One-dimensional Tb (III) coordination polymer as well as preparation method and application thereof

Abstract

The invention relates to a one-dimensional Tb (III) coordination polymer as well as a preparation method and application thereof. The chemical formula of the one-dimensional Tb (III) coordination polymer is [Tb4 (TC4A4-) (HTC4A3-) (OBBA2-) 2 (CH3OH) 4 (mu4-OH)] n, green fluorescence is emitted under laser excitation, and the one-dimensional Tb (III) coordination polymer can be used for preparing green fluorescent materials or devices and can be used as a temperature-sensitive fluorescent material for preparing temperature-sensitive fluorescent materials or devices. Besides, the one-dimensional Tb (III) coordination polymer can be synthesized by adopting a solvothermal method, the synthesis method is simple, the yield is relatively high, and the structure and fluorescence stability can be well maintained in an organic solvent and different pH environments, so that the one-dimensional Tb (III) coordination polymer has a wide application prospect.

Description

Technical Field

[0001] The present invention belongs to the technical fields of fluorescent sensing materials and rare earth materials, and particularly relates to a one-dimensional Tb(III) coordination polymer, a preparation method thereof, and uses thereof. Background Art

[0002] Stimulus-responsive luminescent materials are a typical type of intelligent materials, whose luminescent properties such as emission intensity, wavelength, and fluorescence lifetime can be adjusted under external stimuli such as light, heat, and mechanical force. Such materials have attracted extensive attention and research in the fields of sensors, medical engineering, information storage, etc. Thermochromic luminescent materials, due to their unique property of changing luminescent characteristics with temperature, exhibit extensive application potential in multiple high-tech fields such as temperature indicators, chemical sensing, and optical anti-counterfeiting.

[0003] Due to their unique advantages such as adjustable structures and easy functionalization, in fluorescent materials, the luminescence of coordination polymers can come from the material's own structure, mainly including organic linkers and central metal ions; it can also come from encapsulated guests such as dyes and perovskites. Due to their unique luminescent properties, they have become one of the most attractive candidate materials in the field of luminescent materials. Using coordination polymers in luminescence thermometry combines the inherent advantageous properties of metal centers and organic linkers, thus generating a pioneering sensing mechanism that can function in a wide temperature range. The temperature-dependent luminescent properties are used as the main indicators for temperature measurement and sensing, and changes in lifetime, intensity, and color are the key variables.

[0004] CN 109293685A discloses an inorganic-organic hybrid copper iodide [(DabcoCH 2 Cl) 4 Cu 5 I 6 [Cu 2 I 5 , and the maximum emission peak of this compound blue-shifts from 648 nm to 610 nm between 180 - 400 K, showing a good linear relationship with temperature (R 2 = 0.9939).

[0005] CN 109053578A discloses a novel inorganic-organic hybrid silver iodide, a preparation method thereof, and an application as a fluorescent thermometer. Between 160 - 340 K, the emission peak position in the low-energy emission region of this compound gradually blue-shifts from 730 nm to 615 nm, showing a good linear relationship with temperature, and the linear correlation coefficient is 0.997.

[0006] CN 114702946A discloses a thermoluminescent color-changing temperature-measuring fluorescent material and a preparation method thereof. The chemical formula of this material is Ca 1-x Nb2 O 6 :xEu 3+ , changes from blue light to red light with increasing temperature in the range of 293 - 413K, and the maximum temperature measurement sensitivity is 3.70%·K -1 .

[0007] In summary, the research and application of fluorescent temperature-sensitive materials have important technical backgrounds. By developing new high-performance fluorescent temperature-sensitive materials with a wide temperature measurement range, a high linear correlation coefficient, and a high temperature measurement sensitivity, the future demand for efficient and accurate temperature measurement in multiple fields can be met, thus promoting the progress and development of related technologies. Summary of the Invention

[0008] To meet the above requirements for fluorescent temperature measurement materials, the present invention combines the fluorescence characteristics of Tb(III) and the structurally peculiar organic ligands 4-tert-butylthiacalix[4]arene and 4,4'-oxydibenzoic acid to obtain a one-dimensional Tb(III) coordination polymer. This one-dimensional Tb(III) coordination polymer has excellent temperature response in the range of 323 - 473K, a good linear relationship between the fluorescence quenching rate and temperature change, R 2 = 0.9993, and has a high temperature measurement sensitivity S r = 8.743%·K -1 , can well maintain the structure and fluorescence stability in organic solvents and different pH environments, and has broad application prospects. In addition, the synthesis method of the one-dimensional Tb(III) coordination polymer of the present invention is simple and has a high yield.

[0009] On the one hand, the present invention provides a one-dimensional Tb(III) coordination polymer, and its chemical formula is:

[0010] [Tb 4 (TC4A 4- )(HTC4A 3- )(OBBA 2- ) 2 (CH 3 OH) 4 (μ 4 -OH)] n ;

[0011] Wherein,

[0012] TC4A 4- / HTC4A 3- is deprotonated 4-tert-butylthiacalix[4]arene,

[0013] OBBA 2- is deprotonated 4,4'-oxydibenzoic acid,

[0014] n represents the degree of polymerization and is a positive integer.

[0015] Preferably, the one-dimensional Tb(III) coordination polymer is monoclinic, P2 1 / c space group, and the unit cell parameters are: α = 90°, β = 130.9770(10)°, γ = 90°, Z = 2.

[0016] The basic structural unit of the one-dimensional Tb(III) coordination polymer of the present invention contains four central Tb 3+ , two 4-tert-butylthiacalix[4]arenes, four 4,4'-diphenylether dicarboxylic acids, four methanol and one OH - ; four Tb 3+ all exhibit a nine-coordination mode. Figure 1 a schematically shows the coordination mode (left), the front view (middle) and the side view (right) of the basic structural unit of the central Tb 3+ , but the present invention is not limited thereto.

[0017] In particular, the coordination bonding modes of the four central Tb 3+ are as follows: four Tb 3+ coordinate and bond with eight sulfur atoms and eight oxygen atoms in two 4-tert-butylthiacalix[4]arenes, four carboxylate oxygen atoms in four 4,4'-diphenylether dicarboxylic acids, oxygen atoms in four methanol and oxygen atoms in one OH - .

[0018] In the basic structural unit of the one-dimensional Tb(III) coordination polymer of the present invention, four central metal Tb1 and Tb2, and Tb1# and Tb2# are connected by a μ 4 -O to form a Tb 4 nucleus. Each Tb 3+ is nine-coordinated, and seven coordination sites are respectively coordinated with a μ4-O and two phenolic hydroxyl oxygen atoms and one sulfur atom provided by the H 4 TC4A molecules at both ends to form a four-core secondary structure Tb 4 (TC4A) 2 . The remaining two coordination sites are occupied by oxygen atoms provided by 4,4'-diphenylether dicarboxylic acid ligands and solvent molecules. The four-core secondary structure units are connected by 4,4'-diphenylether dicarboxylic acid to form a one-dimensional structure. Figure 1 b schematically shows the front view of the structural bowl diagram of coordination polymer 1, and c schematically shows the structural stacking diagram of coordination polymer 1 along the c-axis and b-axis, but the present invention is not limited thereto.

[0019] On the other hand, the present invention provides a preparation method of the one-dimensional Tb(III) coordination polymer, including:

[0020] S1: Mix 4-tert-butylthiacalix[4]arene (H 4 TC4A), 4,4'-oxybisbenzoic acid (H 2 OBBA), methanol and a Tb(III) ion source to obtain a mixed solution;

[0021] S2: React the mixed solution obtained in step S1 above by solvothermal method to obtain a one-dimensional Tb(III) coordination polymer.

[0022] The CAS number of 4-tert-butylthiacalix[4]arene (4-tert-butylthiacalix[4]arene, H4TC4A) is 182496-55-5, and its structure is as follows:

[0023]

[0024] The CAS number of 4,4'-oxybisbenzoic acid (4,4'-Oxybisbenzoic acid, H 2 OBBA) is 2215-89-6, and its structure is as follows:

[0025]

[0026] In an embodiment, in step S1, the Tb(III) ion source can be selected from inorganic or organic salts of Tb(III), such as nitrates, hydrochlorides, sulfates, acetates and their solvates, such as terbium nitrate hexahydrate, terbium sulfate octahydrate, terbium acetate hydrate.

[0027] In an embodiment, in step S1, the molar ratio of 4-tert-butylthiacalix[4]arene, 4,4'-oxybisbenzoic acid and Tb(III) ions can be 0.5-1.5:1-3:1-3, such as 0.5:2:2, 1:3:3, 1.5:1:1, 1:1.5:1.5, etc., and particularly preferably about 1:2:2.

[0028] In an embodiment, in step S1, based on 1 mmol of Tb(III) ions, the amount of methanol used can be more than 10 mL, such as more than 15 mL, more than 20 mL, more than 40 mL, more than 60 mL, preferably more than 60 mL, and less than 200 mL, less than 100 mL, etc. Too little methanol is not conducive to the formation of the coordination polymer, while too much methanol is not conducive to the precipitation of the coordination polymer, thus reducing the yield.

[0029] In an embodiment, in step S1, other organic solvents can also be added, such as dimethylformamide (DMF) and dimethylacetamide (DMA). The volume ratio of the other organic solvent to methanol can be from 10:1 to 1:0, preferably from 6:1 to 1:6, such as 1:6, 1:5, 1:4, 1:3, 1:2, 1:1, etc.

[0030] In an embodiment, in step S1, 4-tert-butylthiacalix[4]arene, 4,4'-diphenylether dicarboxylic acid, terbium acetate, methanol and dimethylformamide are mixed to obtain a mixed solution. Among them, the molar ratio of 4-tert-butylthiacalix[4]arene, 4,4'-diphenylether dicarboxylic acid and Tb(III) ions is about 1:2:2. Based on 1 mmol of Tb(III) ions, the total amount of methanol and dimethylformamide is about 60 - 100 mL, and the volume ratio of methanol to dimethylformamide is about 6:1 to 1:6.

[0031] In an embodiment, in step S1, conventional methods can be used to promote mixing, such as ultrasonic treatment, stirring, etc.

[0032] In an embodiment, in step S2, the solvothermal method is carried out in a closed system. There is no particular limitation on the closed system, as long as it can withstand the temperature and pressure during the reaction, for example, it can be a reaction kettle.

[0033] In an embodiment, in step S2, the reaction temperature of the solvothermal method is 100 - 200 °C, preferably 120 - 180 °C, such as 120, 130, 140, 150, 160, 170 °C, etc., especially 130 - 150 °C. The reaction time is not particularly limited, as long as the target one-dimensional Tb(III) coordination polymer can be obtained, for example, it can be more than 1 hour, more than 5 hours, more than 12 hours, more than 24 hours, more than 48 hours, such as 72 hours. There is no limit on the upper limit of the reaction time, but too long a time is uneconomical. Therefore, it can be less than 5 days, less than 4 days, etc.

[0034] In an embodiment, step S2 further includes a post-treatment step, including cooling, filtration, and washing the obtained solid. The washing solvent can be an alcohol solvent, such as methanol, ethanol, etc.

[0035] The one-dimensional Tb(III) coordination polymer of the present invention can emit green fluorescence under laser excitation. The maximum excitation wavelength is 364 nm, and under this excitation, it exhibits the characteristic emission of Tb 3+ namely 490, 548, 586, 622, 649, 668 and 679 nm. In addition, the fluorescence emission of the one-dimensional Tb(III) coordination polymer of the present invention has temperature dependence, and thus can be used as a temperature-sensitive fluorescent material.

[0036] Therefore, on the other hand, the present invention relates to the use of the one-dimensional Tb(III) coordination polymer in the preparation of green fluorescent materials or devices, and / or in the preparation of temperature-sensitive fluorescent materials or devices.

[0037] In summary, the one-dimensional Tb(III) coordination polymer and the preparation method thereof of the present invention have the following technical effects:

[0038] 1. The method of the present invention uses a simple solvothermal method. Compared with most reaction conditions for obtaining Tb-MOF at 150 °C or higher temperatures, the reaction conditions are relatively mild. The mild reaction temperature makes the large-scale production less demanding on experimental conditions, and the cost is greatly reduced, and the product yield is high.

[0039] 2. The maximum excitation wavelength of the one-dimensional Tb(III) coordination polymer of the present invention is 364 nm, and it exhibits the characteristic emission of Tb 3+ under this excitation, namely 490, 548, 586, 622, 649, 668 and 679 nm.

[0040] 3. The linear relationship between the fluorescence quenching rate and the temperature of the one-dimensional Tb(III) coordination polymer of the present invention is very good, and the R 2 value is as high as 0.9995, and the relative thermal sensitivity is as high as 8.743%·K -1 , which is higher than the latest literature report (Eu x / Tb 1-x (phen)@MOF-808: The relative thermal sensitivity is at most 8.65% K in the range of 293 - 383 K -1 ).

[0041] 4. The raw materials for synthesizing the one-dimensional Tb(III) coordination polymer of the present invention are easily available, the synthesis method is simple, the yield is high, the linear relationship between the fluorescence intensity and the temperature change is good, and it has broad application prospects in temperature-sensitive fluorescence sensing materials. BRIEF DESCRIPTION OF THE DRAWINGS

[0042] Figure 1 Showing the crystal structure schematic diagram of the coordination polymer 1 prepared in Example 1 of the present invention, where a schematically shows the coordination mode of the central Tb 3+ in the coordination polymer 1 (left), the front view (middle) and the side view (right) of the basic structural unit, b schematically shows the front view of the structural bowl diagram of the coordination polymer 1, and c schematically shows the structural stacking diagram of the coordination polymer 1 along the c-axis and the b-axis.

[0043] Figure 2 Showing the powder X-ray diffraction pattern and the simulated pattern of the coordination polymer 1 prepared in Example 1 of the present invention.

[0044] Figure 3Show the excitation-emission spectrum (a) and the solid fluorescence lifetime test curve (b) of coordination polymer 1 prepared in Example 1 of the present invention at 298K.

[0045] Figure 4 Show the powder X-ray diffraction (PXRD) pattern (a) and the emission spectrum (b) of coordination polymer 1 prepared in Example 1 of the present invention in different solvents.

[0046] Figure 5 Show the powder X-ray diffraction (PXRD) pattern (a) and the emission spectrum (b) of coordination polymer 1 prepared in Example 1 of the present invention at different pH values.

[0047] Figure 6 Show the 5 D 4 → 7 F 5 Normalized temperature-dependent intensity and its fitting line graph (a) and relative sensitivity values at different temperatures (b). Detailed implementation manners

[0048] To facilitate the understanding of the present invention, the technical solutions of the present invention will be further described below through specific implementation manners. Those skilled in the art should understand that the embodiments are only for helping to understand the present invention and should not be regarded as specific limitations on the present invention.

[0049] The materials, reagents, etc. used in the following embodiments can be obtained from commercial channels without special instructions.

[0050] Reagents

[0051] 4,4'-Diphenylether dicarboxylic acid (H2OBBA) was purchased from Jinan Henghua Biotechnology Co., Ltd., CAS No. 2215-89-6.

[0052] Terbium nitrate hexahydrate, terbium chloride hexahydrate, and terbium acetate hydrate were purchased from Shanghai Titan Technology Co., Ltd.

[0053] Chloroform, acetone, and concentrated hydrochloric acid were purchased from Xilong Scientific Co., Ltd., all of which are of analytical grade.

[0054] Triethylamine, N,N-dimethylformamide (DMF), and N,N-dimethylacetamide (DMA) were purchased from Aladdin Reagent Co., Ltd., all of which are of reagent grade.

[0055] Methanol was purchased from Shanghai Macklin Biochemical Co., Ltd.

[0056] p-tert-Butylcalix[4]arene was synthesized according to the method in the reference (DOI: 10.1016 / S0040-4020(00)00030-2) as follows:

[0057] Weigh 8.86 g of sodium hydroxide into a three-necked flask, add 19 mL of tetraethylene glycol dimethyl ether, heat to 130 °C under nitrogen protection, and reflux to remove water in the reaction system. After 1 h, stop heating. After the reaction reaches room temperature, add the well-mixed sublimed sulfur (27.5 g) and powdered p-tert-butylphenol (65 g) to the three-necked flask. Under nitrogen protection, slowly raise the temperature to 230 °C with mechanical stirring, stir and react for 3 to 4 hours, stop the reaction and take out the mechanical stirring paddle, and cool to room temperature. Add diethyl ether (140 mL) and toluene (35 mL) in sequence, continue stirring until the solid is evenly dispersed, add dilute sulfuric acid (4 M H 2 SO 4 140 mL) and continue stirring thoroughly. Filter under reduced pressure and rinse with alcohol to obtain the solid crude product, and purify it by recrystallization with chloroform.

[0058] Example 1

[0059] Put H 4 TC4A (0.025 mmol), Tb(AcO) 3 ·6H 2 O (0.05 mmol), H 2 OBBA (0.05 mmol) into a glass bottle, add CH 3 OH (3 mL) and DMF (0.5 mL), and ultrasonically form a mixed solution. Then transfer the above mixed solution to a reaction kettle with a polytetrafluoroethylene lining, put it into an oven, and set the oven program to heat to 130 °C within 100 min, keep the temperature constant for 72 h, then cool to room temperature at 4 °C / h, filter, and wash with methanol to obtain coordination polymer 1, which is a blocky pale yellow crystal with a yield of 70.1%.

[0060] Structure and Property Characterization

[0061] 1. Crystal Structure

[0062] The crystal structure analysis was carried out by single-crystal X-ray diffraction technology, and a Bruker D8 QUEST (Cu-Kα, ) instrument was used for collection, and the diffraction data was corrected for reduction and absorption. The crystal structure of coordination polymer 1 was analyzed by the direct method, and the crystal structure was refined by the F 2 full matrix least squares method. During the refinement process, all non-hydrogen atoms were refined anisotropically. For the carbon atoms in the compound, the method of theoretical hydrogen addition was used, and for the oxygen atoms, hydrogen atoms were added manually. The crystal refinement parameters of coordination polymer 1 are shown in Table 1.

[0063] Table 1

[0064]

[0065]

[0066] The results of crystal structure analysis show that, as shown in a of Figure 1 , the basic structural unit of Tb(III) coordination polymer 1 contains four central Tb 3+ , two 4-tert-butylthiacalix[4]arenes, four 4,4'-oxydibenzoic acids, four methanol molecules and one OH - , and four Tb 3+ all exhibit a nine-coordination mode.

[0067] The four central Tb 3+ mentioned above coordinate and form bonds in the following way: four Tb 3+ coordinate and form bonds with eight sulfur atoms and eight oxygen atoms in two 4-tert-butylthiacalix[4]arenes, four oxygen atoms in four 4,4'-oxydibenzoic acids, oxygen atoms in four methanol molecules and the oxygen atom in one OH - .

[0068] In the basic structural unit of the one-dimensional Tb(III) coordination polymer of the present invention, the four central metal Tb1 and Tb2, as well as Tb1# and Tb2#, are connected by a μ4-O to form a Tb 4 nucleus, as shown in the left figure of a in Figure 1 , and each Tb 3+ is nine-coordinated. Among them, as shown in the middle figure and the right figure of a in Figure 1 , seven coordination sites are coordinated with a μ4-O, and the H 4 at both ends of TC4A molecules each provide two phenolic hydroxyl oxygen atoms and one sulfur atom to coordinate with it to form a four-nuclear secondary structure Tb 4 (TC4A) 2 , and the remaining two coordination sites are occupied by oxygen atoms provided by 4,4'-oxydibenzoic acid ligands and solvent molecules. The four-nuclear secondary structure units are connected by 4,4'-oxydibenzoic acid to form a one-dimensional structure, as shown in b and c of Figure 1 .

[0069] 2. Powder X-ray diffraction (PXRD) analysis

[0070] The PXRD analysis of coordination polymer 1 was carried out using a Bruker D8 Advance X-ray powder diffractometer in Germany, and combined with the crystal structure data of coordination polymer 1, a simulated diagram was obtained through Mercury software.

[0071] Figure 2 shows the powder X-ray diffraction pattern and the simulated diagram of coordination polymer 1. See Figure 2, the powder X-ray diffraction pattern of coordination polymer 1 coincides with its simulated curve, indicating the successful synthesis of the coordination polymer and the relatively high phase purity of the sample.

[0072] 3. Fluorescence analysis

[0073] The solid-state luminescence properties of coordination polymer 1 were studied at ambient temperature. The solid-state spectra and lifetimes were measured on an Edinburgh FLS1000 steady-state and transient fluorescence spectrometer, and the absolute quantum yield was measured on a C9920-2.

[0074] See Figure 3 a of, the emission spectrum of coordination polymer 1 under 364 nm excitation shows emission peaks at 490, 548, 586, 622, 649, 668, and 679 nm, showing the characteristic emission of Tb 3+ characteristic emission.

[0075] The results of the fluorescence lifetime test are as shown in Figure 3 b of, and the fitted calculated lifetime is 1.20 ms. The measured solid-state quantum yield is 6.5%.

[0076] 4. Stability detection

[0077] Prepare aqueous solutions with pH = 1, 6, 9, 14:

[0078] Prepare a sodium hydroxide aqueous solution with pH = 14: Weigh 2 g of solid NaOH, add the weighed sodium hydroxide to a small amount of pure water, stir with a glass rod until completely dissolved, and transfer the cooled solution along the wall to a 50 mL volumetric flask. Dilute to the scale of the volumetric flask with pure water, shake well, and calibrate the pH value of the solution with a pH meter.

[0079] Prepare an HCl aqueous solution with pH = 1: Take 0.5 mL of 10 M concentrated hydrochloric acid, slowly add it to about 40 mL of deionized water, stir evenly, transfer to a 50 mL volumetric flask, and dilute to the scale line, and calibrate the pH value with a pH meter.

[0080] Dilute the above NaOH / HCl aqueous solutions to aqueous solutions with pH = 9 or 6, and calibrate with a pH meter.

[0081] Place coordination polymer 1 in organic solvents such as CH 3 OH, CHCl 3 , CH 3 COCH 3 , DMF and in aqueous solutions with different pH values (pH = 1, 6, 9, 14), and after sealing and placing at room temperature for two days, perform PXRD analysis and fluorescence analysis as above respectively. The results are shown in Figure 4 and Figure 5 .

[0082] It was found that the powder X-ray diffraction curve still coincided with the simulated curve, as shown in Figure 4 a of Figure 5 and a of Figure 4 b of Figure 5 and b of

[0083] 5. Thermosensitivity test

[0084] To study the temperature-dependent fluorescence properties of coordination polymer 1, fluorescence analysis of coordination polymer 1 was carried out as above at temperatures from 323 K to 448 K.

[0085] Figure 6 shows the 5 D 4 → 7 F 5 normalized temperature-dependent intensity and its fitting line graph (a) and relative sensitivity values at different temperatures (b). As shown in Figure 6 , as the temperature increases, the fluorescence intensity gradually decreases. In this temperature range, it conforms to the linear equation: I = 3.0138 - 0.00625·T, where I represents the fluorescence quenching rate and T represents the temperature value. The experimental data fits well with the linear equation, and R 2 = 0.9993, with a relatively high relative thermal sensitivity, up to 8.743%·K -1 .

[0086] Examples 2 - 5

[0087] A one-dimensional Tb(III) coordination polymer material was synthesized in the same manner as in Example 1, except that the organic solvent was changed as shown in Table 2.

[0088] Table 2

[0089] Example Organic solvent Yield 2 <![CDATA[CH 3 OH(3 mL)+DMF(1 mL)]]> 65.8％ 3 <![CDATA[CH 3 OH(2mL)+DMF(2mL)]]> 22.2％ 4 <![CDATA[CH 3 OH(1 mL)+DMF(3 mL)]]> 18.9％ 5 <![CDATA[CH 3 OH(0.5mL)+DMF(3mL)]]> 19.6％

[0090] From the results of Examples 1 - 5, it can be seen that based on 0.05 mmol of Tb, when the reaction organic solvent is 3 mL of CH 3 OH and 0.5 mL of DMF, the yield is the best.

[0091] Example 6

[0092] Dissolve H 4 TC4A (0.025 mmol), Tb(AcO) 3 ·6H 2 O (0.05 mmol), H 2OBBA (0.05 mmol) was weighed into a glass bottle, 3 mL of methanol and 0.5 mL of DMF were added, and the mixture was sonicated to form a mixed solution. Then, the above mixed solution was transferred to a reaction kettle with a polytetrafluoroethylene liner, placed in an oven, and the oven program was set to heat up to 110 °C within 100 min, keep the temperature constant for 72 h, and then cool down to room temperature at 4 °C / h. After filtration and washing with methanol, blocky pale yellow crystals were obtained, and the yield was 20.1%.

[0093] Examples 7 - 10

[0094] Except for changing the reaction temperature as shown in Table 3, the one-dimensional Tb(III) coordination polymer fluorescent material was synthesized in the same manner as in Example 6.

[0095] Table 3

[0096] Example Reaction temperature Yield 7 120℃ 50.8％ 8 130℃ 70.1％ 9 140℃ 71.9％ 10 150℃ 69.1％

[0097] From the results of Examples 6 - 10, it can be seen that when the reaction temperature is about 130 - 150 °C, the yield is the best.

[0098] Example 11

[0099] H 4 TC4A (18.1 mg, 0.025 mmol), Tb(AcO) 3 ·6H 2 O (16.8 mg, 0.05 mmol), H 2 OBBA (12.9 mg, 0.05 mmol) was weighed into a glass bottle, 3 mL of methanol and 0.5 mL of DMF were added, and the mixture was sonicated to form a mixed solution. Then, the above mixed solution was transferred to a reaction kettle with a polytetrafluoroethylene liner, placed in an oven, and the oven program was set to heat up to 130 °C within 100 min, keep the temperature constant for 48 h, and then cool down to room temperature at 4 °C / h. After filtration and washing with methanol, blocky pale yellow crystals were obtained, and the yield was 38.4%.

[0100] Examples 12 - 13

[0101] Except for changing the reaction time as shown in Table 4, the one-dimensional Tb(III) coordination polymer fluorescent material was synthesized in the same manner as in Example 11.

[0102] Table 4

[0103] Example Reaction time Yield 12 72h 70.1％ 13 96h 72.6％

[0104] From the results of Examples 11 - 13, it can be seen that the yield increases with the increase of the reaction time, and when it is above 72 h, the increasing amplitude slows down. Therefore, the reaction time is preferably above 72 h.

[0105] The present invention provides a one-dimensional Tb(III) coordination polymer co-assembled by thiacalix[4]arene and V-shaped dicarboxylic acid ligands, with a simple synthesis method, readily available raw materials, low cost, high yield and good reproducibility. In addition, there is a very good linear relationship between the fluorescence intensity and temperature of the one-dimensional Tb(III) coordination polymer of the present invention, providing new ideas for the further development of novel temperature-sensitive fluorescence sensing materials and devices.

[0106] The above has described the embodiments of the present invention in detail, but the present invention is not limited to the described embodiments. For those skilled in the art, without departing from the principle and spirit of the present invention, various changes, modifications, substitutions and variations made to these embodiments still fall within the protection scope of the present invention.

Claims

1. A one-dimensional Tb(III) coordination polymer, the chemical formula of which is: [Tb4(TC4A 4- )(HTC4A 3- )(OBBA 2- )2(CH3OH)4(µ4-OH)] n 4 in, TC4A 4- / HTC4A 3- To deprotonate 4-tert-butylthiacalix[4]arene, OBBA 2- To deprotonate 4,4'-diphenyl ether dicarboxylic acid, n represents the degree of polymerization, which is a positive integer.

2. The one-dimensional Tb(III) coordination polymer according to claim 1, characterized in that The one-dimensional Tb(III) coordination polymer is a monoclinic crystal with a P21 / c space group and unit cell parameters: α=90°, β=130.9770(10)°, γ=90°, Z=2.

3. A method for preparing the one-dimensional Tb(III) coordination polymer according to claim 1 or 2, comprising: S1: mixing 4-tert-butylthiacalix[4]arene, 4,4'-diphenylether dicarboxylic acid, methanol and a Tb(III) ion source to obtain a mixed solution; S2: The mixed solution obtained in the above step S1 is reacted by a solvothermal method to obtain a one-dimensional Tb(III) coordination polymer.

4. The method according to claim 3, characterized in that In step S1, The source of Tb(III) ions is selected from inorganic or organic acid salts of Tb(III), such as nitrates, hydrochlorides, sulfates, acetates and solvates thereof, such as terbium nitrate hexahydrate, terbium sulfate octahydrate, terbium acetate hydrate; and / or The molar ratio of 4-tert-butylthiacalix[4]arene, 4,4'-diphenylether dicarboxylic acid and Tb(III) ion is 0.5-1.5:1-3:1-3, preferably 1:2:2; and / or The amount of methanol used is 10 mL or more, preferably 60 mL or more, and 200 mL or less, 100 ml or less, based on 1 mmol of Tb(III) ions.

5. The method according to claim 3, characterized in that: In step S1, other organic solvents, such as dimethylformamide and dimethylacetamide, may also be added; Particularly, the volume ratio of the other organic solvent to methanol is 10:1 to 1:0, preferably 6:1 to 1:

6.

6. The method according to claim 5, characterized in that In step S1, 4-tert-butylthiacalix[4]arene, 4,4'-diphenyl oxide dicarboxylic acid, terbium acetate, methanol and dimethylformamide are mixed to obtain a mixed solution, wherein the molar ratio of 4-tert-butylthiacalix[4]arene, 4,4'-diphenyl oxide dicarboxylic acid and Tb(III) ions is 1:2:2, based on 1 mmol of Tb(III) ions, the total amount of methanol and dimethylformamide is 60-100 mL, and the volume ratio of methanol and dimethylformamide is 6:1 to 1:

6.

7. The method according to claim 3, characterized in that In step S2, the solvothermal method is performed in a closed system.

8. The method according to claim 3, characterized in that In step S2, The reaction temperature of the solvothermal method is 100-200°C, preferably 120-180°C, especially 130-150°C; and / or The reaction time is more than 1 hour, more than 5 hours, more than 12 hours, or more than 24 hours.

9. The method according to claim 3, characterized in that: Step S2 includes a post-treatment step, including cooling, filtering, and washing the obtained solid; Particularly, the washing solvent is an alcohol solvent, such as methanol or ethanol.

10. Use of the one-dimensional Tb(III) coordination polymer according to claim 1 or 2 in preparing a green fluorescent material or device, and / or use of the one-dimensional Tb(III) coordination polymer in preparing a temperature-sensitive fluorescent material or device.

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