An inorganic-organic hybrid carbonyl radical luminescent material, its preparation method and application

Abstract

The present invention discloses an inorganic-organic hybrid carbonyl radical luminescent material, its preparation method and application, belonging to the technical field of luminescent materials. In the inorganic-organic hybrid carbonyl radical luminescent material provided by the present invention, the common feature is that the tris-carbonyl substituted benzene derivative molecule after weak coordination with metal is used as the guest, and a series of imidazolium salt ionic liquid molecules are used as the host, and a supramolecular assembly is formed by the way of host-guest doping; the electrostatic interaction and electron delocalization effect generated in the system protect the carbonyl radical to emit stable light; the metal ions coordinated with the radical molecules in the assembly regulate the photophysical properties of the inorganic-organic hybrid carbonyl radical luminescent material through charge transfer. The synergistic effect of the three components enables the inorganic-organic hybrid carbonyl radical luminescent material of this type to obtain the property of adjustable emission color and realize the dual-mode detection of Cd<supgt;3+< / supgt; (turn off type) and Pb<supgt;3+< / supgt; (turn on type).

Description

Technical Field

[0001] The present invention belongs to the technical field of luminescent materials, and particularly relates to an inorganic-organic hybrid carbonyl radical luminescent material, a preparation method thereof, and an application thereof. Background Art

[0002] Due to their unique open-shell structures and excellent optical, electronic, and magnetic properties, organic radicals have good application prospects in organic light-emitting devices, spin probes, electron-hole transport, and magnetic materials. Organic radical luminescent materials with unique dual-state luminescence characteristics have gradually become a research hotspot. Generally, they have unusual photophysical properties such as long-wavelength emission, stimulus-responsive emission, and high electroluminescence quantum efficiency. However, most radicals are transient because they have incredible reactivity due to unpaired electrons. They are also easily structurally damaged by dimerization, hydrogen abstraction, and other chemical reactions. Therefore, most radicals usually exhibit weak luminescence or no luminescence under environmental conditions due to rapid quenching in the environment. Thus, the types of organic luminescent radicals under environmental conditions are still scarce. Only a few radicals have been reported to emit light stably at room temperature, such as triarylmethyl radical derivatives, carbonyl radicals, imidazole radicals, and triphenylamine radicals. However, these radicals generally have relatively low luminescence efficiencies. Therefore, there is an urgent need to develop new strategies to promote the release of radicals.

[0003] Currently, methods for stabilizing organic radicals include steric protection, host-guest interactions, polymer environments, etc. Among them, using steric protection or spin delocalization effects to stabilize organic radicals is a practical and widely used method. However, the complex synthesis steps greatly increase the cost and hinder their practical application. In contrast, materials that protect organic radicals through supramolecular interactions are usually inexpensive and easily available. However, most of the current supramolecular methods for protecting emissive radicals are only based on hydrogen bonding, π-π, CH-π interactions, etc. These methods can restrict the exciton movement of radicals, but cannot regulate the spin delocalization of radicals, let alone precisely control the luminescence properties of radicals. Therefore, it is of great significance to develop a new method that combines molecular motion constraint and regulation of spin delocalization, and on this basis, a radical luminescent material with dynamic luminescence changes and multiple light stimulus responses can be obtained. Summary of the Invention

[0004] Aiming at the above-mentioned prior art, the present invention provides an inorganic-organic hybrid carbonyl radical luminescent material, a preparation method thereof, and an application thereof, which solves the problem of low stabilization efficiency in the prior art.

[0005] In order to achieve the above object, the technical solution adopted by the present invention is: to provide an inorganic-organic hybrid carbonyl radical luminescent material, the structure of which is shown in formula (Ⅰ):

[0006]

[0007] (I),

[0008] Wherein, R is H or CH3, M is a transition metal ion, and X is an inorganic acid radical.

[0009] The beneficial effects of the present invention are as follows: The present invention provides an organic-inorganic hybrid radical luminescent material with a tricarbonyl-substituted benzene derivative as a radical center molecule and weakly coordinated with an inorganic metal salt. This material has good charge transfer ability, exhibits good EPR signal intensity in EPR tests, and combined with the fact that it can return to the ground state without being quenched for a long time in the natural state after being activated by ultraviolet light, so the above-mentioned organic-inorganic hybrid radical luminescent material has good radical stability.

[0010] Based on the above technical solutions, the present invention can be further improved as follows.

[0011] Further, M is Mn 2+ , Co 2+ , Fe 3+ or Ni 2+ .

[0012] Further, X is SO4 2- or NO3 - .

[0013] Further, the luminescent material is one of the compounds represented by formula (a) to formula (h):

[0014]

[0015] (a),

[0016]

[0017] (b),

[0018]

[0019] (c),

[0020]

[0021] (d),

[0022]

[0023] (e),

[0024]

[0025] (f),

[0026]

[0027] (g) or

[0028]

[0029] (h).

[0030] The beneficial effect of adopting the further technical solution is that after metal coordination, there is a drastic charge transfer and weak interaction within the range of van der Waals force between the organic radical molecules and metal ions, such that the organic-inorganic radical emission system of the present invention has multiple excited states and emission states, thereby obtaining multiple stimulus-responsive properties, and the organic-inorganic radical emission system of the present invention can form a bridging effect with other metals, thereby changing the emission intensity, and thus multiple heavy metal ions can be detected with high sensitivity.

[0031] The present invention also provides a preparation method of an inorganic-organic hybrid carbonyl radical luminescent material, comprising the following steps:

[0032] S1: Prepare an acetone solution of a tricarbonyl-substituted benzene organic small molecule as solution one, prepare an acetone solution of an imidazolium salt ionic liquid as solution two, and prepare a mixed solution of water and THF of an inorganic metal salt as solution three;

[0033] S2: Mix solution one and solution three at a volume ratio of 5:1, heat to 126 °C and reflux for 6 h, cool to room temperature after the reaction is completed, purify by column chromatography, and vacuum dry at 60 °C to constant weight to obtain an intermediate product;

[0034] S3: Dissolve the intermediate product in a mixed solution of water, DMF and THF to obtain solution four;

[0035] S4: Mix solution two and solution four at a volume ratio of 50:1, then ultrasonicate for 30 - 40 min, and dry the mixed solution at 70 °C until the sample is in a fluid state after ultrasonication is completed, to obtain the inorganic-organic hybrid carbonyl radical luminescent material.

[0036] The beneficial effect of the present invention is that the preparation method provided by the present invention forms a weak coordination effect between the metal ions in the tricarbonyl-substituted benzene derivative molecules and the inorganic metal salt through the foregoing reaction, and then takes it as the guest and performs supramolecular self-assembly in the ionic environment of the host molecule imidazolium salt ionic liquid molecules, so as to protect the luminescence of the carbonyl radical through electrostatic interaction and electron delocalization effect, and finally obtain the inorganic-organic hybrid carbonyl radical luminescent material; this method has simple steps and avoids problems such as complex synthesis routes and low stabilization efficiency when using traditional methods such as steric hindrance effect or polymer engineering to stabilize radical emission.

[0037] Further, the tricarbonyl-substituted benzene organic small molecule is 1,3,5-triacetylbenzene or 1,3,5-triformylbenzene, and the molar concentration of Solution 1 is 5×10 -3 mol / L.

[0038] Further, the imidazolium salt ionic liquids are as shown in Formula (i) to Formula (m):

[0039] (i), (j), (k), (l) or (m);

[0040] The molar concentration of Solution 2 is 1×10 -2 mol / L.

[0041] Further, the molar concentration of Solution 3 is 1×10 -3 mol / L, and the volume ratio of water to THF is 1:9.

[0042] Further, the volume ratio of water, DMF and THF in the mixed solution of water, DMF and THF is 2:3:5, and the concentration of Solution 4 is 5×10 −3 M.

[0043] The beneficial effect of adopting the further technical solution is that in the imidazolium salt ionic liquid environment, the metal ions that produce a coordination effect with the organic radical molecules undergo a violent charge transfer with the radical molecules, thereby changing the excited state and emission state of the radical luminescence system, and can cause a change in the emission wavelength of the radical luminescent material.

[0044] The present invention also provides an application of the inorganic-organic hybrid carbonyl radical luminescent material in the detection of metal ions.

[0045] The beneficial effect of the present invention is that due to the good radical stability of the inorganic-organic hybrid carbonyl radical luminescent material of the present invention, it can detect metal ions such as Cd 3+ , Pb 3+ etc. through the ferroelectric effect and the metal bridge effect, and the detection sensitivity is high and stable, and it has excellent industrial prospects. Description of the Drawings

[0046] Figure 1 It is the emission spectrum of the inorganic-organic hybrid carbonyl radical luminescent material in Examples 1 to 6;

[0047] Figure 2 It is the absorption spectrum of the inorganic-organic hybrid carbonyl radical luminescent material in Examples 1 to 6;

[0048] Figure 3EPR spectrum of AC5-Fe;

[0049] Figure 4 FT-IR spectra of AC5 and AC5-Fe after light irradiation;

[0050] Figure 5 X-ray photoelectron spectra of AC5 and AC5-Fe;

[0051] Figure 6 Fluorescence lifetime graphs of AC5 and AC5-Fe;

[0052] Figure 7 Steady-state emission spectral kinetic decay curves of AC5 and AC5-Fe;

[0053] Figure 8 Emission spectra of AC5-Fe in response to different concentrations of Cd 3+ ;

[0054] Figure 9 Graph of the linear relationship between AC5-Fe and luminescence intensity - heavy metal ion (Cd 3+ );

[0055] Figure 10 Emission spectra of AC5-Fe in response to different concentrations of Pb 2+ ;

[0056] Figure 11 Graph of the linear relationship between AC5-Fe and luminescence intensity - heavy metal ion (Pb 2+ );

[0057] Figure 12 Schematic diagram of the change in fluorescence emission intensity of AC5-Fe for detecting other metal ions Figure 1 ;

[0058] Figure 13 Schematic diagram of the change in fluorescence emission intensity of AC5-Fe for detecting other metal ions Figure 2 ;

[0059] Figure 14 Actual on-site diagram of AC5-Fe for detecting Pb in industrial wastewater 2+ ;

[0060] Figure 15 Actual on-site diagram of AC5-Fe for detecting Cd in industrial wastewater 3+ ; Specific implementation mode

[0061] The following describes the specific implementation mode of the present invention in detail in combination with embodiments.

[0062] Embodiment 1

[0063] An inorganic-organic hybrid carbonyl radical luminescent material, the structure of which is shown in formula (a):

[0064] Formula (a);

[0065] Its preparation method includes the following steps:

[0066] S1: Dissolve 1,3,5-triacetylbenzene in acetone to obtain solution 1 with a molar concentration of 5×10 -3 mol / L, dissolve imidazolium salt ionic liquid in acetone to obtain solution 2 with a molar concentration of 1×10 -2 mol / L, dissolve Fe(NO3)3 in a mixed solution of water and THF (the volume ratio of water to THF is 1:9) to obtain solution 3 with a molar concentration of 1×10 -3 mol / L; the structural formula of the imidazolium salt ionic liquid used is as follows:

[0067] ;

[0068] S2: Mix solution 1 and solution 3 in a volume ratio of 5:1, heat to 126°C and reflux for 6 h. After the reaction is completed, cool to room temperature, and purify by column chromatography (using analytical pure silica gel powder as the stationary phase, loading the sample dry, first rinse the stationary phase in the column with petroleum ether, and then elute with a mixed solvent of methanol and dichloromethane with a volume ratio of 1:50, collect the target section of the solvent, and spin-dry the solvent after collection), and vacuum dry at 60°C to constant weight to obtain an intermediate product;

[0069] S3: Dissolve the intermediate product in a mixed solution of water, DMF and THF (the volume ratio of water, DMF and THF is 2:3:5) to obtain solution 4 (with a concentration of 5×10 -3 M);

[0070] S4: Mix solution 2 and solution 4 in a volume ratio of 50:1, then ultrasonicate for 30 min. After ultrasonication, dry the mixed solution at 70°C until the sample becomes a fluid state, and the inorganic-organic hybrid carbonyl radical luminescent material AC5-Fe is obtained.

[0071] Example 2

[0072] An inorganic-organic hybrid carbonyl radical luminescent material, the structure of which is shown in formula (b):

[0073] Formula (b);

[0074] Its preparation method includes the following steps:

[0075] S1: Dissolve 1,3,5-triformylbenzene in acetone to obtain a solution with a molar concentration of 5×10-3 Solution I with a concentration of 1×10 -2 mol / L is prepared by dissolving imidazolium salt ionic liquid in acetone. Solution II with a concentration of 1×10 -3 mol / L is prepared by dissolving Fe(NO3)3 in a mixed solution of water and THF (volume ratio of water to THF is 1:9). The structural formula of the imidazolium salt ionic liquid used is as follows:

[0076] ;

[0077] S2: Mix Solution I and Solution III in a volume ratio of 4:1, heat to 126 °C and reflux for 6 h. After the reaction is completed, cool to room temperature, and purify by column chromatography (using analytical pure silica gel powder as the stationary phase, loading the sample dry, first rinsing the stationary phase in the column with petroleum ether, then eluting with a mixed solvent of methanol and dichloromethane with a volume ratio of 1:50, collecting the target fraction of the solvent, and rotary evaporating the solvent after collection). Then dry in vacuo at 60 °C to constant weight to obtain the intermediate product;

[0078] S3: Dissolve the intermediate product in a mixed solution of water, DMF and THF (volume ratio of water, DMF and THF is 2:3:5) to obtain Solution IV (with a concentration of 5×10 -3 M);

[0079] S4: Mix Solution II and Solution IV in a volume ratio of 50:1, then sonicate for 40 min. After sonication, dry the mixed solution at 70 °C until the sample becomes a fluid state to obtain the inorganic-organic hybrid carbonyl radical luminescent material BC5-Fe.

[0080] Example 3

[0081] An inorganic-organic hybrid carbonyl radical luminescent material, whose structure is shown in formula (c):

[0082] Formula (c);

[0083] Its preparation method includes the following steps:

[0084] S1: Dissolve 1,3,5-triacetylbenzene in acetone to obtain Solution I with a concentration of 5×10 -3 mol / L. Dissolve imidazolium salt ionic liquid in acetone to obtain Solution II with a concentration of 1×10 -2 mol / L. Dissolve Ni(NO3)2 in a mixed solution of water and THF (volume ratio of water to THF is 1:9) to obtain Solution III with a concentration of 1×10 -3 mol / L. The structural formula of the imidazolium salt ionic liquid used is as follows:

[0085] ;

[0086] S2: Mix solution one and solution three at a volume ratio of 6:1, heat to 126 °C and reflux for 6 h. After the reaction is completed, cool to room temperature, and purify by column chromatography (using analytical pure silica gel powder as the stationary phase, dry loading, first rinse the stationary phase in the column with petroleum ether, then elute with a mixed solvent of methanol and dichloromethane at a volume ratio of 1:50, collect the target section of the solvent, and spin-dry the solvent after collection), and vacuum dry to constant weight at 60 °C to obtain the intermediate product;

[0087] S3: Dissolve the intermediate product in a mixed solution of water, DMF and THF (the volume ratio of water, DMF and THF is 2:3:5) to obtain solution four (with a concentration of 5×10 -3 M);

[0088] S4: Mix solution two and solution four at a volume ratio of 50:1, then sonicate for 30 min. After sonication, dry the mixed solution at 70 °C until the sample becomes a fluid state, and thus obtain the inorganic-organic hybrid carbonyl radical luminescent material AC5-Ni.

[0089] Example 4

[0090] An inorganic-organic hybrid carbonyl radical luminescent material, whose structure is shown in formula (d):

[0091] Formula (d);

[0092] Its preparation method includes the following steps:

[0093] S1: Dissolve 1,3,5-triformylbenzene in acetone to obtain solution one with a molar concentration of 5×10 -3 mol / L, dissolve the imidazolium salt ionic liquid in acetone to obtain solution two with a molar concentration of 1×10 -2 mol / L, dissolve Ni(NO3)2 in a mixed solution of water and THF (the volume ratio of water and THF is 1:9) to obtain solution three with a molar concentration of 1×10 -3 mol / L; The structural formula of the used imidazolium salt ionic liquid is as follows:

[0094] ;

[0095] S2: Mix solution one and solution three at a volume ratio of 5:1, heat to 126 °C and reflux for 6 h. After the reaction is completed, cool to room temperature, and purify by column chromatography (using analytical pure silica gel powder as the stationary phase, dry loading, first rinse the stationary phase in the column with petroleum ether, then elute with a mixed solvent of methanol and dichloromethane at a volume ratio of 1:50, collect the target section of the solvent, and spin-dry the solvent after collection), and vacuum dry to constant weight at 60 °C to obtain the intermediate product;

[0096] S3: Dissolve the intermediate product in a mixed solution of water, DMF, and THF (the volume ratio of water, DMF, and THF is 2:3:5) to obtain Solution IV (with a concentration of 5×10 -3 M);

[0097] S4: Mix Solution II and Solution IV at a volume ratio of 50:1, then ultrasonicate for 30 min. After the ultrasonication ends, dry the mixed solution at 70 °C until the sample becomes a fluid state, thus obtaining the inorganic-organic hybrid carbonyl radical luminescent material BC5-Ni.

[0098] Example 5

[0099] An inorganic-organic hybrid carbonyl radical luminescent material, whose structure is shown in Formula (e):

[0100] Formula (e);

[0101] Its preparation method includes the following steps:

[0102] S1: Dissolve 1,3,5-triacetylbenzene in acetone to obtain Solution I with a molar concentration of 5×10 -3 mol / L, dissolve the imidazolium salt ionic liquid in acetone to obtain Solution II with a molar concentration of 1×10 -2 mol / L, dissolve MnSO4 in a mixed solution of water and THF (the volume ratio of water and THF is 1:9) to obtain Solution III with a molar concentration of 1×10 -3 mol / L; The structural formula of the used imidazolium salt ionic liquid is as follows:

[0103] ;

[0104] S2: Mix Solution I and Solution III at a volume ratio of 5:1, then heat to 126 °C and reflux for 6 h. After the reaction is completed, cool to room temperature, and purify by column chromatography (using analytical pure silica gel powder as the stationary phase, loading the sample dry, first rinse the stationary phase in the column with petroleum ether, then elute with a mixed solvent of methanol and dichloromethane with a volume ratio of 1:50, collect the target section of the solvent, and spin-dry the solvent after collection), and vacuum dry at 60 °C to constant weight to obtain the intermediate product;

[0105] S3: Dissolve the intermediate product in a mixed solution of water, DMF, and THF (the volume ratio of water, DMF, and THF is 2:3:5) to obtain Solution IV (with a concentration of 5×10 -3 M);

[0106] S4: Mix solution two and solution four at a volume ratio of 50:1, then sonicate for 30 min. After sonication, dry the mixed solution at 70 °C until the sample becomes a fluid state, thus obtaining the inorganic-organic hybrid carbonyl radical luminescent material AC5-Mn.

[0107] Example 6

[0108] An inorganic-organic hybrid carbonyl radical luminescent material, whose structure is shown in formula (f):

[0109] Formula (f);

[0110] Its preparation method includes the following steps:

[0111] S1: Dissolve 1,3,5-triformylbenzene in acetone to obtain solution one with a molar concentration of 5×10 -3 mol / L. Dissolve the imidazolium salt ionic liquid in acetone to obtain solution two with a molar concentration of 1×10 -2 mol / L. Dissolve MnSO4 in a mixed solution of water and THF (the volume ratio of water to THF is 1:9) to obtain solution three with a molar concentration of 1×10 -3 mol / L. The structural formula of the used imidazolium salt ionic liquid is as follows:

[0112] ;

[0113] S2: Mix solution one and solution three at a volume ratio of 5:1, then heat to 126 °C and reflux for 6 h. After the reaction is completed, cool to room temperature, and purify by column chromatography (using analytical pure silica gel powder as the stationary phase, loading the sample dry, first rinse the stationary phase in the column with petroleum ether, then elute with a mixed solvent of methanol and dichloromethane with a volume ratio of 1:50, collect the target section of the solvent, and rotary evaporate the solvent after collection) and vacuum dry at 60 °C to constant weight to obtain the intermediate product;

[0114] S3: Dissolve the intermediate product in a mixed solution of water, DMF and THF (the volume ratio of water, DMF and THF is 2:3:5) to obtain solution four (with a concentration of 5×10 -3 M);

[0115] S4: Mix solution two and solution four at a volume ratio of 50:1, then sonicate for 30 min. After sonication, dry the mixed solution at 70 °C until the sample becomes a fluid state, thus obtaining the inorganic-organic hybrid carbonyl radical luminescent material BC5-Mn.

[0116] Example 7

[0117] An inorganic-organic hybrid carbonyl radical luminescent material, whose structure is shown in formula (g):

[0118] Formula (g);

[0119] The preparation method thereof comprises the following steps:

[0120] S1: Dissolve 1,3,5-triacetylbenzene in acetone to obtain Solution 1 with a molar concentration of 5×10 -3 mol / L, dissolve the imidazolium salt ionic liquid in acetone to obtain Solution 2 with a molar concentration of 1×10 -2 mol / L, dissolve Co(NO3)2 in a mixed solution of water and THF (the volume ratio of water to THF is 1:9) to obtain Solution 3 with a molar concentration of 1×10 -3 mol / L; the structural formula of the used imidazolium salt ionic liquid is as follows:

[0121] ;

[0122] S2: Mix Solution 1 and Solution 3 at a volume ratio of 5:1, heat to 126°C and reflux for 6 h, cool to room temperature after the reaction is completed, purify by column chromatography, and vacuum dry at 60°C to constant weight to obtain an intermediate product;

[0123] S3: Dissolve the intermediate product in a mixed solution of water, DMF and THF (the volume ratio of water, DMF and THF is 2:3:5) to obtain Solution 4 (with a concentration of 5×10 -3 M);

[0124] S4: Mix Solution 2 and Solution 4 at a volume ratio of 50:1, then ultrasonicate for 30 min, and dry the mixed solution at 70°C until the sample becomes a fluid state to obtain the inorganic-organic hybrid carbonyl radical luminescent material AC1-Co.

[0125] Example 8

[0126] An inorganic-organic hybrid carbonyl radical luminescent material, whose structure is as shown in Formula (h):

[0127] Formula (h);

[0128] The preparation method thereof comprises the following steps:

[0129] S1: Dissolve 1,3,5-triformylbenzene in acetone to obtain Solution 1 with a molar concentration of 5×10 -3 mol / L, dissolve the imidazolium salt ionic liquid in acetone to obtain Solution 2 with a molar concentration of 1×10 -2 mol / L, dissolve Co(NO3)2 in a mixed solution of water and THF (the volume ratio of water to THF is 1:9) to obtain Solution 3 with a molar concentration of 1×10 -3Solution III with a concentration of

[0130] ;

[0131] S2: Mix Solution I and Solution III in a volume ratio of 5:1, heat to 126 °C and reflux for 6 h. After the reaction is completed, cool to room temperature. Purify by column chromatography (using analytical pure silica gel powder as the stationary phase, loading the sample dry, first rinse the stationary phase in the column with petroleum ether, then elute with a mixed solvent of methanol and dichloromethane with a volume ratio of 1:50, collect the target section of the solvent, and rotary evaporate the solvent after collection), and dry under vacuum at 60 °C to constant weight to obtain the intermediate product;

[0132] S3: Dissolve the intermediate product in a mixed solution of water, DMF and THF (the volume ratio of water, DMF and THF is 2:3:5) to obtain Solution IV (with a concentration of 5×10 -3 M);

[0133] S4: Mix Solution II and Solution IV in a volume ratio of 50:1, then sonicate for 30 min. After sonication, dry the mixed solution at 70 °C until the sample becomes a fluid state to obtain the inorganic-organic hybrid carbonyl radical luminescent material BC2-Co.

[0134] Example 9

[0135] An inorganic-organic hybrid carbonyl radical luminescent material, whose structure is shown in formula (a):

[0136] Formula (a);

[0137] Its preparation method includes the following steps:

[0138] S1: Dissolve 1,3,5-triacetylbenzene in acetone to obtain Solution I with a molar concentration of 5×10 -3 mol / L, dissolve the imidazolium salt ionic liquid in acetone to obtain Solution II with a molar concentration of 1×10 -2 mol / L, dissolve Fe(NO3)3 in a mixed solution of water and THF (the volume ratio of water and THF is 1:9) to obtain Solution III with a molar concentration of 1×10 -3 mol / L; The structural formula of the imidazolium salt ionic liquid used is as follows:

[0139] ;

[0140] S2: Mix Solution 1 and Solution 3 in a volume ratio of 5:1, heat to 126 °C and reflux for 6 h. After the reaction is completed, cool to room temperature. Purify by column chromatography (using analytical pure silica gel powder as the stationary phase, dry loading, first rinse the stationary phase in the column with petroleum ether, then elute with a mixed solvent of methanol and dichloromethane with a volume ratio of 1:50, collect the target section of the solvent, and rotary evaporate the solvent after collection), and vacuum dry at 60 °C to constant weight to obtain the intermediate product;

[0141] S3: Dissolve the intermediate product in a mixed solution of water, DMF and THF (the volume ratio of water, DMF and THF is 2:3:5) to obtain Solution 4 (concentration is 5×10 -3 M);

[0142] S4: Mix Solution 2 and Solution 4 in a volume ratio of 50:1, then sonicate for 30 min. After sonication, dry the mixed solution at 70 °C until the sample becomes a fluid state to obtain the inorganic-organic hybrid carbonyl radical luminescent material AC3-Fe.

[0143] Example 10

[0144] An inorganic-organic hybrid carbonyl radical luminescent material, whose structure is shown in formula (b):

[0145] Formula (b);

[0146] Its preparation method includes the following steps:

[0147] S1: Dissolve 1,3,5-triformylbenzene in acetone to obtain Solution 1 with a molar concentration of 5×10 -3 mol / L, dissolve the imidazolium salt ionic liquid in acetone to obtain Solution 2 with a molar concentration of 1×10 -2 mol / L, dissolve Fe(NO3)3 in a mixed solution of water and THF (the volume ratio of water and THF is 1:9) to obtain Solution 3 with a molar concentration of 1×10 -3 mol / L; The structural formula of the used imidazolium salt ionic liquid is as follows:

[0148] ;

[0149] S2: Mix Solution 1 and Solution 3 in a volume ratio of 4:1, heat to 126 °C and reflux for 6 h. After the reaction is completed, cool to room temperature. Purify by column chromatography (using analytical pure silica gel powder as the stationary phase, dry loading, first rinse the stationary phase in the column with petroleum ether, then elute with a mixed solvent of methanol and dichloromethane with a volume ratio of 1:50, collect the target section of the solvent, and rotary evaporate the solvent after collection), and vacuum dry at 60 °C to constant weight to obtain the intermediate product;

[0150] S3: Dissolve the intermediate product in a mixed solution of water, DMF and THF (the volume ratio of water, DMF and THF is 2:3:5) to obtain Solution IV (with a concentration of 5×10 -3 M);

[0151] S4: Mix Solution II and Solution IV at a volume ratio of 50:1, then ultrasonicate for 40 min. After the ultrasonication ends, dry the mixed solution at 70 °C until the sample becomes a fluid state, thus obtaining the inorganic-organic hybrid carbonyl radical luminescent material BC4-Fe.

[0152] Comparative Example

[0153] A carbonyl radical luminescent material, the preparation method thereof includes the following steps:

[0154] S1: Prepare an acetone solution of 1,3,5-triacetylbenzene as Solution I (with a molar concentration of 5×10 -3 mol / L), and prepare an acetone solution of an imidazolium salt ionic liquid as Solution II (with a molar concentration of 1×10 -2 mol / L). The structural formula of the imidazolium salt ionic liquid used is as follows:

[0155] ;

[0156] S2: Mix Solution I and Solution IV at a volume ratio of 50:1, then ultrasonicate for 30 min. After the ultrasonication ends, dry the mixed solution at 70 °C until the sample becomes a fluid state, thus obtaining the inorganic-organic hybrid carbonyl radical luminescent material AC5.

[0157] Experimental Example 1

[0158] Emission spectrum test: Add 300 μL of AC5-Mn, AC5-Fe, AC5-Ni, BC5-Mn, BC5-Fe, and BC5-Ni into six four-way cuvettes (with an optical path of 2 mm) respectively. First, use a handheld ultraviolet lamp with an emission wavelength of 365 nm and a power of 3 W to photoactivate each sample for 30 seconds, and then use ultraviolet light with an excitation wavelength of 365 nm in a HORIBA FluoreMax+ fluorescence spectrometer to perform emission spectrum tests on the above three samples under the condition of a slit of 2 nm. The results are as Figure 1 shown. The emission spectrum of AC5-Fe shows a cyan-blue emission near 475 nm. Although the emission spectra of the other systems are slightly different from that of AC5-Fe, their emission colors are almost the same as that of AC5-Fe in terms of the visible emission color.

[0159] Experimental Example 2

[0160] UV-Visible absorption spectrum test: The absorption spectrum test of the free radical sample used to test the emission spectrum in Experimental Example 1 was performed using Shimazu ultraviolet spectrophotometer UV3600PLUS. The results are as follows: Figure 2 As shown, both have significant absorption peaks and broad absorption bands at 350nm and 400nm-500nm, respectively, with typical free radical absorption characteristics.

[0161] Experimental Example 3

[0162] Electron paramagnetic resonance test: Use Bruker EMXnano spectrometer to perform EPR test on AC5-Fe. Dilute the prepared AC5-Fe sample with acetone solvent to 500μL, then add 20mg of 5,5-dimethyl-1-pyrroline N-oxide (DMPO) to the sample, and ultrasonicate the mixed sample for 10 minutes. After using a capillary to absorb the sample, irradiate the capillary with a handheld UV lamp with an emission wavelength of 365nm for 1 minute. After completion, put the capillary into the instrument test chamber for testing. The results are as follows: Figure 3 As shown, it shows obvious signal characteristics of carbonyl radical.

[0163] Experimental Example 4

[0164] Fourier transform infrared spectroscopy test: AC5-Fe and AC5 were mixed with potassium bromide and pressed into tablets for testing. The results are as follows: Figure 4 As shown in the figure, compared with the infrared spectrum of AC5, the carbonyl vibration peak on pyromellitic trialdehyde shifts significantly to a lower wave number, indicating that Fe in the organic-inorganic hybrid free radical system of the present invention 3+ Interaction with the carbonyl group.

[0165] Experimental Example 5

[0166] X-ray photoelectron spectroscopy: AC5 and AC5-Fe were tested by X-ray photoelectron spectroscopy using Thermo Scientific K-Alpha. Figure 5 As shown in the figure, compared with AC5, there is no new binding energy diffraction peak in the O1s high-resolution spectrum of AC5-Fe, which proves that no covalent bond is formed between compound A and the metal ion; however, the O1s spectrum of AC5-Fe has an overall shift toward the high binding energy direction, indicating that the carbonyl group and Fe 3+ There are non-covalent interactions between them.

[0167] Experimental Example 6

[0168] Photoluminescence fluorescence lifetime measurement: The fluorescence lifetimes of AC5 and AC5-Fe were measured using a HORIBA FluoreMax+ fluorometer. As Figure 6 shown, the fluorescence lifetimes of AC5 and AC5-Fe were 7.28 ns and 8.56 ns, respectively.

[0169] Experimental Example 7

[0170] Photoluminescence steady-state kinetics measurement: The kinetics curves of the steady-state emission spectra of AC5 and AC5-Fe were also measured using a HORIBA FluoreMax+ fluorometer. As Figure 7 shown, the natural quenching rate of AC5 in the dark environment was much greater than that of AC5-Fe, indicating that the radical lifetime of the organic-inorganic hybrid radical system doped with Fe 3+ was much greater than that of the carbonyl organic radical system without doping.

[0171] Experimental Example 8

[0172] Metal ion detection application 1: Using AC5-Fe as a sensing probe, its sensing performance for two heavy metal ions, Pb 2+ and Cd 3+ , was investigated. First, Pb 2+ solutions (H2O:THF, v / v = 1:9) with different concentrations were prepared, and the concentrations were 10 - 8 M, 2×10 -8 M, 4×10 -8 M, 6×10 -8 M, 8×10 -8 M, 10 -7 M, 2×10 -7 M, 4×10 -7 M, 6×10 -7 M, 8×10 -7 M from low to high. The UV-light-activated AC5-Fe was incubated in the Pb 2+ solutions with increasing concentrations for 5 minutes in sequence, and then the emission spectra at each incubation concentration were measured. For the sensing linear experiment of Cd 3+ , except that the incubation solution was Cd 3+ solution, the others were the same.

[0173] The experimental results are as Figures 8 - 11 shown. The response of AC5-Fe to Pb 2+ was a Turn on-type response ( Figure 8 ), and the linear equation was: Lg(I R / I B ) = 0.0197c Pb+0.6669, R 2 =0.9953, the linear range is 10 -7 ~7×10 -7 mol / L, the detection limit is 3.3×10 -8 mol / L ( Figure 9 ), where I R is Figure 8 the emission peak intensity near 550 nm in B and I Figure 8 is 3+ the emission peak intensity near 470 nm in Figure 10 ); The response of AC5-Fe to Cd -6 is a Turn off-type response ( Cd ), and the linear equation is: 10 2 LgI=-0.2363c -6 =+0.8575, R Cd =0.9957 and 10 2 LgI=-0.6857c -5 +3.129, R -5 =0.9978, the linear range is 1.3×10 -6 ~9.1×10 Figure 11 mol / L, the detection limit is 4.3×10 Figure 10 mol / L (

[0174] Experimental Example 9

[0175] Metal ion detection application 2: Prepare solutions of other metal ions with a concentration of 8×10 -8 M (H2O:THF, v / v = 1:9). It includes Na + , Hg 2+ , Ni 2+ , Co 2+ and Cr 3+ . The test process is the same as that in Experimental Example 8. As Figures 12 - 13 shown, the emission of AC5-Fe hardly changes in the presence of other metal ions, indicating that the AC5-Fe free radical system provided by the present invention has good detection specificity for Pb 2+ and Cd 3 + .

[0176] Experimental Example 10

[0177] Practical application of simulated industrial wastewater: Prepare a solution of Pb with a concentration of 10 -7 M 2+Solution (with tap water as the solvent). To simulate the industrial wastewater environment containing heavy metal particles, the above solution also contains Na + , Hg 2+ , Ni 2+ , Co 2+ and Cr 3+ and other metal ions (with a concentration of 10 -7 M). Take 15 μL of the above-prepared simulated wastewater and add it drop by drop to the AC5-Fe system that has been prepared in advance and activated by ultraviolet light. Ultrasonic for 5 minutes, and then activate AC5-Fe again by ultraviolet light. The experimental results are as shown in Figure 14 . For the actual sample AC5-Fe@Pb containing Pb 2+ , the radical emission intensity is significantly increased compared with that before responding to the actual sample; for the response to Cd 3+ , during the preparation of the simulated wastewater, except replacing Pb 2+ with Cd 3+ , the other steps are the same as those for preparing the simulated industrial wastewater containing Pb 2+ . The experimental results are as shown in Figure 15 . For the actual sample AC5-Fe@Cd containing Cd 3+ , the radical emission intensity is significantly quenched compared with that before responding to the actual sample.

[0178] Although the specific implementation manners of the present invention have been described in detail in combination with the embodiments, it should not be construed as a limitation on the protection scope of this patent. Within the scope described in the claims, various modifications and deformations that can be made by those skilled in the art without creative labor still fall within the protection scope of this patent.

Claims

1. An inorganic-organic hybrid carbonyl radical luminescent material, characterized in that: The preparation method comprises the following steps: S1: preparing an acetone solution of tricarbonyl-substituted benzene organic small molecule as solution 1, preparing an acetone solution of imidazole salt ionic liquid as solution 2, and preparing a mixed solution of water and THF of inorganic metal salt as solution 3; S2: Solution 1 and solution 3 were mixed in a volume ratio of 4-6:1, heated to 126°C and refluxed for 6 hours, cooled to room temperature after the reaction was completed, purified by column chromatography, and vacuum dried at 60°C to constant weight to obtain an intermediate product; S3: dissolving the intermediate product in a mixture of water, DMF and THF to obtain solution 4; S4: Solution 2 and Solution 4 are mixed at a volume ratio of 50:1, and then ultrasonicated for 30-40 minutes. After the ultrasonication, the mixed solution is dried at 70°C until the sample is in a fluid state, thereby obtaining an inorganic-organic hybrid carbonyl free radical luminescent material; The structure of the intermediate product is shown in formula (I): （Ⅰ）， Where R is H or CH3, M is Mn 2+ 、Co 2+ , Fe 3+ or Ni 2+ , X is SO4 2- or NO3 - .

2. The inorganic-organic hybrid carbonyl free radical luminescent material according to claim 1, characterized in that: The intermediate product is one of the compounds represented by formula (a) to formula (h): （a）、 （b）、 （c）、 （d）、 (g) or （h）。 3. The inorganic-organic hybrid carbonyl free radical luminescent material according to claim 1, characterized in that: The tricarbonyl-substituted benzene organic small molecule is 1,3,5-triacetylbenzene or 1,3,5-trialdehydebenzene, and the molar concentration of the solution is 5×10 -3 mol / L.

4. The inorganic-organic hybrid carbonyl free radical luminescent material according to claim 1, characterized in that: The imidazolium salt ionic liquid is one of the compounds represented by formula (i) to formula (m): (i) (j) (k) (l) or (m); The molar concentration of solution 2 is 1×10 -2 mol / L.

5. The inorganic-organic hybrid carbonyl free radical luminescent material according to claim 1, characterized in that: The molar concentration of solution three is 1×10 -3 mol / L, the volume ratio of water and THF is 1:

9.

6. The inorganic-organic hybrid carbonyl free radical luminescent material according to claim 1, characterized in that: The volume ratio of water, DMF and THF in the mixed solution of water, DMF and THF is 2:3:5, and the concentration of the solution 4 is 5×10 -3 M.

7. The inorganic-organic hybrid carbonyl radical luminescent material according to any one of claims 1 to 6 in Pb 2+ or Cd 3+ Applications in ion detection.

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