Temperature-sensitive organic luminescent molecules, thin films doped with organic luminescent molecules, and preparation methods and applications thereof

Abstract

The invention discloses a temperature-sensitive organic light-emitting molecule, a film doped with an organic light-emitting molecule, and a preparation method and application thereof. After precise molecular design, temperature-sensitive organic light-emitting molecules of square acid and fluorene styrene are invented. On the one hand, in order to solve the problems of luminescence quenching, difficulty in solid-state accumulation and conformational transition, no response to thermal stimulation or slow response, etc. in the current solid state, a series of square acid molecules are provided by introducing different side groups into the square acid core, and fluorescent response organic materials sensitive to different temperature ranges (medium temperature, medium-high temperature, high temperature) are constructed. On the other hand, in order to overcome the interference of the intrinsic fluorescence background in certain occasions, a room temperature phosphorescent organic light-emitting film material based on fluorene styrene is developed, that is, fluorene styrene small molecules are incorporated into the polymer polyvinyl alcohol, and the multiple hydrogen bonds generated by polyvinyl alcohol and molecules are used to construct a rigid environment to realize the construction of room temperature phosphorescence and fluorescence dual response materials to temperature stimulation.

Description

Technical Field

[0001] The present invention relates to the technical field of thermal response, and more particularly to temperature-sensitive organic luminescent molecules, thin films doped with organic luminescent molecules, and preparation methods and applications thereof. Background Art

[0002] Temperature is one of the commonly used physical quantities in industrial production and daily life. Temperature changes have an important impact on people's production and life. When the ambient temperature is too high, product quality or performance will often decline, such as fresh food spoilage, vaccine and medicine failure, and integrated circuit damage. For precision aerospace instruments, after experiencing high temperatures, the material properties of their parts will be affected, resulting in more dangerous situations. Therefore, detecting product temperature changes is of great significance to the normal operation of people's production and life. At present, there are mainly two methods commonly used to detect temperature changes or thermal history: (1) Real-time monitoring with thermometers, mainly including contact temperature measurement of thermoelectric thermometers and expansion thermometers, and non-contact temperature measurement with infrared thermometers. However, the above methods all have their own shortcomings. Contact temperature measurement requires waiting for the thermal equilibrium between the object and the probe, and it is difficult to measure the temperature of fast-moving objects in real time. The sensitivity and accuracy of non-contact infrared temperature measurement are difficult to meet the requirements in some occasions; (2) The second method is that after the product undergoes a high-temperature process, professionals are required to conduct a comprehensive inspection of the quality and structure of the product itself to eliminate the places where high temperature occurs one by one. For example, when repairing a circuit that has been damaged by high temperature, professional electricians need to use professional tools, such as multimeters and clamp-type ammeters, to check and troubleshoot every part of the circuit, so this detection method is very time-consuming and economically expensive. Therefore, it is urgent to develop a simple, low-cost, and responsive means to detect and characterize temperature changes.

[0003] Thermosensitive luminescent materials are a type of material that can produce changes in luminescent signals under the influence of external temperature changes. With its non-invasive characteristics, it can easily detect and record the thermal history of an object, that is, trace the temperature changes experienced by the object. At present, most of the thermosensitive luminescent materials are concentrated on inorganic and metal materials. For example, patent CN202210374546.8 designs a luminescent thermosensitive material containing a variety of metal elements such as lutetium, bismuth, vanadium, etc. For thermosensitive organic luminescent materials, there is no need to use expensive heavy metals with strong toxicity, and it has unique advantages such as low cost, simple processing, and easy structure adjustment. It can be made into various forms such as thin films and coatings, and has received extensive attention and research in the fields of temperature sensing and thermal history detection. However, due to the existence of solid-state molecular interactions, it is difficult to achieve temperature-responsive luminescent color changes in organic materials in the solid state. Therefore, the development of new thermosensitive solid-state organic luminescent materials is an attractive but challenging problem, and there is no specific design strategy so far. It can be seen from a large number of studies that efficient temperature stimulus responsive materials not only depend on the design of molecular structure, but are also closely related to their aggregation microenvironment. Aggregate microenvironmental factors such as molecular conformation, non-covalent interactions, molecular stacking, etc. can significantly regulate the different excited state behaviors of organic light-emitting materials. Given their potential technological importance, it is urgent to develop new temperature-sensitive organic light-emitting materials and have a deeper understanding of their structure-property relationships and potential mechanisms.

[0004] Fluorescent materials account for a large part of the existing thermosensitive organic light-emitting materials. They can present the thermal history of materials through the enhancement and reduction of fluorescence intensity, the blue shift and red shift of fluorescence emission, etc. However, the temperature range for detecting thermal history is relatively narrow. For example, the public literature (Polym.Chem., 2014, 5, 5978-5984) uses fluorescent molecules to modify polymers to obtain thermosensitive materials that rely on changes in fluorescence intensity. They can only detect temperature changes in the range of 5-60°C. Fluorescent materials that respond to a wide temperature range still need to continue to be researched and developed. In addition, in some cases, the object being detected will have inherent fluorescence background interference, which limits its application. Phosphorescent materials have a long lifespan and obvious afterglow that can overcome the above interference problems and then detect thermal history temperature. Therefore, thermosensitive room temperature phosphorescent materials or thermosensitive fluorescence-phosphorescence dual response materials also have very important research value. However, due to the stringent requirements of phosphorescent materials for special molecular structures and aggregation microenvironments, the types of thermosensitive solid-state organic room temperature phosphorescent materials currently developed are relatively scarce. Therefore, it is a major challenge in current science and technology to construct universal and stable thermal history detection materials based on organic small molecules, achieve obvious fluorescence or phosphorescence changes, and be adaptable to thermal history detection over a wide temperature range. Summary of the invention

[0005] To solve the problems in the prior art, the present invention proposes a temperature-sensitive organic light-emitting molecule, an organic light-emitting molecule-doped film, and a preparation method and application thereof. The present invention is to avoid the high cost and cumbersomeness of the traditional detection thermal history method, and through precise molecular design, the temperature-sensitive organic light-emitting small molecules of square acid and fluorene styrene are studied and invented. On the one hand, in order to solve the problems of luminescence quenching, solid-state accumulation and conformational transition difficulties, no response to thermal stimulation or slow response, etc., by introducing different side groups to the square acid core, a series of square acid molecules are provided, and sensitive fluorescent response organic materials to different temperature ranges (medium temperature, medium and high temperature, high temperature) are constructed. On the other hand, the present invention is to overcome the interference of intrinsic fluorescence background in certain occasions, and develops a room temperature phosphorescent organic light-emitting film material based on fluorene styrene, that is, fluorene styrene small molecules are incorporated into polymer polyvinyl alcohol, and multiple hydrogen bonds generated by polyvinyl alcohol and molecules are used to construct a rigid environment to realize the construction of room temperature phosphorescence and fluorescence dual response materials of temperature stimulation.

[0006] One of the purposes of the present invention is to provide a temperature-sensitive organic light-emitting molecule, wherein the organic light-emitting molecule has the following general structural formula:

[0007]

[0008] The two Rs are independent of each other: i is each independently an integer from 0 to 10, and m is each independently an integer from 0 to 18; n is an integer of 0-10, X is hydrogen, halogen, alkoxy, alkyl, or aromatic ring group; o is an integer of 0-10, Y is hydrogen, halogen, alkoxy, alkyl, or aromatic ring group; p is an integer of 0-10, Z is hydrogen, halogen, alkoxy, alkyl, or aromatic ring group;

[0009] Two R's are independently: halogen; n is an integer of 0-10, X is hydrogen, halogen, alkoxy, alkyl, or aromatic ring group; o is an integer of 0-10, Y is hydrogen, halogen, alkoxy, alkyl, or aromatic ring group; p is an integer of 0-10, and Z is hydrogen, halogen, alkoxy, alkyl, or aromatic ring group;

[0010] Alternatively, the organic light-emitting molecule has the following general structural formula:

[0011]

[0012] Wherein q is independently an integer of 0-10; R1 and R1' are independently aryl or alkyl;

[0013] Alternatively, the organic light-emitting molecule has the following general structural formula:

[0014]

[0015] Wherein R2 is independently r is an integer from 0 to 20.

[0016] In the temperature-sensitive organic light-emitting molecule of the present invention, preferably, the organic light-emitting molecule has one of the following molecular structural formulas I to IV:

[0017] Molecule I: The two Rs are independent of each other. i is each independently an integer of 0-10, m is each independently an integer of 0-18; two R's are each independently halogen, preferably -Cl;

[0018] Molecule II: wherein n is independently an integer of 0 to 10; X is independently hydrogen, halogen, alkoxy, alkyl, or aromatic ring group;

[0019] Molecule III: Wherein o is an integer of 0-10; Y is hydrogen, halogen, alkoxy, alkyl, or aromatic ring group;

[0020] Molecule IV: Wherein p is an integer of 0-10, and Z is hydrogen, halogen, alkoxy, alkyl, or aromatic ring group.

[0021] The second object of the present invention is to provide a method for preparing the temperature-sensitive organic light-emitting molecule described in any one of the objects of the present invention, wherein the preparation of the organic light-emitting molecule is selected from the following methods:

[0022] Method 1: Under anhydrous and oxygen-free conditions, the square acid molecules and reacting in a solvent to obtain the organic light-emitting molecule;

[0023] Among them, the square acid is:

[0024] The R in is: i is each independently an integer from 0 to 10, and m is each independently an integer from 0 to 18; n is an integer of 0-10, X is hydrogen, halogen, alkoxy, alkyl, or aromatic ring group; p is an integer of 0-10, and Z is hydrogen, halogen, alkoxy, alkyl, or aromatic ring group;

[0025] R' is a halogen, n is an integer of 0-10, X is hydrogen, halogen, alkoxy, alkyl, or aromatic ring group; p is an integer of 0-10, and Z is hydrogen, halogen, alkoxy, alkyl, or aromatic ring group;

[0026] Method 2: Under the condition of anhydrous and oxygen-free conditions, in the presence of a catalyst, the molecule III-1, the molecule III-2 and a base are subjected to a substitution reaction in a solvent to obtain the organic light-emitting molecule;

[0027] Among them, molecule III-1: Molecule III-2: o is an integer of 0-10, Y is hydrogen, halogen, alkoxy, alkyl, or aromatic ring group;

[0028] Preferably, in method 2,

[0029] The solvent is at least one of toluene, N,N-dimethylformamide, and tetrahydrofuran; and / or,

[0030] The catalyst is selected from at least one of tetrakis(triphenylphosphine)palladium and cuprous iodide; and / or,

[0031] The reaction uses an organic base; preferably at least one of triethylamine and piperidine; and / or,

[0032] The molar ratio of molecule III-1 to molecule III-2 is 1:(1-10); preferably 1:(6-8); and / or,

[0033] The molar volume ratio of molecule III-1 to the organic base is 1 mmol:(10 mL to 30 mL), preferably 1 mmol:(15 mL to 20 mL); and / or,

[0034] The amount of the catalyst is 20% to 180% of the amount of the substance of molecule III-1; preferably, both tetrakis(triphenylphosphine)palladium and cuprous iodide are added to the reaction system as catalysts, and further preferably, cuprous iodide is 80% to 120% of the amount of the substance of molecule III-1, preferably 80% to 110%; tetrakis(triphenylphosphine)palladium is 40% to 60% of the amount of the substance of molecule III-1, preferably 40% to 50%; and / or,

[0035] The molar volume ratio of molecule III-1 to the solvent is 1 mmol:(10 mL to 25 mL), preferably 1 mmol:(15 mL to 20 mL); and / or,

[0036] The reaction temperature is 80-100°C and the reaction time is 48-72h;

[0037] Method 3: Under the condition of anhydrous and oxygen-free conditions, molecule VI, molecule VI-1 and a base are reacted in a solvent to obtain the organic light-emitting molecule;

[0038] Among them, molecule VI: Molecule VI-1: r is an integer from 0 to 20;

[0039] Preferably, in method three,

[0040] The solvent is selected from at least one of N,N-dimethylformamide, dimethyl sulfoxide and methanol;

[0041] The base comprises at least one selected from potassium carbonate, sodium hydroxide, and sodium tert-butoxide;

[0042] The molar ratio of molecule VI to molecule VI-1 is 1:(2-5), preferably 1:(2.5-3);

[0043] The molar ratio of molecule VI to base is 1:(2-10), preferably 1:(2-5);

[0044] The molar volume ratio of molecule VI to the solvent is 1 mmol:(10 mL to 55 mL), preferably 1 mmol:(30 mL to 50 mL);

[0045] The reaction temperature is raised to 80-100°C and the reaction time is 12-24h.

[0046] In the method for preparing the temperature-sensitive organic light-emitting molecule of the present invention, preferably,

[0047] The preparation method of the molecule I is as follows:

[0048] 1) Optionally, under anhydrous and oxygen-free conditions, the molecule I-1 and the compound represented by the molecule I-2 and a base are subjected to a substitution reaction in a solvent to obtain a molecule I-3;

[0049] Molecule I-1: i is an integer from 0 to 10 independently;

[0050] Molecule I-2: Br-R", R"=-C m H 2m+1 , m is an integer from 0 to 18;

[0051] Preferably, in step 1),

[0052] The solvent is selected from at least one of acetonitrile, methanol and acetone; and / or,

[0053] The base is selected from at least one of potassium carbonate, sodium hydroxide and sodium tert-butoxide; and / or,

[0054] The molar ratio of molecule I-1 to molecule I-2 is 1:(1-4), preferably 1:(1-2); and / or,

[0055] The molar ratio of molecule I-1 to base is 1:(1-4), preferably 1:(1-2); and / or,

[0056] The molar volume ratio of molecule I-1 to the solvent is 1 mmol:(2.5 mL to 5 mL), preferably 1 mmol:(3 mL to 4 mL); and / or,

[0057] The reaction temperature is 60-100°C and the reaction time is 8-24h;

[0058] 2) Under anhydrous and oxygen-free conditions, in the presence of a catalyst, a compound represented by molecule I-4, a compound represented by molecule I-3 or a compound represented by molecule I-3' and a base are subjected to a substitution reaction in a solvent to obtain molecule I-5;

[0059] Molecule I-3: The two R" are each independently -C m H 2m+1 , i is each independently an integer from 0 to 10; m is each independently an integer from 0 to 18;

[0060] Molecule I-3': R" is -C m H 2m+1 , i is an integer from 0 to 10, and m is an integer from 0 to 18;

[0061] Molecule I-4: R' is a halogen, preferably a chlorine element;

[0062] Preferably, in step 2),

[0063] The solvent is selected from at least one of tetrahydrofuran and dioxane; and / or,

[0064] The base is selected from at least one of sodium tert-butoxide and potassium tert-butoxide; and / or,

[0065] The catalyst is selected from at least one of 1,1'-bis(diphenylphosphino)ferrocene and 1,1-bis(diphenylphosphino)ferrocene palladium(II) chloride; and / or

[0066] The molar ratio of one of the molecules I-3 or I-3' to the molecule I-4 is 1:(1-2); preferably 1:(1-1.5); and / or,

[0067] The amount of the catalyst is 1% to 20% of the amount of the molecule 1-3; and / or,

[0068] The molar ratio of one of the molecules I-3 or I-3' to the base is 1:(0.5-3), preferably 1:(1-2); and / or,

[0069] The molar volume ratio of one of the molecules I-3 or I-3' to the solvent is 1 mmol:(1 mL to 3 mL), preferably 1 mmol:(1.5 mL to 2 mL); and / or,

[0070] The reaction temperature is 60-100°C and the reaction time is 2-12h;

[0071] 3) Under anhydrous and oxygen-free conditions, the square acid represented by molecule I-6 is reacted with molecule I-5 in a solvent to obtain the final product molecule I;

[0072] Molecule I-5: R is i is each independently an integer of 0-10, m is an integer of 0-18; R' is a halogen;

[0073] Molecule I-6:

[0074] Preferably, in step 3),

[0075] The solvent is toluene and n-butanol, wherein the volume ratio of toluene to n-butanol is 1:(0.5-2); preferably 1:(1-1.5); and / or,

[0076] The molar ratio of molecules I-6 to I-5 in the reaction is 1:(2-2.5), preferably 1:(2-2.3); and / or,

[0077] The molar volume ratio of molecule I-5 to solvent toluene is 1 mmol:(1.5 mL to 3 mL), preferably 1 mmol:(1.5 mL to 2.5 mL); and / or,

[0078] The reaction temperature is 100-140°C, and the reaction time is 8-24h.

[0079] In the method for preparing the temperature-sensitive organic light-emitting molecule of the present invention, preferably,

[0080] The preparation method of the molecule II is:

[0081] 1) Under anhydrous and oxygen-free conditions, in the presence of a catalyst, molecule II-1, molecule II-2 and a base are reacted in a solvent to obtain molecule II-3;

[0082] Molecule II-1:

[0083] Molecule II-2: n is an integer of 0-10, X is hydrogen, halogen, alkoxy, alkyl, or aromatic ring group;

[0084] Preferably, in step 1),

[0085] The solvent is tetrahydrofuran and water; preferably, the volume ratio of water to tetrahydrofuran is 1:(2.5-7); and / or,

[0086] The base is selected from at least one of potassium carbonate and sodium tert-butoxide; and / or,

[0087] The catalyst is selected from at least one of tetrakis(triphenylphosphine)palladium, tris(dibenzylideneacetone)dipalladium, and 1,1-bis(diphenylphosphino)ferrocenepalladium(II) dichloride; and / or,

[0088] The molar ratio of molecule II-2 to the base is 1:(1-3), preferably 1:(1-2); and / or,

[0089] The molar ratio of molecule II-1 to molecule II-2 is 1:(2-5), preferably 1:(2.5-3); and / or,

[0090] The amount of the catalyst is 1% to 20% of the amount of the molecule II-1; and / or,

[0091] The molar volume ratio of molecule II-1 to solvent water is 1 mmol:(2 mL to 5 mL), preferably 1 mmol:(3 mL to 4.5 mL); and / or,

[0092] The reaction temperature is 60-100°C and the reaction time is 6-12h;

[0093] 2) Under anhydrous and oxygen-free conditions, the square acid represented by molecule I-6 is reacted with molecule II-3 to obtain the final product molecule II;

[0094] The structure of molecule II-3 is n is independently an integer of 0-10, and X is independently hydrogen, halogen, alkoxy, alkyl, or aromatic ring group;

[0095] Molecule I-6:

[0096] Preferably, in step 2),

[0097] The solvent is toluene and n-butanol, wherein the volume ratio of toluene to n-butanol is 1:(0.5-2); preferably 1:(1-1.5); and / or,

[0098] The molar ratio of molecule I-6 to molecule II-3 in the reaction is 1:(2-2.5), preferably 1:(2-2.3); and / or,

[0099] The molar volume ratio of molecule II-3 to solvent toluene is 1 mmol:(2 mL to 5 mL), preferably 1 mmol:(3 mL to 5 mL); and / or,

[0100] The reaction temperature is 80-120°C and the reaction time is 10-24h.

[0101] In the method for preparing the temperature-sensitive organic light-emitting molecule of the present invention, preferably,

[0102] The preparation method of the molecule IV comprises:

[0103] 1) Under the condition of anhydrous and oxygen-free conditions, in the presence of a catalyst, molecule IV-1, molecule IV-2 and a base are reacted in a solvent to obtain molecule IV-3;

[0104] Molecule IV-1:

[0105] Molecule IV-2: p is 0-10; Z is hydrogen, halogen, alkoxy, alkyl, or aromatic ring group;

[0106] Preferably, in step 1),

[0107] The solvent is ethanol, water and toluene; the volume ratio of ethanol, water and toluene is 1:1:4 to 1:1:1, preferably 1:1:1.5 to 1:1:2; and / or,

[0108] The base is at least one of cesium carbonate and potassium carbonate; and / or,

[0109] The catalyst is selected from at least one of tetrakis(triphenylphosphine)palladium, 1,1-bis(diphenylphosphino)ferrocenepalladium(II) dichloride, and tris(dibenzylideneacetone)dipalladium; and / or,

[0110] The molar ratio of molecule IV-1 to molecule IV-2 is 1:(2-5), preferably 1:(2.5-3); and / or,

[0111] The amount of the catalyst is 1% to 20% of the amount of the molecule IV-1; and / or,

[0112] The molar volume ratio of molecule IV-1 to solvent water is 1 mmol:(2 mL to 5 mL), preferably 1 mmol:(3 mL to 4 mL); and / or,

[0113] The molar ratio of molecule IV-2 to the base is 1:(1-3), preferably 1:(1-2); and / or,

[0114] The reaction temperature is independently 80-120°C, and the reaction time is 12-24h;

[0115] 2) Under anhydrous and oxygen-free conditions, the square acid represented by molecule I-6 is reacted with molecule IV-3 to obtain the final product molecule IV;

[0116] Molecule IV-3: p is an integer of 0-10; Z is independently hydrogen, halogen, alkoxy, alkyl, or aromatic ring group;

[0117] Molecule I-6:

[0118] Preferably, in step 2),

[0119] The solvent is toluene and n-butanol, wherein the volume ratio of toluene to n-butanol is 1:(0.5-2); preferably 1:(1.1-1:5);

[0120] The molar ratio of molecule I-6 to molecule IV-3 in the reaction is 1:(2 to 2.5), preferably 1:(2 to 2.3);

[0121] The molar volume ratio of molecule IV-3 to solvent toluene is 1 mmol:(2 mL to 5 mL), preferably 1 mmol:(3 mL to 5 mL);

[0122] The reaction temperature is 100-120°C, and the reaction time is 12-24h.

[0123] In the method for preparing the temperature-sensitive organic light-emitting molecule of the present invention, preferably,

[0124] The preparation method of molecule V is:

[0125] When q is not 1, the molecules V-1 and V-2 are reacted under anhydrous and oxygen-free conditions to obtain the molecule V.

[0126] Among them, the molecule V-1 is q is independently an integer from 0 to 10, and q is not 1

[0127] The molecule V-2 is R1 and R1' are each independently aryl or alkyl;

[0128] Preferably,

[0129] The solvent is toluene and n-butanol, wherein the volume ratio of toluene to n-butanol is 1:(0.5-2); preferably 1:(1-1.5); and / or,

[0130] The molar ratio of molecules V-1 to V-2 in the reaction is 1:(1-2), preferably 1:(1.2-1.5); and / or,

[0131] The molar volume ratio of the molecule V-2 to the solvent toluene is 1 mmol:(1.5 mL to 3 mL), preferably 1 mmol:(1.5 mL to 2.5 mL); and / or,

[0132] The reaction temperature is 100-140°C and the reaction time is 8-24h;

[0133] The reaction route is:

[0134] The literature Angew.Chem.Int.Ed.2020,59,10136–10142 reports that when q=1 in the molecule V Preparation method.

[0135] The third object of the present invention is to provide a method for preparing a film doped with a temperature-sensitive organic light-emitting molecule as described in any one of the first objects of the present invention or a temperature-sensitive organic light-emitting molecule as described in any one of the second objects of the present invention, wherein the film is prepared by the following method:

[0136] Method A:

[0137] The temperature-sensitive organic light-emitting molecules are ground and mixed with component A, and then component B is added, mixed evenly, and heated and cured to obtain a fluorescent molecule-doped PDMS film;

[0138] Component A includes polydimethylsiloxane and a platinum catalyst;

[0139] The B component includes a prepolymer polydimethylsiloxane with vinyl side chains and a crosslinker poly(dimethyl-methylhydrogensiloxane);

[0140] In the present invention, component A (purchased from Dow Corning, model SYLGARDA 184, product name PART A, specification 1KG) and component B (purchased from Dow Corning, model SYLGARDA 184, product name PART B, specification 0.1KG) are preferred;

[0141] Preferably,

[0142] The mass ratio of the temperature-sensitive organic light-emitting molecule to component A is 1:(10-100);

[0143] The mass ratio of the temperature-sensitive organic light-emitting molecule to component B is 1:(5-20);

[0144] The temperature of heating and curing is 50-70°C;

[0145] The heating curing time is 3 to 6 hours;

[0146] Method B:

[0147] The temperature-sensitive organic light-emitting molecular alcohol solution and the aqueous solution of polyvinyl alcohol are mixed evenly to obtain a mixed solution, the mixed solution is coated on a substrate, and then dried to obtain a molecular VI-doped PVA film;

[0148] Preferably,

[0149] The solvent in the temperature-sensitive organic luminescent molecule alcohol solution is ethanol;

[0150] The mass ratio of the organic luminescent molecules in the temperature-sensitive organic luminescent molecule alcohol solution to the polyvinyl alcohol in the aqueous solution of polyvinyl alcohol is (0.1-3):100, preferably (0.1-0.5):100;

[0151] The coated substrate is a quartz wafer;

[0152] The drying temperature is 55-70°C;

[0153] The drying time is 3 to 6 hours.

[0154] The fourth object of the present invention is to provide a temperature-sensitive organic light-emitting molecule-doped thin film prepared by the preparation method described in the third object of the present invention.

[0155] The fifth object of the present invention is to provide a thermosensitive organic luminescent molecule as described in any one of the objects of the present invention, a thermosensitive organic luminescent molecule prepared by the method described in any one of the objects of the present invention, or a thin film doped with the thermosensitive organic luminescent molecule as described in the fourth object of the present invention, and use it in temperature sensing and thermal history detection, preferably in thermal history detection of electronic components and photothermal patterning.

[0156] The endpoints and any values ​​of the scope disclosed in the present invention are not limited to the precise scope or value, and these scopes or values ​​should be understood to include values ​​close to these scopes or values. For numerical ranges, the endpoint values ​​of each scope, the endpoint values ​​of each scope and the individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be regarded as specifically disclosed in this article. Hereinafter, in principle, each technical solution can be combined with each other to obtain a new technical solution, which should also be regarded as specifically disclosed in this article.

[0157] Compared with the prior art, the present invention has at least the following advantages:

[0158] The present invention first introduces different modification units into the square acid cyanine molecule as the molecular building core to prepare a series of temperature-responsive organic fluorescent small molecules; due to the flexibility of the molecular conformation and the change of the aggregation state, this series of molecules can produce fluorescence changes in response to different stages of temperature, thereby realizing novel thermal response applications such as thermal history detection of electronic components and photothermal patterning applications.

[0159] We used the rigid environment of the external polymer polyvinyl alcohol as the doping matrix of another multi-conformational fluorene styrene derivative molecule, and utilized the transformation of molecular conformation and the rigidification of multiple hydrogen bonds to obtain an organic light-emitting material that responds to both thermally stimulated phosphorescence and fluorescence, thus realizing the afterglow monitoring of electronic components against the fluorescence background at high temperature. The above invention breaks through the difficulty of solid-state organic light-emitting materials in responding to changes in thermal stimulation, and provides a novel idea and method for constructing thermally responsive solid-state light-emitting materials. BRIEF DESCRIPTION OF THE DRAWINGS

[0160] Figure 1 is the hydrogen spectrum of the final product molecule I-C16 prepared in Example 1;

[0161] Figure 2 is the carbon spectrum of the final product molecule I-C16 prepared in Example 1;

[0162] Figure 3 is a graph showing the relationship between the temperature-dependent spectrum and the fluorescence emission and temperature of the molecule I-C16 in Example 2;

[0163] in, Figure 3 a is the temperature-dependent fluorescence spectrum of I-C16 powder; Figure 3 b is the relationship between the fluorescence emission of I-C16 powder and temperature;

[0164] Figure 4 It is the DSC test curve and photothermal curve of molecule I-C16 in Example 2;

[0165] in, Figure 4 a is the DSC test curve of molecule I-C16 powder; Figure 4 b is the photothermal curve of molecule I-C16 powder;

[0166] Figure 5 It is the photothermal patterning application of the PDMS film doped with molecules I-C16 and I-C14 in Example 3;

[0167] Figure 6 is the hydrogen spectrum of the final product molecule II (n=1) prepared in Example 4;

[0168] Figure 7 is the temperature-variable fluorescence spectrum of molecule II (n=1) in Example 5 and the fluorescence photographs before and after the temperature change;

[0169] Figure 8 is the hydrogen spectrum of molecule III (o=0) in Example 6;

[0170] Fig. 9 is the carbon spectrum of molecule III (o=0) in Example 6;

[0171] Fig.10 is the temperature-dependent fluorescence spectrum of molecule III (o=0) in Example 7 and the relationship between fluorescence emission and temperature;

[0172] in, Fig.10 a is the variable temperature fluorescence spectrum of molecule III (o=0) powder; Fig.10 b is the relationship between the fluorescence emission and temperature of the molecule III (o=0) powder;

[0173] Fig.11 It is a schematic diagram of the operation process and application diagram of the circuit diagnosis of the molecule III (o=0) doped PDMS composite in Example 8;

[0174] in, Fig.11 a is the preparation process of molecule III-doped PDMS film; Fig.11 b is a schematic diagram of diagnostic electronic components;

[0175] Fig.12 is the hydrogen spectrum of the final product molecule IV (p=1) prepared in Example 9;

[0176] Fig.13 is the carbon spectrum of the final product molecule IV (p=1) prepared in Example 9;

[0177] Fig.14 is the temperature-dependent fluorescence spectrum of molecule IV (p=1) doped PDMS in Example 10;

[0178] Fig.15 It is a thermal history detection diagram and infrared thermal imaging diagram of electronic components of the molecule IV (p=1) doped PDMS composite in Example 11;

[0179] in, Fig.15 a is the thermal history fluorescence detection diagram of electronic components of molecule IV (p=1) doped PDMS composite; Fig.15 b is the detection and infrared thermal imaging of molecule IV (p=1) doped PDMS composite;

[0180] Fig.16 is a fluorescent photograph of the ground powder of molecule IV (p=0) in Example 12 before and after heating;

[0181] Fig.17is a fluorescent photograph of the powder of molecule V (q=1) in Example 13 before and after heating;

[0182] Fig.18 The fluorescence and phosphorescence emission diagrams of the molecule VI (r=0) doped with polyvinyl alcohol before and after heating, and the lifetime diagram of the phosphorescence peak in Example 14;

[0183] in, Fig.18 Figure a shows the fluorescence spectra of the VI (r=0)-doped polyvinyl alcohol film before and after heating;

[0184] Fig.18 Figure b shows the steady-state spectrum and delayed spectrum of the VI (r=0) doped polyvinyl alcohol film after heating;

[0185] Fig.18 Figure c shows the lifetime of 554 nm in the delayed spectrum of the heated polyvinyl alcohol film doped with molecule VI (r = 0);

[0186] Fig.18 Figure d shows the lifetime at 600 nm in the delayed spectrum of the heated polyvinyl alcohol film doped with molecule VI (r = 0);

[0187] Fig.19 The thermal history fluorescence detection, infrared thermal imaging and phosphorescence detection images of the circuit board doped with polyvinyl alcohol by molecule VI (r=0) in Example 15;

[0188] in, Fig.19 a is the thermal history fluorescence detection diagram of electronic components doped with polyvinyl alcohol by molecule VI (r=0);

[0189] Fig.19 b is an infrared thermal image of the thermal history detection of electronic components doped with polyvinyl alcohol with molecule VI (r=0);

[0190] Fig.19 c is a thermal history phosphorescence detection diagram of the thermal history of electronic components doped with polyvinyl alcohol by molecule VI (r=0);

[0191] Fig. 20 is the hydrogen spectrum of molecule VI (r=3) in Example 16;

[0192] Fig.21 These are the fluorescence and afterglow photographs of the polyvinyl alcohol film doped with molecule VI (r=3) in Example 17 before and after heating. DETAILED DESCRIPTION

[0193] The present invention is described in detail below in conjunction with specific drawings and embodiments. It is necessary to point out that the following embodiments are only used to further illustrate the present invention and cannot be understood as limiting the scope of protection of the present invention. Some non-essential improvements and adjustments made to the present invention by those skilled in the art based on the content of the present invention still fall within the scope of protection of the present invention.

[0194] It should also be noted that the various specific technical features described in the following specific embodiments can be combined in any suitable manner without contradiction. To avoid unnecessary repetition, the present invention will not further describe various possible combinations.

[0195] In addition, the various embodiments of the present invention may be arbitrarily combined as long as they do not violate the concept of the present invention. The technical solutions thus formed belong to part of the original disclosure of this specification and also fall within the protection scope of the present invention.

[0196] The raw materials used in the examples and comparative examples, unless otherwise specified, are disclosed in the prior art, for example, they can be directly purchased or prepared according to the preparation methods disclosed in the prior art.

[0197] The following examples are a series of preparation methods and application examples of thermal stimulus responsive organic light-emitting molecules of the present invention.

[0198] Example 1

[0199] The method for preparing molecule I, taking i=0, m=16, i.e. molecule I-C16 as an example, the preparation steps are as follows:

[0200] Preparation of I-3-C16:

[0201] In a 100mL two-necked flask, under the protection of nitrogen, add p-iodophenol (1.76g, 8.0mmol), potassium carbonate (2.21g, 15.99mmol), then add acetonitrile (20mL) and hexadecane bromide (4.9mL, 16.09mmol). Gradually heat to 80°C and stir to react for 12h. After the reaction is completed, filter out the potassium carbonate in the system while hot, separate the filtrate by rotary evaporator, extract the crude product with dichloromethane and saturated brine, and purify it by silica gel column chromatography with pure petroleum ether as eluent to obtain molecule I-3-C16;

[0202] Preparation of I-5-C16:

[0203] In a 100mL two-necked bottle, under the protection of nitrogen, add molecule I-3-C16 (3.55g, 7.99mmol), p-chloroaniline (1.11g, 8.73mmol), 1,1'-bis(diphenylphosphino)ferrocene (536.4mg, 0.98mmol), 1,1-bis(diphenylphosphino)ferrocene dichloropalladium (II) (268.4mg, 0.37mmol), sodium tert-butoxide (770mg, 8.01mmol), and add 15mL tetrahydrofuran, gradually heat to 100℃, and stir to react for 3h. After the reaction is completed, cool to room temperature, add a solution of 10 times diluted concentrated hydrochloric acid under stirring to adjust the reaction solution to pH = 1, and then add a saturated sodium bicarbonate solution to adjust the reaction solution to pH = 9; extract with ethyl acetate, purify by silica gel column chromatography, and use petroleum ether / ethyl acetate (volume ratio of 100:1) as eluent to obtain a white solid powder;

[0204] Preparation of I-C16:

[0205] In a 50mL two-necked bottle, under the protection of nitrogen, add molecule I-6 square acid (114.97mg, 1.01mmol) and molecule I-5-C16 (938.8mg, 2.12mmol), and add 5mL toluene and 5mL n-butanol. Gradually heat to 120°C and stir the reaction for 12h. After the reaction is completed, the reaction solvent is separated by rotary evaporator, and the crude product is extracted with dichloromethane and saturated brine. Silica gel column chromatography is used to purify the eluent with petroleum ether / ethyl acetate (100:1) gradually increasing the polarity to petroleum ether / ethyl acetate (20:1). Finally, further recrystallization is carried out in a mixed solvent of dichloromethane / n-hexane to obtain an orange-red powder. The hydrogen spectrum is as follows Figure 1 As shown, the carbon spectrum is Figure 2 shown.

[0206] The above reaction process is as follows:

[0207]

[0208] Preparation of molecule I-C14: When i=0, m=14, the preparation path and conditions of molecule I-C14 are the same as those of molecule I-C16. 16 H 33 Replace with Br-C 14 H 29 That's it.

[0209] Example 2

[0210] Temperature stimulus response of molecule I-C16

[0211] The fluorescence spectrophotometer was used to test the change of the emission spectrum of I-C16 orange-red powder with temperature. Figure 3 As shown, the temperature was increased from 298K to 348K, and data was collected every 10K for 10 minutes. When the temperature increased from 298K to 348K, the fluorescence emission of the orange-red powder remained unchanged, and the emission peak was stabilized at around 593nm. When the temperature was increased to 358K, the emission peak of the orange-red powder blue-shifted to 535nm, and the emission peak remained unchanged when the temperature was further increased to 490K, stabilizing at around 535nm. After testing, the long alkyl chain has a good photothermal effect at 405nm laser, 400mW / cm 2 Under the irradiation of , the photothermal effect can be used to reach the phase transition temperature of 85℃, realizing the process of light-heat-phase transition. Figure 4 .

[0212] Example 3

[0213] Photothermal patterning applications of molecules I-C16 and I-C14

[0214] Accurately weigh the molecule I-C16 into three portions (5 mg, 12.5 mg, 25 mg), and accurately weigh the orange-red powder of I-C14 into three portions (5 mg, 12.5 mg, 25 mg); each portion is first mixed with PDMS component A (250 mg) (purchased from Dow Corning, model SYLGARDA 184, product name PART A, specification 1 KG), and then add curing agent component B (25 mg) (purchased from Dow Corning, model SYLGARDA 184, product name PART B, specification is 0.1KG), after being fully stirred, it is placed in an oven and heated and cured at 60°C for 4 hours to obtain I-C16-doped PDMS films with a mass ratio of component A: component B: I-C16 of 100:10:2, 100:10:5, and 100:10:10; and I-C14-doped PDMS films with a mass ratio of component A: component B: I-C14 of 100:10:2, 100:10:5, and 100:10:10.

[0215] Place the 405nm laser, mask, I-C16-doped PDMS membrane or I-C14-doped PDMS membrane from top to bottom and adjust the laser power to 700mW / cm 2 Irradiation, exposure to laser can use the photothermal effect to reach a phase transition temperature of 85°C, achieving a transition from orange-red fluorescence to yellow-green fluorescence, and realizing photothermal patterning applications such as Figure 5 As shown (the pattern color in the figure is yellow-green).

[0216] Example 4

[0217] The method for preparing molecule II-3 (n=1) comprises the following steps:

[0218] Under nitrogen atmosphere, a 100 mL two-necked bottle was selected, and molecule II-1 (986 mg, 3.02 mmol), molecule II-2 (1.75 g, 9.02 mmol), catalyst tetrakis(triphenylphosphine)palladium (523 mg, 0.45 mmol), potassium carbonate (2.53 g, 18.31 mmol) were added respectively, and then redistilled tetrahydrofuran (25 mL) and water (9 mL) were measured with a syringe and injected into the two-necked bottle, stirring and heating were started, and the temperature was gradually raised to 80° C. and reacted for 8 hours. After the reaction was completed, the reaction solvent was separated by a vacuum rotary evaporator, extracted with ethyl acetate and saturated brine, and purified by silica gel column chromatography with ethyl acetate and petroleum ether (volume ratio of 1:10) as eluents to obtain molecule II-3.

[0219] The method for preparing molecule II (n=1) comprises the following steps:

[0220] In a 50mL two-necked bottle, under the protection of nitrogen, add molecule I-6 square acid molecule (59.66mg, 0.52mmol) and molecule II-3 (487.3mg, 1.05mmol), and add 5mL toluene and 5mL n-butanol. Gradually heat to 120℃ and stir to react for 12h. The solid precipitated and was recrystallized and purified with dichloromethane and petroleum ether to obtain the product. The H NMR spectrum is as follows: Figure 6 shown.

[0221] The above reaction process is as follows:

[0222]

[0223] Example 5

[0224] Temperature stimulus response of molecule II (n=1)

[0225] Grind the powder thoroughly with a mortar to obtain a powder of molecule II (n=1) emitting orange fluorescence, such as Figure 7 As shown, the fluorescence blue shifted from orange to yellow-green after heat treatment at 130°C. The fluorescence spectrophotometer was used to test the change of the powder fluorescence of the molecule II after grinding with temperature. The temperature was increased from 294K to 454K, and the temperature was stabilized for 180s every 10K. The spectral data was collected. The fluorescence peak gradually blue shifted. The temperature-varying spectrum is shown in Figure 7 shown.

[0226] Example 6

[0227] The method for preparing molecule III (o=0) comprises the following steps:

[0228] In a 100mL two-necked flask, under nitrogen protection, add molecule III-1 (0.74g, 1.01mmol), cuprous iodide (0.20g, 1.05mmol), tetrakis(triphenylphosphine)palladium (0.47g, 0.41mmol) and molecule III-2 phenylacetylene (0.84g, 8.24mmol), and add 20mL toluene and 20mL triethylamine. Gradually heat to 100°C and stir the reaction for 48h. After the reaction, the reaction solvent was separated by a rotary evaporator, and the crude product was extracted with dichloromethane and purified by silica gel column chromatography with petroleum ether / dichloromethane (volume ratio of 1:3) as the eluent. Finally, further recrystallization was performed in a dichloromethane / petroleum ether mixed solution to obtain an orange-red powder. The hydrogen nuclear magnetic resonance spectrum is as follows Figure 8 As shown, the carbon spectrum is Fig. 9 shown.

[0229] The above reaction process is as follows:

[0230]

[0231] Example 7

[0232] Temperature stimulus response of molecule III (o=0)

[0233] Fluorescence spectrophotometer was used to test the change of the emission spectrum of the orange-red powder of molecule III with temperature. Fig.10 As shown in the figure, the temperature was increased from 290K to 490K, and the data were collected for stabilization time of 2, 4, 6, 8, and 10 minutes every 10K. Among them, the fluorescence emission of the orange-red powder remained unchanged when the temperature was increased from 290K to 410K, and the emission peak was stabilized at around 605nm. When the temperature was increased to 436K, the emission peak of the orange-red powder blue-shifted to 570nm, and the emission peak remained unchanged and stabilized at around 570nm when the temperature was further increased to 490K.

[0234] Example 8

[0235] Fluorescence line diagnosis of molecule III (o=0)

[0236] Accurately weigh 3 mg of molecular III orange-red powder, first mix it with component A (300 mg) (purchased from Dow Corning, model SYLGARDA 184, product name PART A, specification 1 KG), then add curing agent component B (30 mg) (purchased from Dow Corning, model SYLGARDA 184, product name PART B, specification 0.1 KG), and stir evenly. Finally, apply it on the electronic components of the circuit board and heat it at 60 degrees Celsius for 4 hours.

[0237] Compared with the prior art, the present invention is the first to use fluorescent organic small molecules with tunable solid-state emission properties for circuit diagnosis. Fig.11 As shown in the figure, when the circuit is normal, the electronic components coated with PDMS composite on the circuit board all emit orange-yellow light. When the load voltage exceeds the rated voltage, a chip is broken down and a short circuit occurs. The temperature of the short circuit part rises rapidly to 180°C, and the fluorescence emission of the PDMS composite changes from orange-yellow to green. Thus, the change of the fluorescence emission color can quickly and accurately identify the faulty electronic components.

[0238] Example 9

[0239] The method for preparing molecule IV (p=1) comprises the following steps:

[0240] Preparation method of molecule IV-3;

[0241] Under nitrogen atmosphere, weigh molecule IV-1 (668.4 mg, 2.04 mmol), molecule IV-2 (956.8 mg, 6.12 mmol), cesium carbonate (1.99 g, 6.11 mmol), tetrakis(triphenylphosphine)palladium (447.4 mg, 0.39 mmol) and add them to the reaction device, use a syringe to measure ethanol (8 mL), water (8 mL), and toluene (12 mL), inject them into the reaction device, start stirring and heating, gradually heat to 100 ° C, and react for 12 hours. The reaction solvent is separated by a vacuum rotary evaporator, purified by silica gel column chromatography, and gradually purified by gradient purification with petroleum ether and ethyl acetate (volume ratio 9:1 to 7:1) as eluents to obtain molecule IV-3.

[0242] Preparation method of molecule IV (p=1):

[0243] Under nitrogen atmosphere, weigh molecule IV-3 (309 mg, 0.79 mmol) and molecule I-6 (45 mg, 0.39 mmol) and add them to the reaction device, and add 3 mL of toluene and 3 mL of n-butanol. Gradually heat to 120 ° C and stir to react for 12 hours. After the reaction is completed, the reaction solvent is separated by rotary evaporator and purified by silica gel column chromatography with dichloromethane as eluent to obtain the final product molecule IV. The nuclear magnetic resonance hydrogen spectrum is as follows Fig.12 As shown, the carbon spectrum is Fig.13 shown.

[0244] The above reaction process is as follows:

[0245]

[0246] Example 10

[0247] Temperature stimulus response of molecule IV (p=1)

[0248] Accurately weigh the ground molecule IV powder (3.59 mg), first mix it with the A component of PDMS (352 mg) (purchased from Dow Corning, model SYLGARDA 184, product name PART A, specification 1 KG), and then add the curing agent B component (35.1 mg) (purchased from Dow Corning, model SYLGARDA 184, product name PART B, specification 0.1 KG). After fully stirring, place it in an oven at 60°C for heating and curing for 4 hours to obtain a molecule IV-doped PDMS film.

[0249] Fluorescence spectrophotometer was used to test the change of fluorescence of molecular IV-doped PDMS film with temperature. The temperature was increased from 298K to 498K. The spectrum was collected every 10K after stabilization. The spectral data was collected. The fluorescence peak gradually blue-shifted, such as Fig.14 .

[0250] Embodiment 11:

[0251] Temperature stimulus response of molecule IV (p=1)

[0252] Accurately weigh 3.59 mg of molecular IV orange-red powder, first mix it with component A (352 mg) (purchased from Dow Corning, model SYLGARDA 184, product name PART A, specification 1 KG), then add curing agent component B (35.1 mg) (purchased from Dow Corning, model SYLGARDA 184, product name PART B, specification 0.1 KG), and stir evenly. Finally, apply it on the electronic components of the circuit board and cure it at room temperature for 1 day. When the circuit is normal, the electronic components on the circuit board coated with PDMS composites all emit orange-yellow. When the load voltage exceeds the rated voltage, the temperature of the short-circuit part rises rapidly, causing the fluorescence emission of the PDMS composite to change from orange-yellow to yellow-green. Fig.15 .

[0253] Example 12

[0254] Temperature stimulus response of molecule IV (p=0):

[0255] The preparation method thereof refers to the open document J.Am.Chem.Soc.2021,143,3856-3864.

[0256] After grinding molecule IV (p = 0), the fluorescence changes from yellow to green under heat treatment at 300 °C, as shown in Fig.16 .

[0257] Example 13

[0258] The temperature stimulus response of the molecule V(q=1):

[0259] The preparation method thereof refers to the public document Angew.Chem.Int.Ed.2020,59,10136–10142.

[0260] When molecule V is heated at 250°C, its fluorescence changes from red to yellow, as shown in Fig.17 .

[0261] Embodiment 14

[0262] Temperature stimulus response of molecule VI (r = 0)

[0263] The preparation method thereof refers to the public document Adv. Funct. Mater. 2012, 22, 4862-4872.

[0264] Temperature stimulus response of VI (r=0) doped PVA:

[0265] Weigh 1.09 mg of molecule VI (r = 0) at a time and dissolve it in 1820 μL of ethanol solution. Weigh 100 mg of PVA powder with a hydrolysis degree of 90% and ultrasonically heat it to 80°C to dissolve it in 1 mL of Wahaha water. Then use a pipette to take 500 μL of molecule VI (r = 0) ethanol solution and evenly disperse it into the above PVA aqueous solution. Then use a pipette to take about 50 μL and drop it on a thin quartz disc. Place it in an oven and bake it at 65°C for about 4 hours. Then take out the quartz disc and heat it at 95°C on a hot stage for 5 hours until the fluorescence turns blue. Use the FLS1000 instrument with an excitation wavelength of 375nm to test the steady-state and delayed spectra of the heated quartz disc, and use a xenon lamp light source to test the kinetic lifetime of phosphorescence. The heated quartz disc shows long-life phosphorescence peaks at 554nm and 600nm, with lifetimes of 1057.63ms and 1001.86ms, respectively. Fig.18 .

[0266] Embodiment 15

[0267] Molecular VI (r = 0) circuit board high temperature anti-fluorescence background afterglow detection

[0268] Take 100 μL of the PVA solution of molecule VI (r=0) prepared as described above with a pipette and apply it on the circuit board. After the circuit board is powered on and heated, the fluorescence at the high temperature of 100°C changes from yellow to blue. After turning off the flashlight, a yellow afterglow appears. Fig.19 .

[0269] Example 16

[0270] Preparation of molecule VI (r = 3):

[0271] Under anhydrous and oxygen-free conditions, weigh the molecule VI-1 triethylene glycol mono-p-toluenesulfonate molecule (270 mg, 0.89 mol) and the molecule VI (r = 1) (100.3 mg, 0.28 mmol), potassium carbonate (86.4 mg, 0.63 mmol) to react, add 15 mL DMF, the reaction temperature is raised to 90 ° C, the reaction time is 15 h, after stopping the reaction, spin dry the solvent DMF, use dichloromethane and salt water to extract. Purify with ethyl acetate and petroleum ether (volume ratio of 2: 1) to obtain a yellow oily product molecule VI (r = 3). H NMR spectrum is shown in Fig. 20 .

[0272] The above reaction process is as follows:

[0273]

[0274] Embodiment 17

[0275] Temperature stimulus response of molecule VI (r=3)

[0276] The preparation method of the PVA film of molecule VI is the same as that of Example 13. After heating, the fluorescence changes from yellow to blue, and a yellow afterglow appears. Fig.21 .

[0277] The present invention has been described in detail above in conjunction with specific implementations and exemplary examples, but these descriptions cannot be understood as limiting the present invention. Those skilled in the art understand that, without departing from the spirit and scope of the present invention, a variety of equivalent substitutions, modifications or improvements may be made to the technical solution of the present invention and its implementation methods, all of which fall within the scope of the present invention. The scope of protection of the present invention shall be subject to the attached claims.

[0278] All publications, patent applications, patents and other references mentioned in this specification are incorporated herein by reference. Unless otherwise defined, all technical and scientific terms used in this specification have the meanings conventionally understood by those skilled in the art. In the event of a conflict, the definition in this specification shall prevail.

[0279] When this specification uses the prefix "well-known to those skilled in the art", "prior art" or similar terms to introduce materials, substances, methods, steps, devices or components, etc., the objects introduced by the prefix cover those commonly used in the art when this application is filed, but also include those that are not commonly used at present but will become recognized in the art as being suitable for similar purposes.

[0280] In the context of the present specification, any matters or items not mentioned are directly applicable to those known in the art without any changes except those explicitly stated.

Claims

1. A temperature-sensitive organic light-emitting molecule, characterized in that: The organic light-emitting molecule has the following general structural formula: The two Rs are independent of each other: i is each independently an integer from 0 to 10, and m is each independently an integer from 1 to 18; n is an integer of 0-10, X is hydrogen or halogen; o is an integer from 0 to 10, and Y is hydrogen or halogen; p is an integer of 1-10, Z is hydrogen or halogen; Two R's are independently: halogen; n is an integer of 0-10, X is hydrogen or halogen; o is an integer from 0 to 10, and Y is hydrogen or halogen; p is an integer of 0-10, and Z is hydrogen or halogen; Alternatively, the organic light-emitting molecule has the following general structural formula: Wherein R2 is independently r is an integer from 3 to 20.

2. The temperature-sensitive organic light-emitting molecule according to claim 1, characterized in that: The organic light-emitting molecule has one of the following molecular structural formulas I to IV: Molecule I: The two Rs are independent of each other. i is each independently an integer of 0-10, m is each independently an integer of 1-18; two R's are each independently halogen; Molecule II: wherein n is independently an integer of 0 to 10; X is independently hydrogen or halogen; Molecule III: Wherein o is an integer of 0-10; Y is hydrogen or halogen; Molecule IV: Wherein p is an integer of 1-10, and Z is hydrogen or halogen.

3. The temperature-sensitive organic light-emitting molecule according to claim 2, characterized in that: Both R' are -Cl.

4. A method for preparing a temperature-sensitive organic light-emitting molecule as claimed in claim 1, characterized in that: The preparation of the organic light-emitting molecule is selected from the following methods: Method 1: Under anhydrous and oxygen-free conditions, the square acid molecules and reacting in a solvent to obtain the organic light-emitting molecule; Among them, the square acid is: The R in is: i is each independently an integer from 0 to 10, and m is each independently an integer from 1 to 18; n is an integer of 0-10, X is hydrogen or halogen; p is an integer of 1-10, Z is hydrogen or halogen; R' is a halogen, n is an integer of 0-10, X is hydrogen or halogen; p is an integer of 1-10, Z is hydrogen or halogen; Method 2: Under the condition of anhydrous and oxygen-free conditions, in the presence of a catalyst, the molecule III-1, the molecule III-2 and a base are subjected to a substitution reaction in a solvent to obtain the organic light-emitting molecule; Among them, molecule III-1: Molecule III-2: o is an integer from 0 to 10, and Y is hydrogen or halogen; Method 3: Under the condition of anhydrous and oxygen-free conditions, molecule VI, molecule VI-1 and a base are reacted in a solvent to obtain the organic light-emitting molecule; Among them, molecule VI: Molecule VI-1: r is an integer from 3 to 20.

5. The method for preparing a temperature-sensitive organic light-emitting molecule according to claim 4, characterized in that: In method 2, The solvent is at least one of toluene, N,N-dimethylformamide, and tetrahydrofuran; and / or, The catalyst is selected from at least one of tetrakis(triphenylphosphine)palladium and cuprous iodide; and / or, An organic base is used for the reaction; and / or, The molar ratio of molecule III-1 to molecule III-2 is 1:(1-10); and / or, The molar volume ratio of molecule III-1 and the organic base is 1 mmol:(10 mL to 30 mL); and / or, The amount of the catalyst is 20% to 180% of the amount of the molecule III-1; and / or, The molar volume ratio of molecule III-1 to the solvent is 1 mmol:(10 mL to 25 mL); and / or, The reaction temperature is 80-100°C and the reaction time is 48-72h; In method three, The solvent is selected from at least one of N,N-dimethylformamide, dimethyl sulfoxide and methanol; The base comprises at least one selected from potassium carbonate, sodium hydroxide, and sodium tert-butoxide; The molar ratio of molecule VI to molecule VI-1 is 1:(2-5); The molar ratio of molecule VI to base is 1:(2-10); The molar volume ratio of molecule VI and solvent is 1mmol:(10mL~55mL); The reaction temperature is raised to 80-100°C and the reaction time is 12-24h.

6. The method for preparing a temperature-sensitive organic light-emitting molecule according to claim 5, characterized in that: The organic base selected for the reaction is at least one of triethylamine and piperidine.

7. The method for preparing a temperature-sensitive organic light-emitting molecule according to claim 5, characterized in that: In method 2, The molar ratio of molecule III-1 to molecule III-2 is 1:(6-8); and / or, The molar volume ratio of molecule III-1 and the organic base is 1 mmol:(15 mL to 20 mL); and / or, The amount of the catalyst is 20% to 180% of the amount of the molecule III-1; tetrakis(triphenylphosphine)palladium and cuprous iodide are both added to the reaction system as catalysts; and / or, The molar volume ratio of molecule III-1 to the solvent is 1 mmol:(15 mL to 20 mL); and / or, In method three, The molar ratio of molecule VI to molecule VI-1 is 1:(2.5-3); The molar ratio of molecule VI to base is 1:(2-5); The molar volume ratio of molecule VI and solvent is 1 mmol:(30 mL to 50 mL).

8. The method for preparing a temperature-sensitive organic light-emitting molecule according to claim 7, characterized in that: The amount of the catalyst used is 20% to 180% of the amount of the substance of molecule III-1; tetrakis(triphenylphosphine)palladium and cuprous iodide are both added to the reaction system as catalysts, cuprous iodide is 80% to 120% of the amount of the substance of molecule III-1; tetrakis(triphenylphosphine)palladium is 40% to 60% of the amount of the substance of molecule III-1.

9. The method for preparing a temperature-sensitive organic light-emitting molecule according to claim 8, characterized in that: The amount of cuprous iodide is 80% to 110% of the amount of the substance of molecule III-1; the amount of tetrakis(triphenylphosphine)palladium is 40% to 50% of the amount of the substance of molecule III-1.

10. A method for preparing a temperature-sensitive organic light-emitting molecule as claimed in claim 2, characterized in that: The preparation method of the molecule I is as follows: 1) Optionally, under anhydrous and oxygen-free conditions, the molecule I-1 and the compound represented by the molecule I-2 and a base are subjected to a substitution reaction in a solvent to obtain a molecule I-3; Molecule I-1: i is an integer from 0 to 10 independently; Molecule I-2: Br-R", R" = -C m H 2m+1 , m is an integer from 1 to 18; 2) Under anhydrous and oxygen-free conditions, in the presence of a catalyst, a compound represented by molecule I-4, a compound represented by molecule I-3 or a compound represented by molecule I-3' and a base are subjected to a substitution reaction in a solvent to obtain molecule I-5; Molecule I-3: The two R's are each independently -C m H 2m+1 , i is each independently an integer from 0 to 10; m is each independently an integer from 1 to 18; Molecule I-3': R" is -C m H 2m+1 , i is an integer from 0 to 10, and m is an integer from 1 to 18; Molecule I-4: R' is halogen; 3) Under anhydrous and oxygen-free conditions, the square acid represented by molecule I-6 is reacted with molecule I-5 in a solvent to obtain the final product molecule I; Molecule I-5: R is i is each independently an integer of 0-10, m is an integer of 1-18; R' is a halogen; Molecule I-6:

11. The method for preparing a temperature-sensitive organic light-emitting molecule according to claim 10, characterized in that: In step 1), The solvent is selected from at least one of acetonitrile, methanol and acetone; and / or, The base is selected from at least one of potassium carbonate, sodium hydroxide and sodium tert-butoxide; and / or, The molar ratio of molecule I-1 to molecule I-2 is 1:(1-4); and / or, The molar ratio of molecule I-1 to base is 1:(1-4); and / or, The molar volume ratio of molecule I-1 to solvent is 1 mmol:(2.5 mL to 5 mL); and / or, The reaction temperature is 60-100°C and the reaction time is 8-24h; In step 2), The solvent is selected from at least one of tetrahydrofuran and dioxane; and / or, The base is selected from at least one of sodium tert-butoxide and potassium tert-butoxide; and / or, The catalyst is selected from at least one of 1,1'-bis(diphenylphosphino)ferrocene and 1,1-bis(diphenylphosphino)ferrocene palladium(II) chloride; and / or The molar ratio of one of the molecules I-3 or I-3' to the molecule I-4 is 1:(1-2); and / or, The amount of the catalyst is 1% to 20% of the amount of the molecule 1-3; and / or, The molar ratio of one of the molecules I-3 or I-3' to the base is 1:(0.5-3); and / or, The molar volume ratio of one of the molecules I-3 or I-3' to the solvent is 1 mmol:(1 mL to 3 mL); and / or, The reaction temperature is 60-100°C and the reaction time is 2-12h; In step 3), The solvent is toluene and n-butanol, wherein the volume ratio of toluene to n-butanol is 1:(0.5-2); and / or, The molar ratio of molecules I-6 to I-5 in the reaction is 1:(2 to 2.5); and / or, The molar volume ratio of molecule I-5 to solvent toluene is 1 mmol:(1.5 mL to 3 mL); and / or, The reaction temperature is 100-140°C, and the reaction time is 8-24h.

12. The method for preparing a temperature-sensitive organic light-emitting molecule according to claim 11, characterized in that: In step 1), The molar ratio of molecule I-1 to molecule I-2 is 1:(1-2); and / or, The molar ratio of molecule I-1 to base is 1:(1-2); and / or, The molar volume ratio of molecule I-1 to solvent is 1mmol:(3mL~4mL); In step 2), The molar ratio of one of the molecules I-3 or I-3' to the molecule I-4 is 1:(1 to 1.5); and / or, The molar ratio of one of the molecules I-3 or I-3' to the base is 1:(1-2); and / or, The molar volume ratio of one of the molecules I-3 or I-3' to the solvent is 1 mmol:(1.5 mL to 2 mL); In step 3), The solvent is toluene and n-butanol, wherein the volume ratio of toluene to n-butanol is 1:(1-1.5); and / or, The molar ratio of molecules I-6 to I-5 in the reaction is 1:(2-2.3); and / or, The molar volume ratio of molecule I-5 to solvent toluene is 1 mmol:(1.5 mL to 2.5 mL).

13. A method for preparing a temperature-sensitive organic light-emitting molecule as claimed in claim 2, characterized in that: The preparation method of the molecule II is: 1) Under anhydrous and oxygen-free conditions, in the presence of a catalyst, molecule II-1, molecule II-2 and a base are reacted in a solvent to obtain molecule II-3; Molecule II-1: Molecule II-2: n is an integer of 0-10, X is hydrogen or halogen; 2) Under anhydrous and oxygen-free conditions, the square acid represented by molecule I-6 is reacted with molecule II-3 to obtain the final product molecule II; The structure of molecule II-3 is n is each independently an integer of 0-10, and X is each independently hydrogen or halogen; Molecule I-6:

14. The method for preparing a temperature-sensitive organic light-emitting molecule according to claim 13, characterized in that: In step 1), The solvent is tetrahydrofuran and water; and / or, The base is selected from at least one of potassium carbonate and sodium tert-butoxide; and / or, The catalyst is selected from at least one of tetrakis(triphenylphosphine)palladium, tris(dibenzylideneacetone)dipalladium, and 1,1-bis(diphenylphosphino)ferrocenepalladium(II) dichloride; and / or, The molar ratio of molecule II-2 to base is 1:(1-3); and / or, The molar ratio of molecule II-1 to molecule II-2 is 1:(2-5); and / or, The amount of the catalyst is 1% to 20% of the amount of the molecule II-1; and / or, The molar volume ratio of molecule II-1 to solvent water is 1mmol:(2mL~5mL); and / or, The reaction temperature is 60-100°C and the reaction time is 6-12h; In step 2), The solvent is toluene and n-butanol, wherein the volume ratio of toluene to n-butanol is 1:(0.5-2); and / or, The molar ratio of molecule I-6 to molecule II-3 in the reaction is 1:(2-2.5); and / or, The molar volume ratio of molecule II-3 to solvent toluene is 1 mmol:(2 mL to 5 mL); and / or, The reaction temperature is 80-120°C and the reaction time is 10-24h.

15. The method for preparing a temperature-sensitive organic light-emitting molecule according to claim 14, characterized in that: In step 1), The volume ratio of water to tetrahydrofuran is 1:(2.5-7); and / or, The molar ratio of molecule II-2 to base is 1:(1-2); and / or, The molar ratio of molecule II-1 to molecule II-2 is 1:(2.5-3); and / or, The molar volume ratio of molecule II-1 to solvent water is 1mmol:(3mL~4.5mL); In step 2), The volume ratio of toluene to n-butanol is 1:(1-1.5); and / or, The molar ratio of molecule I-6 to molecule II-3 in the reaction is 1:(2-2.3); and / or, The molar volume ratio of molecule II-3 to solvent toluene is 1 mmol:(3 mL to 5 mL).

16. A method for preparing a temperature-sensitive organic light-emitting molecule as claimed in claim 2, characterized in that: The preparation method of the molecule IV comprises: 1) Under the condition of anhydrous and oxygen-free conditions, in the presence of a catalyst, molecule IV-1, molecule IV-2 and a base are reacted in a solvent to obtain molecule IV-3; Molecule IV-1: Molecule IV-2: p is 1-10; Z is hydrogen or halogen; 2) Under anhydrous and oxygen-free conditions, the square acid represented by molecule I-6 is reacted with molecule IV-3 to obtain the final product molecule IV; Molecule IV-3: p is an integer of 1-10; Z is independently hydrogen or halogen; Molecule I-6:

17. The method for preparing a temperature-sensitive organic light-emitting molecule according to claim 16, characterized in that: In step 1), The solvent is ethanol, water and toluene; the volume ratio of ethanol, water and toluene is 1:1:4 to 1:1:1; and / or, The base is at least one of cesium carbonate and potassium carbonate; and / or, The catalyst is selected from at least one of tetrakis(triphenylphosphine)palladium, 1,1-bis(diphenylphosphino)ferrocenepalladium(II) dichloride, and tris(dibenzylideneacetone)dipalladium; and / or, The molar ratio of molecule IV-1 to molecule IV-2 is 1:(2-5); and / or, The amount of the catalyst is 1% to 20% of the amount of the molecule IV-1; and / or, The molar volume ratio of molecule IV-1 to solvent water is 1mmol:(2mL~5mL); and / or, The molar ratio of molecule IV-2 to base is 1:(1-3); and / or, The reaction temperature is 80-120°C and the reaction time is 12-24h; In step 2), The solvent is toluene and n-butanol, wherein the volume ratio of toluene to n-butanol is 1:(0.5-2); The molar ratio of molecule I-6 to molecule IV-3 in the reaction is 1:(2 to 2.5); The molar volume ratio of molecule IV-3 to solvent toluene is 1mmol:(2mL~5mL); The reaction temperature is 100-120°C, and the reaction time is 12-24h.

18. The method for preparing a temperature-sensitive organic light-emitting molecule according to claim 17, characterized in that: In step 1), The volume ratio of ethanol, water and toluene is 1:1:1.5 to 1:1:2; and / or, The molar ratio of molecule IV-1 to molecule IV-2 is 1:(2.5-3); and / or, The molar volume ratio of molecule IV-1 to solvent water is 1mmol:(3mL~4mL); and / or, The molar ratio of molecule IV-2 and base is 1:(1-2); In step 2), The solvent is toluene and n-butanol, wherein the volume ratio of toluene to n-butanol is 1:(1.1-1:5); The molar ratio of molecule I-6 to molecule IV-3 in the reaction is 1:(2-2.3); The molar volume ratio of molecule IV-3 to solvent toluene is 1 mmol:(3 mL to 5 mL).

19. A method for preparing a temperature-sensitive organic light-emitting molecule-doped thin film, characterized in that: The film is prepared by the following method: Method A: The temperature-sensitive organic light-emitting molecules are ground and mixed with component A, and then component B is added, mixed evenly, and heated and cured to obtain a temperature-sensitive organic light-emitting molecule-doped PDMS film; Component A includes polydimethylsiloxane and a platinum catalyst; The B component includes a prepolymer polydimethylsiloxane with vinyl side chains and a crosslinker poly(dimethyl-methylhydrogensiloxane); Method B: The temperature-sensitive organic light-emitting molecule alcohol solution and the polyvinyl alcohol aqueous solution are uniformly mixed to obtain a mixed solution, the mixed solution is coated on a substrate, and then dried to obtain a temperature-sensitive organic light-emitting molecule doped PVA film; The temperature-sensitive organic light-emitting molecule is the temperature-sensitive organic light-emitting molecule according to any one of claims 1 to 3 or or 20. The method for preparing a temperature-sensitive organic light-emitting molecule-doped thin film according to claim 19, characterized in that: Method A: The mass ratio of the temperature-sensitive organic light-emitting molecule to component A is 1:(10-100); The mass ratio of the temperature-sensitive organic light-emitting molecule to component B is 1:(5-20); The temperature of heating and curing is 50-70°C; The heating curing time is 3 to 6 hours; Method B: The solvent in the temperature-sensitive organic luminescent molecule alcohol solution is ethanol; The mass ratio of the organic luminescent molecules in the temperature-sensitive organic luminescent molecule alcohol solution to the polyvinyl alcohol in the aqueous solution of polyvinyl alcohol is (0.1-3):100; The coated substrate is a quartz wafer; The drying temperature is 55-70°C; The drying time is 3 to 6 hours.

21. A thin film doped with temperature-sensitive organic light-emitting molecules prepared according to the preparation method according to any one of claims 19 to 20.

22. A temperature-sensitive organic light-emitting molecule according to any one of claims 1 to 3, or or Or the use of the temperature-sensitive organic light-emitting molecule-doped film as described in claim 21 in temperature sensing.

23. The use according to claim 22, characterized in that: Application in thermal history detection.

24. The use according to claim 23, characterized in that: Application in thermal history detection of electronic components.

25. The use according to claim 22, characterized in that: Applications in photothermal patterning.

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