:

[0025]

[0026] described The ligand is a bidentate polypyridine ligand, wherein X includes an oxygen atom, a sulfur atom or an azanyl group, and R includes one of a hydrogen atom, a methoxy group, a trifluoromethyl group and a benzo group.

[0027] The metal ruthenium complex contains more low-light excited states and high-light excited states, which makes The number of photons generated from the low-light excited state to the ground state and the number of photons generated from the high-light excited state to the ground state increases, thereby reducing the peak of the small light, increasing the peak of the large light, and increasing the energy difference. The results of the embodiment show that the energy difference of the luminescent material of the present invention is greater than 146nm. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] Figure 1is the H NMR spectrum of the compound in Example 1 of the present invention;

[0029] Figure 2 is the C NMR spectrum of the compound of Example 1 of the present invention;

[0030] Figure 3 : The emission spectra of the compounds of Examples 1 to 3 of the present invention. DETAILED DESCRIPTION

[0031] The present invention provides a luminescent material having the structural formula shown in Formula I,

[0032]

[0033] described The bidentate polypyridine ligand is a compound in which X includes an oxygen atom, a sulfur atom or an alkyl group, and R includes one of hydrogen, a methoxy group, a trifluoromethyl group and a benzo group.

[0034] In the present invention, the bidentate polypyridine ligand preferably includes 2,2′-bipyridine or 1,10-phenanthroline;

[0035] The azoalkyl group preferably includes a nitrogenmethyl group.

[0036] In the present invention, the luminescent material preferably has any one of the structural formulas shown in Formulas 1 to 18:

[0037]

[0038] The present invention also provides a method for preparing the luminescent material described in the above scheme, comprising the following steps:

[0039] A 2,5-bis(N-methyl-N′-(2-pyridyl)amino)pyrazine derivative, a polypyridyl dichloride ruthenium precursor complex and a polar solvent are mixed to carry out a chelation reaction to obtain a metal ruthenium complex;

[0040] Mixing the metal ruthenium complex with a hexafluorophosphate solution to perform an anion replacement reaction to obtain the luminescent material;

[0041] The 2,5-bis(N-methyl-N′-(2-pyridyl)amino)pyrazine derivative has the structural formula shown in Formula II:

[0042]

[0043] The polypyridyl ruthenium dichloride precursor complex has the structural formula shown in Formula III:

[0044]

[0045] In the present invention, the molar ratio of the 2,5-bis(N-methyl-N′-(2-pyridyl)amino)pyrazine derivative to the polypyridyl ruthenium dichloride precursor complex is preferably 1 to 1.2:1.

[0046] In the present invention, the mass ratio of the polypyridyl ruthenium dichloride precursor complex to the volume ratio of the polar solvent is preferably 1:0.1-0.2 mg / mL; the polar solvent includes ethylene glycol and / or N,N-dimethylformamide.

[0047] In the present invention, the temperature of the chelation reaction is preferably 150-300°C, more preferably 200-250°C; the time is preferably 0.5-12h, more preferably 2-10h, further preferably 4-8h; the chelation reaction is preferably carried out in nitrogen or inert gas.

[0048] The method of reaching the chelating reaction temperature preferably includes oil bath heating and / or microwave heating; the power of the microwave heating is preferably 325W.

[0049] After the chelate reaction, the present invention also preferably cools and separates the obtained chelate reaction product to obtain the metal ruthenium complex.

[0050] In the present invention, the separation method preferably includes reduced pressure rotary evaporation.

[0051] After obtaining the metal ruthenium complex, the present invention mixes the metal ruthenium complex with a hexafluorophosphate solution to carry out anion replacement reaction to obtain the luminescent material.

[0052] In the present invention, before mixing the metal ruthenium complex with the hexafluorophosphate solution, the metal ruthenium complex is preferably mixed with a polar solvent and then mixed with the hexafluorophosphate solution.

[0053] The present invention has no special requirements for the amount of the polar solvent used, and a method well known to those skilled in the art can be used to allow the anion exchange reaction to complete.

[0054] In the present invention, the molar ratio of the metal ruthenium complex to the hexafluorophosphate is preferably 1:1-10, more preferably 1:2-8, and further preferably 1:4-6; the hexafluorophosphate solution is preferably a saturated solution; and the hexafluorophosphate includes potassium hexafluorophosphate.

[0055] The temperature of the anion exchange reaction is preferably room temperature.

[0056] After the anion replacement reaction is completed, the present invention preferably filters, washes and passes through a column in sequence to obtain the luminescent material.

[0057] The present invention has no particular limitation on the filtration, and liquid-solid separation can be performed using a method well known to those skilled in the art. Specifically, in the embodiment of the present invention, the method is suction filtration.

[0058] The present invention has no particular limitation on the washing, and any method well known to those skilled in the art may be used to sufficiently remove impurities from the solid obtained by filtration.

[0059] The present invention also provides the use of the luminescent material described in the above scheme or the luminescent material obtained by the preparation method described in the above scheme in the preparation of ratio detection imaging materials and in the construction of single-molecule white light materials.

[0060] The luminescent material, preparation method and application thereof provided by the present invention are described in detail below with reference to the embodiments, but they should not be construed as limiting the scope of protection of the present invention.

[0061] Example 1

[0062] Synthesis of compounds having the structural formula 1:

[0063]

[0064] Under nitrogen, 38.7 mg (0.11 mmol) of 2,5-bis(N-methyl-N′-(4-methoxy-2-pyridyl)amino)pyrazine and 51.9 mg (0.1 mmol) of bis(2,2′-bipyridyl)ruthenium dichloride were weighed into a microwave reaction vial. 10 mL of ethylene glycol was added, and the microwave power was set to 325 W for 30 minutes. The reaction was cooled to room temperature, and most of the polar solvent was removed by vortexing under reduced pressure, leaving only 1-2 mL of the polar solvent. Saturated potassium hexafluorophosphate solution was then added, filtered, and washed. The crude product was passed through a silica gel column to obtain 155 mg of the compound as a yellow solid in a 52% yield.

[0065] Example 2

[0066] Synthesis of compounds with formula 2:

[0067]

[0068] Under nitrogen, 42.8 mg (0.1 mmol) of 2,5-bis(N-methyl-N′-(4-trifluoromethyl-2-pyridyl)amino)pyrazine and 51.9 mg (0.1 mmol) of bis(2,2′-bipyridyl)ruthenium dichloride were weighed into a microwave reaction vial. 10 mL of ethylene glycol was added, and the microwave power was set to 325 W for 30 minutes. The reaction was cooled to room temperature, and most of the polar solvent was removed by vortexing under reduced pressure, leaving only 1-2 mL of the polar solvent. Saturated potassium hexafluorophosphate solution was then added, filtered, and washed. The crude product was passed through a silica gel column to obtain 280 mg of the compound as a yellow solid in a 71% yield.

[0069] Example 3

[0070] Synthesis of compounds with formula 3:

[0071]

[0072] Under a nitrogen atmosphere, 39.2 mg (0.1 mmol) of 2,5-bis(N-methyl-N′-(2-quinolyl)amino)pyrazine and 51.9 mg (0.1 mmol) of bis(2,2′-bipyridyl)ruthenium dichloride were weighed into a sealed reaction bottle, 10 mL of N,N-dimethylformamide was added and heated in an oil bath. The temperature was controlled at 160°C. The reaction was stopped after 12 h, and the mixture was cooled to room temperature. Most of the polar solvent was removed by vortexing under reduced pressure, leaving 1 to 2 mL of polar solvent. Saturated potassium hexafluorophosphate solution was then added, filtered, washed, and the crude product was passed through a silica gel column to obtain 362 mg of a yellow solid compound with a yield of 56%.

[0073] Structural analysis

[0074] The H NMR spectrum of the compound in Example 1 is as follows: Figure 1 As shown, 1HNMR (400MHz, CD3CN): δ

[0075] [ppm]:3.35(s,3H),3.44(s,3H),3.82(s,3H),3.85(s,3H),6.38(s,1H),6.43(dd,J=8.0and4.0Hz,1H) ,6.56(dd,J=4.0and2.0Hz,1H),6.71(d,J=4.0Hz,1H),7.15(t,J=8.0Hz,2H),7.29(t,J=4.0Hz,1H),7.5 6-7.64(m,6H),7.87(t,J=8.0Hz,1H),7.92(t,J=8.0Hz,1H),8.10(t,J=8.0Hz,1H),8.15(t,J=8.0Hz,1 H), 8.29 (s, 1H), 8.33-8.36 (m, 3H), 8.40 (d, J = 8.0Hz, 1H), 8.49 (d, J = 8.0Hz, 1H), 8.58 (d, J = 4.0Hz, 1H).

[0076] The NMR carbon spectrum of the compound in Example 1 is as follows Figure 2Shown: 13C NMR (100MHz, CD3CN): δ [ppm]: 41.0, 57.2, 101.4, 106.6, 109.3, 124.9, 125.0, 125.1, 125.4, 127.4, 128.0, 128.3, 135.9, 137.1, 138.3, 138.5, 138.8, 138.9, 152.1, 152.6, 152.8, 153.5, 154.1, 158.0, 158.1, 158.2, 169.2.

[0077] Depend on Figures 1-2 It can be seen that the structure of the compound in Example 1 is consistent with that of Formula 1.

[0078] The emission spectra of the compounds prepared in Examples 1 to 3 in acetonitrile solution are as follows: Figure 3 As shown, the maximum emission wavelengths of the three compounds are: 1 (451 and 646 nm, Δλ = 195 nm), 2 (455 and 608 nm, Δλ = 153 nm) and 3 (467 and 613 nm, Δλ = 146 nm). Figure 3 It can be seen that the two maximum emission peak energies of the compounds prepared in Examples 1 to 3 have a large difference. In addition, the intensities of the two emission peaks are comparable, indicating that the luminescent material of the present invention is a dual-emission material with excellent performance and has potential applications in the field of ratiometric luminescence imaging detection.

[0079] The lifetimes of the two emission peaks of the compound having the structural formula 1 in acetonitrile solution are 16 ns and 193 ns, respectively;

[0080] The lifetimes of the two emission peaks of the compound having the structural formula 2 in acetonitrile solution are 13 ns and 219 ns, respectively;

[0081] The lifetimes of the two emission peaks of the compound having the structural formula 3 in acetonitrile solution are 15 ns and 189 ns, respectively.

[0082] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principles of the present invention. These improvements and modifications should also be regarded as within the scope of protection of the present invention.

Claims

1. A luminescent material, characterized in that: It has the structural formula shown in any one of Formula 1 to Formula 3: 。 2. The method for preparing the luminescent material according to claim 1, characterized in that: The following steps are involved: A 2,5-bis(N-methyl-N'-(2-pyridyl)amino)pyrazine derivative, a polypyridyl ruthenium dichloride precursor complex and a polar solvent are mixed to carry out a chelation reaction to obtain a metal ruthenium complex; Mixing the metal ruthenium complex with a hexafluorophosphate solution to perform an anion replacement reaction to obtain the luminescent material; The 2,5-bis(N-methyl-N'-(2-pyridyl)amino)pyrazine derivative has a structural formula shown in any one of Formula II-1 to Formula II-3: Formula II-1; Formula II-2; Formula II-3; The polypyridyl ruthenium dichloride precursor complex has the structural formula shown in Formula III: Formula III.

3. The preparation method according to claim 2, characterized in that The molar ratio of the 2,5-di(N-methyl-N'-(2-pyridyl)amino)pyrazine derivative to the polypyridyl ruthenium dichloride precursor complex is 1-1.2:

1.

4. The preparation method according to claim 2, characterized in that The polar solvent includes ethylene glycol and / or N,N-dimethylformamide.

5. The preparation method according to claim 2, characterized in that The molar ratio of the metal ruthenium complex to the hexafluorophosphate is 1:1-10.

6. The preparation method according to claim 2 or 3, characterized in that The chelating reaction temperature is 150-300° C., and the reaction time is 0.5-12 hours.

7. The preparation method according to claim 4 or 6, characterized in that: The mass ratio of the polypyridyl ruthenium dichloride precursor complex to the volume ratio of the polar solvent is 1:0.1-0.2 mg / mL.

8. Use of the luminescent material according to claim 1 or the luminescent material obtained by the preparation method according to any one of claims 2 to 7 in the preparation of ratio detection imaging materials and the construction of single-molecule white light materials.

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