CN109293685B - Inorganic and organic hybrid copper iodide, preparation method thereof and application thereof as fluorescence thermometer - Google Patents
Inorganic and organic hybrid copper iodide, preparation method thereof and application thereof as fluorescence thermometer Download PDFInfo
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- GBRBMTNGQBKBQE-UHFFFAOYSA-L copper;diiodide Chemical compound I[Cu]I GBRBMTNGQBKBQE-UHFFFAOYSA-L 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title description 10
- 239000010949 copper Substances 0.000 claims abstract description 32
- -1 Octane cation Chemical class 0.000 claims abstract description 6
- 125000000129 anionic group Chemical group 0.000 claims abstract description 6
- 125000002091 cationic group Chemical group 0.000 claims abstract description 5
- 230000009471 action Effects 0.000 claims abstract description 3
- 239000000126 substance Substances 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 25
- 150000001875 compounds Chemical class 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 17
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 14
- 239000013078 crystal Substances 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 2
- 238000006073 displacement reaction Methods 0.000 abstract description 7
- 238000011160 research Methods 0.000 abstract description 6
- 150000001450 anions Chemical group 0.000 abstract description 5
- 239000011540 sensing material Substances 0.000 abstract description 3
- 238000002474 experimental method Methods 0.000 abstract description 2
- 239000011521 glass Substances 0.000 description 22
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 125000004429 atom Chemical group 0.000 description 7
- 238000004020 luminiscence type Methods 0.000 description 5
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 5
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- 238000002447 crystallographic data Methods 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
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- 125000002346 iodo group Chemical group I* 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
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- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
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- 150000001768 cations Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
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- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 229910003480 inorganic solid Inorganic materials 0.000 description 1
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Abstract
An inorganic-organic hybrid copper iodide, the chemical formula of the hybrid copper iodide is [ (DabcoCH)2Cl)4Cu5I6][Cu2I5]Wherein DabcoCH2Cl is 1-chloromethyl-1, 4-diazobicyclo [ 2.2.2%]Octane cation. The inventive hybrid copper iodides consist of dimeric anion units [ Cu2I5]3‑And inorganic-organic hybrid [ (DabcoCH)2Cl)4Cu5I6]3+The cationic unit and the anionic unit form a three-dimensional supermolecular structure through the action of electrostatic attraction. The invention is found by experiments that: the hybrid copper iodide has outstanding fluorescence property and fluorescence thermochromism property, can be used as a fluorescence thermometer, is particularly used as a displacement type fluorescence thermometer in the field of fluorescence temperature sensing, and provides a new idea for the research of temperature sensing materials.
Description
Technical Field
The invention belongs to the technical field of inorganic solid luminescent materials, and particularly relates to a novel inorganic-organic hybrid copper iodide compound, a preparation method thereof and application thereof as a fluorescence thermometer.
Background
The inorganic-organic hybrid halide is an important inorganic functional material and has abundant structure and various physicochemical propertiesHas very important application prospect in the aspects of fluorescence, semiconductivity, nonlinear optics, thermochromism, photochromism, effective visible light catalytic performance and the like [ A.K. Cheetham, G.F. rey, T. L oiseau. Angew. Chem.1997,38: 3268-3292; Q. Hou, J.-H. Yu, J.-N. Xu,CrystEngComm2009, 11,2452-2455; X. Luo, Y. Cao, T. Wang,J. Am. Chem. Soc.,2016,138: 786-789；R.-C. Zhang, J.-J. Wang, J.-C. Zhang, M.-Q. Wang, M. Sun, F. Ding, D.-J. Zhang,Y.-L. An,Inorg. Chem.2016,55, 7556-7563; X.-W. Lei, C.-Y. Yue, J.-Q. Zhao,Cryst. Growth Des.2015,15, 5416−5426；X.-W. Lei, C.-Y. Yue, J.-Q. Zhao,Cryst. Growth & Design,2015,15, 5416-5426.]. Wherein, Cu+The ion having d10Electronic configuration, with I-Various ion coordination modes and flexible polymerization modes, and can form inorganic-organic hybrid copper iodide materials with rich structures [ W. L iu, Y.Fang, G.Z.Wei, S.J.Teat, K.Xiong, Z.Hu, W.P. L ustig, J. L i,J. Am. Chem. Soc.2015,137, 9400; J D. Martin, K B. Greenwood. Angew. Chem.1997,36, 2072-2075; J. R. D. Debor, J. Zubieta,Chem. Commun.1997,1365-1366; J. K, Cheng, Y. B. Chen, L. Wu,. Inorg. Chem.2005,44, 3386-3388.]inorganic-organic hybrid copper iodide has outstanding fluorescence properties, such as high luminous intensity, high quantum yield, large Stock shift and long fluorescence lifetime, is an important luminescent material, and has important application prospects in various aspects such as photoelectric sensors, ion detection, temperature sensing, dangerous goods detection and the like [ Q. Benito, X.F. L e Goff, S. Maron, A.farges, A.Garcia, C. Martineau, F. tauelle, S. Kahlal, T. Gacoin, J. -P.Boilot, S. Perruca,J. Am. Chem. Soc.2014,136, 113-116; X. Zhang, W. Liu,G. Z. Wei, D. Banerjee, Z. Hu, J. Li,J. Am. Chem. Soc.2014,136, 14230; Y.Fang, W. Liu, S. J. Teat, G. Dey, Z. Shen, L. An, D. Yu, L. Wang, D. M. O’Carroll, J. Li,Adv. Funct. Mater.2016, 201603444.]。
researches the synthesis and properties of the novel inorganic-organic hybrid copper iodide,will provide new approaches for the further development of new luminescent solid materials, such as fluorescent thermochromism, fluorescent thermometers and fluorescent gas sensing [ s. -z. Zhan, m. L i, x. -p. Zhou,Chem Commun, 2011, 47, 12441-12442; X.-C. Shan, F.-L. Jiang,D.-Q. Yuan,Chem Sci., 2013,4, 1484-1489; C. R. Kagan, D. B. Mitzi, C. D.Dimitrakopoulos,Science1999,286, 945]exploring the synthesis of novel inorganic-organic hybrid copper iodides, and studying the structure-activity relationship between the structure and the properties thereof, will provide a new idea for developing novel luminescent materials [ R. -C.Zhang, J. -J. Wang, J. -C. Zhang, M. -Q. Wang, M. Sun, F. Ding, D. -J. Zhang, Y. -L. An,Inorg. Chem.2016,55, 7556-7563]。
disclosure of Invention
The invention aims to provide a novel inorganic-organic hybrid copper iodide which has a novel three-dimensional supramolecular skeleton and good fluorescence and can be applied to the field of fluorescent materials.
The invention also provides a preparation method of the inorganic-organic hybrid copper iodide and an application of the inorganic-organic hybrid copper iodide as a fluorescence thermometer.
In order to achieve the purpose, the invention adopts the following technical scheme:
an inorganic-organic hybridized copper iodide has a chemical formula of [ (DabcoCH)2Cl)4Cu5I6][Cu2I5]Wherein, DabcoCH2Cl is 1-chloromethyl-1, 4-diazobicyclo [ 2.2.2%]Octane cation. The compounds consist of dimeric anionic units [ Cu2I5]3-And inorganic-organic hybrid [ (DabcoCH)2Cl)4Cu5I6]3+The cationic unit and the anionic unit form a three-dimensional supermolecular structure through the action of electrostatic attraction. Furthermore, the crystal system of the inorganic and organic hybrid copper iodide belongs to an orthorhombic system and a space groupPbcm. Unit cell parameters:a＝13.929 (2)、b= 14.223(2)、c= 29.419(4)，α= 90.0°。
the preparation method of the inorganic and organic hybrid copper iodide specifically comprises: CuI, 1-chloromethyl-4-fluoro-1, 4-diazobicyclo [2.2.2]Octane bis (tetrafluoroborate) salt (i.e., [ C ]7H14N2FCl][BF4]2) HI and a solvent are mixed uniformly, then the mixture is reacted at the constant temperature of 60-120 ℃ for 100-180 hours, and a product is obtained after the reaction is finished and is washed and dried.
Specifically, the CuI, [ C ]7H14N2FCl][BF4]2And HI in a molar ratio of 1: 0.5-1: 5-10.
Further, in order to obtain a good dissolving effect, the solvent is a mixture of N, N-Dimethylformamide (DMF) and water, further preferably, the solvent is composed of DMF and water in a volume ratio of 1: 1, wherein, preferably, 0.5 to 1.0m L of the solvent is added per 0.1mmol of CuI, and the optimal use amount of the solvent is 0.8m L.
Experiments show that the inorganic and organic hybrid copper iodide has outstanding fluorescence property and can be used as a fluorescent material; furthermore, the fluorescent thermochromic fluorescent material also shows the fluorescent thermochromic property, and can be used as a fluorescent thermometer, particularly as a displacement type fluorescent thermometer applied to the field of fluorescent temperature sensing.
Compared with the prior art, the invention has the following beneficial effects
The invention adopts mild solvothermal synthesis, the reaction temperature is only 60-120 ℃, the method is different from a common high-temperature solid phase method in literature reports, and the method overcomes the defects of high temperature, high risk, low yield, poor repeatability and the like. The preparation method has the advantages of simple process, mild conditions, high yield and good repeatability, and the prepared inorganic-organic hybrid copper iodide has outstanding fluorescence property and fluorescence thermochromism property, can be used as a fluorescence thermometer, is particularly used as a displacement type fluorescence thermometer in the field of fluorescence temperature sensing, and provides a new idea for the research of temperature sensing materials.
Drawings
FIG. 1 is a diagram of the structural unit of the inorganic-organic hybrid copper iodide of the present invention;
FIG. 2 is a three-dimensional supramolecular structure of the inorganic-organic hybrid copper iodide of the invention;
FIG. 3 is an XRD pattern of the inorganic-organic hybrid copper iodide of the present invention;
FIG. 4 is a graph of the UV-VIS spectrum of the inorganic-organic hybrid copper iodide of the present invention;
FIG. 5 is a fluorescence spectrum of the inorganic-organic hybrid copper iodide of the present invention;
FIG. 6 is a graph of temperature-variable fluorescence curves of inorganic-organic hybrid copper iodides according to the present invention;
FIG. 7 is a linear fitting graph of the inorganic-organic hybrid copper iodide of the present invention as a displacement type fluorescence thermometer.
Detailed Description
In order to make the technical purpose, technical scheme and beneficial effects of the present invention clearer, the technical scheme of the present invention is further described with reference to the accompanying drawings and specific examples, but the examples are intended to explain the present invention and should not be construed as limiting the present invention, the examples do not indicate specific techniques or conditions, the examples are performed according to techniques or conditions described in documents in the field or according to product specifications, and the reagents or instruments are not indicated by manufacturers, and all are conventional products which can be obtained commercially.
Example 1
A preparation method of novel inorganic-organic hybrid copper iodide specifically comprises the following steps:
firstly, 0.05mmol of CuI (shinning Fine chemical research institute, Tianjin) and 0.04mmol of C are added into a hard glass tube7H14N2FCl][BF4]2(Shanghai Fluri Fine chemistry Co., Ltd.), 0.4 mmol HI (H104605-100 ml) and 0.4m L solvent (the solvent is composed of DMF and water with a volume ratio of 1: 1), the glass tube filling rate is 10%, the ultrasonic dispersion is uniform, then the tube is sealed on an alcohol lamp (i.e. the glass tube is sealed to make the reaction proceed under a sealed state), the reaction vessel is placed in a reaction kettle, then the reaction vessel is placed in a drying box (without vacuum) at 85 ℃ for 160 hours at a constant temperature, after the reaction is finished, the reaction vessel is naturally cooled to room temperature, transparent blocky crystals are observed in the glass tube, the crystals are respectively washed by acetonitrile and ethanol, and then the crystals are driedAnd drying to obtain the inorganic-organic hybrid copper iodide.
The yield of the obtained inorganic-organic hybrid copper iodide is 90%, and the molecular formula is as follows: c28H56N8Cl4Cu7I11. Scanning electron microscopy photoelectron spectroscopy (EDS) results show that Cu: I: Cl in the compound is 7: 11: 4; elemental analysis results showed that in the compound: the results of structural analysis were consistent with 13.42% C, 2.3% H, and 4.5% N.
Structural determination of the obtained inorganic-organic hybrid copper iodide:
selecting copper iodide single crystal with proper size under microscope, and monochromating Mo-K with graphite monochromator at room temperature on Bruker APEX II CCD plane-detection diffractometerαRay (C)λ= 0.71073 Å), diffraction data were collected in the ω -mode all diffraction data were corrected for semi-empirical absorption using the SADABS program the unit cell parameters were determined using the least squares method the data reduction and structure analysis were done using SAINT and SHE L XT L programs, respectivelyEMap determination, while the other non-hydrogen atoms are determined by difference fourier function and least squares, followed by anisotropic refinement. The detailed crystal assay data of the obtained compound are shown in table 1.
TABLE 1 Compound [ (DabcoCH)2Cl)4Cu5I6][Cu2I5]Crystallographic data of
As can be seen from Table 1, the molecular formula of the inorganic-organic hybrid copper iodide is [ (DabcoCH)2Cl)4Cu5I6][Cu2I5]Its crystal belongs to orthorhombic system, and its space group is space groupPbcm. Unit cell parameters:a＝13.929 (2)、b=14.223(2)、c= 29.4194(8)，α= 90.0 °. The skeleton of the inorganic-organic hybrid copper iodide is a three-dimensional supramolecular skeleton structure (shown in figure 2), and the structural unit diagram is shown in figure 1The resulting compound is an inorganic-organic hybrid of [ (DabcoCH)2Cl)4Cu5I6]3+Clustered and dimerized [ Cu ]2I5]3-Electrostatic attraction between the anion units. In the anionic unit [ Cu2I5]3-In the formula, two Cu atoms are respectively connected with 3I atoms by adopting triangular coordination, and two CuI atoms are respectively connected with3Units joined together by one I atom to form a dimeric anion [ Cu ]2I5]3-And [ (DabcoCH)2Cl)4Cu5I6]3+The cluster of atoms being composed of the anion Cu5I6Unit with four cationic DabcoCH2Cl+Coordination of units. In the reaction of [ (DabcoCH)2Cl)4Cu5I6]3+In the atomic cluster, there are five Cu atoms, wherein, four crystallographically independent Cu atoms are respectively connected with four Dabco-CH2The terminal N atom in Cl is connected with Cu-N coordination bond, and the four Cu atoms adopt tetrahedral coordination mode and are respectively connected with three I atoms and one Dabco-CH around the Cu atoms2The N atom at the Cl terminal forms a tetrahedron; the remaining Cu atom is connected to its adjacent upper and lower I atoms in a linear coordination. In this cluster, the four organic ligands are positively charged, while the anion Cu5I6The unit has a negative charge, which makes the hybridized cluster cationic. The electron cloud density of negative charges in the structural unit is effectively reduced through the cation cluster formed by the Cu-N coordination bond, so that the stability of the structural unit is enhanced, and a new thought is provided for designing and synthesizing novel organic-inorganic hybrid copper iodide with a stable structure.
Powder X-ray diffraction measurement of the resulting inorganic-organic hybrid copper iodide:
after the sample is uniformly ground, powder X-ray diffraction data of the compound is measured by using a Pasnake powder X-ray diffractometer, as shown in figure 3, a characteristic peak of an experimental sample spectrogram corresponds to a characteristic peak of a simulated spectrogram, and the crystal of the compound is a pure phase.
Ultraviolet-visible spectrum determination of the obtained inorganic-organic hybrid copper iodide:
after grinding the sample, performing ultraviolet-visible spectrum determination, wherein the solid ultraviolet-visible spectrum is shown in fig. 4, and the ultraviolet-visible spectrum of the compound shows that the absorption edge of the compound is 410nm, which indicates that the compound has strong absorption in the ultraviolet region.
The fluorescence property of the obtained inorganic-organic hybrid copper iodide is determined as follows:
a proper amount of sample is taken, the luminescence property of the sample is measured by an F L S980 fluorescence spectrometer, as shown in figure 5, the solid material has obvious luminescence property under the excitation of 341nm ultraviolet light at room temperature, the maximum emission peak is 632nm, and the emission is red light.
Fluorescence thermochromism determination of the obtained inorganic-organic hybrid copper iodide compound:
a proper amount of sample is taken, the temperature-variable luminescence property of the compound is measured by an F L S980 fluorescence spectrometer, and the result shows that the luminescence behavior of the compound is very special at different temperatures, as shown in figure 6, the maximum emission peak position of the compound is 648nm under the condition of 180K temperature and when the compound is excited by 341nm ultraviolet light, the maximum emission peak of a fluorescence spectrum is gradually subjected to blue shift along with the gradual rise of the temperature, and the maximum emission peak position is blue-shifted to 610 nm when the temperature is 400K, and the fluorescence intensity is gradually reduced, so that the compound has remarkable fluorescence thermochromism property.
Example 2
A preparation method of novel inorganic-organic hybrid copper iodide specifically comprises the following steps:
firstly, 0.05mmol of CuI (shinning Fine chemical research institute, Tianjin) and 0.05mmol of C are added into a hard glass tube7H14N2FCl][BF4]2(Shanghai Fluri Fine chemistry Co., Ltd.), 0.3 mmol HI (H104605-100 ml) and 0.3 m L solvent (the solvent is composed of DMF and water with the volume ratio of 1: 1), the filling rate of the glass tube is 10%, the ultrasonic dispersion is uniform, then the tube is sealed on the alcohol lamp (i.e. the glass tube is sealed to make the reaction proceed under the sealed state), the reaction vessel is placed in the reaction vessel, then the reaction vessel is placed in a drying box (without vacuum) at 65 ℃ for 160 hours under constant temperature, and after the reaction is finished, the vessel is kept for 160 hoursNaturally cooling to room temperature, observing that transparent blocky crystals exist in the glass tube, washing with acetonitrile and ethanol respectively, and drying to obtain the inorganic-organic hybrid copper iodide.
Example 3
A preparation method of novel inorganic-organic hybrid copper iodide specifically comprises the following steps:
firstly, 0.1mmol of CuI (shinning Fine chemical research institute, Tianjin) and 0.08mmol of [ C ] are added into a hard glass tube7H14N2FCl][BF4]2(Shanghai Fluri Fine chemistry Co., Ltd.), 0.6 mmol HI (H104605-100 ml) and 1.0m L solvent (the solvent is composed of DMF and water with the volume ratio of 1: 1), the filling rate of the glass tube is 10%, the ultrasonic dispersion is uniform, then the glass tube is sealed on an alcohol lamp (namely the glass tube is sealed to enable the reaction to be carried out in a sealed state), the glass tube is placed in a reaction kettle, then the reaction kettle is placed in a drying box (without vacuum) at the constant temperature of 105 ℃ for 160 hours, after the reaction is finished, the glass tube is naturally cooled to the room temperature, transparent blocky crystals are observed in the glass tube, the crystals are respectively washed by acetonitrile and ethanol, and then the inorganic-organic hybrid copper iodide is obtained after the reaction is finished and naturally cooled.
Example 4
A preparation method of novel inorganic-organic hybrid copper iodide specifically comprises the following steps:
firstly, 0.1mmol of CuI (shinning Fine chemical research institute, Tianjin) and 0.1mmol of [ C ] are added into a hard glass tube7H14N2FCl][BF4]2(Shanghai Fluri Fine chemistry Co., Ltd.), 0.5 mmol HI (H104605-100 ml) and 0.6m L solvent (the solvent is composed of DMF and water with the volume ratio of 1: 1), the filling rate of the glass tube is 10%, the ultrasonic dispersion is uniform, then the glass tube is sealed on an alcohol lamp (namely the glass tube is sealed to enable the reaction to be carried out in a sealed state), the glass tube is placed in a reaction kettle, then the reaction kettle is placed in a drying box (without vacuum) at the constant temperature of 120 ℃ for 160 hours, after the reaction is finished, the glass tube is naturally cooled to the room temperature, transparent blocky crystals are observed in the glass tube, the crystals are respectively washed by acetonitrile and ethanol, and then the inorganic-organic hybrid copper iodide is obtained after the reaction is finished and dried.
Application test
The novel inorganic-organic hybrid copper iodide prepared in example 1 of the present invention (i.e., the following samples) was used as a luminescent material for temperature sensing studies:
the temperature-variable fluorescence behavior of the sample is studied by using a fluorescence spectrometer. The study showed that: the response of the luminescence of the compound to the temperature is obviously different at different temperatures, particularly the temperature range is between 180-400K, the maximum emission peak position is 648nm at low temperature of 180K, the maximum emission peak of the fluorescence spectrum gradually generates blue shift along with the gradual rise of the temperature, and the maximum emission peak position is blue shift to 610 nm at 400K. And the maximum emission peak and the temperature show a good linear relationship (R 2= 0.9939), a displacement type fluorescence thermometer may be fitted as shown in fig. 7. The displacement type fluorescence thermometer material is a rare displacement type fluorescence thermometer material, has higher accuracy compared with an intensity or life thermometer, is not influenced by emission intensity and the factors of an instrument, and provides a new direction for developing and researching temperature sensing materials.
Finally, it should be noted that: the above embodiments are merely illustrative and not restrictive of the technical solutions of the present invention, and any equivalent substitutions and modifications or partial substitutions made without departing from the spirit and scope of the present invention should be included in the scope of the claims of the present invention.
Claims (8)
1. An inorganic-organic hybrid copper iodide is characterized in that the chemical formula is [ (DabcoCH)2Cl)4Cu5I6][Cu2I5]Wherein, DabcoCH2Cl is 1-chloromethyl-1, 4-diazobicyclo [ 2.2.2%]Octane cations;
the compounds consist of dimeric anionic units [ Cu2I5]3-And inorganic-organic hybrid [ (DabcoCH)2Cl)4Cu5I6]3+The cationic unit and the anionic unit form a three-dimensional supermolecular structure through the action of electrostatic attraction;
the inorganic and organicThe crystal system of hybridized copper iodide belongs to an orthorhombic system and a space groupPbcm(ii) a Unit cell parameters:a＝13.929(2)、b= 14.223(2)、c= 29.419(4)，α= 90.0°。
2. the method for preparing inorganic-organic hybrid copper iodide as claimed in claim 1, wherein the method comprises the steps of mixing CuI, 1-chloromethyl-4-fluoro-1, 4-diazobicyclo [2.2.2] octane bis (tetrafluoroborate) salt, HI and solvent uniformly, reacting at a constant temperature of 60-120 ℃ for 100-180 hours, and washing and drying the product after the reaction is finished.
3. The method for preparing inorganic-organic hybrid copper iodide as claimed in claim 2, wherein the molar ratio of CuI, 1-chloromethyl-4-fluoro-1, 4-diazobicyclo [2.2.2] octane bis (tetrafluoroborate) salt and HI is 1: 0.5-1: 5-10.
4. The method for preparing inorganic-organic hybrid copper iodide as claimed in claim 2 or 3, wherein the solvent is a mixture of N, N-dimethylformamide and water.
5. The method for preparing inorganic-organic hybrid copper iodide as claimed in claim 4, wherein the solvent is composed of DMF and water at a volume ratio of 1: 1, and 0.5-1.0m L of solvent is added for every 0.1mmol of CuI.
6. Use of the inorganic-organic hybrid copper iodides according to claim 1 as fluorescent materials.
7. Use of the inorganic-organic hybrid copper iodide as claimed in claim 1 as a fluorescence thermometer.
8. Use of the inorganic-organic hybrid copper iodide as defined in claim 1 as a shift-type fluorescence thermometer.
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