Achieving ultra-long near-infrared room-temperature phosphorescence Cu(I)-MOF coordination compound SUST-WZ3 and its preparation method

Abstract

A Cu(I)-MOF coordination compound SUST-WZ3 that achieves ultra-long near-infrared room temperature phosphorescence and a preparation method thereof, wherein the molecular formula of the functionalized metal-organic framework compound is C 48 H 28 Cu4N 16 The coordination compound is self-assembled by hydrothermal reaction using 1,4-bis(4-(1H-tetrazolyl-5-yl)phenyl)naphthalene (H2DTzDphNap, hereinafter referred to as Tz-Nap) as an organic ligand and cuprous iodide as a metal salt. The coordination compound SUST-WZ3 exhibits metal-ligand charge transfer transition (MLCT) emission in the 450-505 nm range (1.07, 2.29, and 5.38 μs at 450, 475, and 505 nm, respectively), triplet emission at 705 nm, and a lifetime of 1.85 ms at 300 K and 25.16 ms at 77 K. White light can be obtained by adjusting the relative intensities of the doublets. Furthermore, under low-temperature conditions, the near-infrared (NIR) long-persistence luminescence (LPL) of SUST-WZ3 can be observed with the naked eye.

Description

Technical Field

[0001] The present invention belongs to the technical field of ultra-long near-infrared room temperature phosphorescent materials, and specifically relates to an organic ligand 1,4-bis(4-(1H-tetrazolyl-5-yl)phenyl)naphthalene (Tz-Nap) and Cu + A self-assembled metal organic framework coordination complex and a preparation method thereof. Background Art

[0002] Room temperature phosphorescence (RTP) materials have been widely used in various fields such as chemical sensors, bioimaging, lighting, and anti-counterfeiting. However, most materials cannot emit RTP due to low intersystem crossing (ISC) efficiency and high non-radiative decay constant. It is well known that the ISC efficiency and non-radiative decay constant are closely related to factors such as heavy atoms, oxygen, and temperature, respectively, which makes RTP more difficult. In particular, long-lasting luminescence (LPL), which can be found in some ultra-long RTP materials, is a phenomenon in which light is emitted for a considerable period of time after light irradiation has ceased, and is particularly suitable for night vision, barcoding and encryption, and display.

[0003] Metal-organic frameworks (MOFs) are combinations of metal ions or metal clusters and organic molecules, which act as nodes and connectors, respectively. Among them, luminescent MOFs (LMOFs) with delicate structures and complex luminescence properties have been widely studied. For most MOFs, the decay lifetime is usually in the nanosecond range, which can be attributed to singlet fluorescence. Recently, some LMOFs containing iridium, ruthenium, platinum-based noble metals and europium / terbium-based rare earths with microsecond lifetimes have been reported. In these MOFs, due to the strong spin-orbit coupling (SOC) imparted by the heavy metals, singlet excitons can be downconverted to triplet excited states through ISC. However, the high cost, unclear toxicity and limitation of these complexes to visible light emission can be disadvantageous. Therefore, the synthesis of efficient LMOFs rich in rare earth metals such as Cu(I) has attracted great attention.

[0004] Contains d 10Cu(I)-MOFs with structured Cu(I) ions have attracted extensive attention in luminescent sensing, but few reports have been published due to the difficulty of their synthesis. However, over the past two decades, a variety of Cu(I) complexes have been developed based on their interesting properties and applications. Currently, most reported Cu(I) materials, whether TADF or phosphorescent, typically exhibit decay lifetimes of microseconds under ambient conditions. The reasons are as follows: (1) Based on the fluorescence properties, the ligands in common complexes are small molecules with low conjugation, so they cannot emit ligand phosphorescence after chelating with Cu(I) atoms because the SOC of the metal is weak compared with Cd(II) or Ir(III), and only complex triplet emission is generated, including metal-ligand charge transfer (MLCT), cluster center (CC), etc.; (2) In materials with both TADF and phosphorescence, long-lived triplet excitons are consumed because most excitons return to the short-lived singlet state through reverse intersystem crossing (RISC), and only a small part returns to the ground state through triplet radiative transition; (3) The small difference in energy levels between multiple triplets (such as the triplet state of MLCT and the triplet state of the ligand center) causes them to vibrate and merge into one of the triplet states, resulting in non-radiative deactivation, which makes the complex non-luminescent or greatly shortens the luminescence lifetime, limiting their application in RTP / LPL. Therefore, it is urgent to develop Cu(I)-MOFs with long RTP lifetime. Summary of the Invention

[0005] The purpose of the present invention is to provide a D-π-A-π-D Cu(I) metal-organic framework (MOFs) coordination compound SUST-WZ3 that achieves ultralong near-infrared room-temperature phosphorescence and a preparation method thereof. The metal-organic framework coordination compound is self-assembled by a hydrothermal reaction using Tz-Nap as an organic ligand and cuprous iodide. The coordination compound has an ultralong NIR lifetime of 1.85 ms at ambient temperature and achieves deep red LPL at 77 K. A detailed study of the photophysical properties of SUST-WZ3 shows that the observed emission originates from a combination of HE MLCT and LE NIR RTP. The excellent photophysical properties of SUSTWZ3 can be attributed to the synergistic effect of D-π-A-π-D type ligands, enhanced SOC and the rigid environment of the framework. The technical problem to be solved is to overcome the short decay lifetime of Cu(I)-MOF under ambient conditions and its limited application in RTP / LPL.

[0006] In order to achieve the above object, the technical solution adopted by the present invention is:

[0007] A D-π-A-π-D Cu(I) metal-organic framework (MOFs) coordination compound SUST-WZ3 that achieves ultralong near-infrared room temperature phosphorescence, characterized in that the molecular formula is: C 48 H 28Cu4N 16 , molecular weight is 1083.02; it belongs to the triclinic crystal system, and the space group of the triclinic crystal system is P-1.

[0008] Furthermore, the coordination compound SUST-WZ3 was obtained by hydrothermal reaction using 1,4-bis(4-(1H-tetrazol-5-yl)phenyl)naphthalene as the organic ligand and cuprous iodide as the metal salt.

[0009] Furthermore, the preparation method of the coordination compound SUST-WZ3 comprises the following steps:

[0010] Step 1, cuprous iodide and Tz-Nap are mixed in a molar mass ratio of 1 to 5:1, and the mixture is put into a stainless steel high-pressure reactor. N, N-dimethylformamide, water, and hydrochloric acid aqueous solution are added to the reactor in a molar mass ratio of 5 to 10:3 to 6:1 to 3, and the mixture is stirred evenly. The amount ratio of N, N-dimethylformamide to Tz-Nap is 5 to 10 mL:0.1 mmol, the amount ratio of water to Tz-Nap is 3 to 6 mL:0.1 mmol, and the amount ratio of hydrochloric acid aqueous solution to Tz-Nap is 1 to 6 mL:0.1 mmol;

[0011] Step 2: Heat the mixture in a sealed pressure-resistant reactor from room temperature to 120-140°C for 1-3 hours, maintain this temperature for 40-60 hours, and then cool it down to room temperature for 8-12 hours;

[0012] Step 3: After cooling to room temperature, pink block crystals are obtained, which are filtered and washed with N,N-dimethylformamide to obtain pure crystals as the coordination compound SUST-WZ3.

[0013] Furthermore, in the step 1, the molar ratio of cuprous iodide to Tz-Nap is 2:1, the volume ratio of N,N-dimethylformamide, water and aqueous hydrochloric acid solution is 6:4:2, the amount ratio of N,N-dimethylformamide to Tz-Nap is 6 mL:0.1 mmol, the amount ratio of water to Tz-Nap is 1-5 mL:0.05 mmol, and the amount ratio of aqueous hydrochloric acid solution to Tz-Nap is 2 mL:0.1 mmol.

[0014] Furthermore, in step 2, the temperature is raised to 140° C. for 2 h, maintained at this temperature for 48 h, and then cooled to room temperature for 10 h.

[0015] Furthermore, the preparation method of the coordination compound SUST-WZ3 single crystal is as follows: a mixture of Tz-Nap (41.7 mg, 0.1 mmol) and cuprous iodide (38.0 mg, 0.2 mmol) is added to a polytetrafluoroethylene liner of a 25 mL reactor, and then 6 mL of N,N-dimethylformamide, 4 mL of water and 2 mL (1 mol / L) of hydrochloric acid aqueous solution are added, stirred evenly, and placed in a matching stainless steel high-temperature reactor; then the reactor is placed in an electric blast drying oven, the temperature is programmed to rise to 140°C for 2 hours, this temperature is maintained for 48 hours, and then cooled to room temperature after 10 hours; finally, it is filtered and washed to obtain a pink block single crystal SUST-WZ3.

[0016] Furthermore, the preparation process of the 1,4-bis(4-(1H-tetrazol-5-yl)phenyl)naphthalene is as follows:

[0017] Step 1, preparation of 4,4'-(naphthalene-1,4-diyl)dibenzonitrile:

[0018] Under a nitrogen atmosphere, 1,4-dibromonaphthalene, 4-cyanophenylboronic acid, tetrakis(triphenylphosphine)palladium, and potassium carbonate in a molar mass ratio of 15-25:45-65:0.5-0.7:95-115 are added to a round-bottom flask containing toluene, mixed evenly, heated under reflux, and cooled to room temperature after the reaction is complete, and the intermediate product 4,4'-(naphthalene-1,4-diyl)dibenzonitrile is obtained through separation;

[0019] Step 2, preparation of 1,4-bis(4-(1H-tetrazol-5-yl)phenyl)naphthalene:

[0020] The intermediate product 4,4'-(naphthalene-1,4-diyl)dibenzonitrile obtained in step S1 is dissolved in a round-bottom flask containing a DMF solution, and then an excess of sodium azide and ammonium chloride are added, wherein the molar mass ratio of the 4,4'-(naphthalene-1,4-diyl)dibenzonitrile, sodium azide, and ammonium chloride is 15-25:15-35:15-35. The mixture is mixed evenly and heated to reflux. After the reaction is complete, the reaction mixture is poured into an ice water / hydrochloric acid aqueous solution to precipitate, and the precipitate is filtered to obtain the target product 1,4-bis(4-(1H-tetrazol-5-yl)phenyl)naphthalene.

[0021] Furthermore, in step 1, the reflux temperature is 100-120° C. and the time is 40-60 h; in step 2, the reflux temperature is 110-130° C. and the time is 40-60 h.

[0022] The present invention is relative to the prior art:

[0023] After extensive research and exploration, the present invention has prepared a Cu(I) metal-organic framework (MOFs) coordination compound SUST-WZ3 based on D-π-A-π-D ligands with ultra-long near-infrared room temperature phosphorescence. The present invention uses Tz-Nap as an organic ligand and cuprous iodide as a metal salt to synthesize the coordination compound SUST-WZ3 through a hydrothermal reaction method. The molecular formula is: Cu4C 48 H 28 N 16 The single crystal of suitable size was selected for single crystal diffraction. The results showed that SUST-WZ3 crystallized in the triclinic system and belonged to the P-1 space group. The asymmetric unit consists of two Tz-Nap 2- ligands, four Cu(I) and some lattice solvent molecules. At the same time, the porosity is estimated to be 17.5%. We can see that all Cu(I) are tri-coordinated, and the coordinated N atoms come from three Tz-Nap 2- Ligand. In SUST-WZ3, there are four Cu(I) centers bridged by four tetrazole groups in a short range, forming a tetranuclear Cu(I)-cluster. The distances between adjacent Cu…Cu of Cu1…Cu4, Cu2…Cu3 and Cu3…Cu4 are 3.794, 3.544 and Cu1 bridges the four-core clusters over long distances to form a one-dimensional Cu ribbon, while Cu4 further connects the Cu ribbons to form a double-layer Cu network. There is a strong accumulation of Cu(I)-clusters in the Cu network with a distance of This greatly rigidifies the ligand, which is beneficial for molecular luminescence. 2- All adopt six teeth (μ6-η 1 :η 1 :η 1 :η 0 :η 1 :η 1 :η 1 :η 0 ) coordination mode connects the six Cu + atoms. Finally, they form a two-dimensional (2D) framework structure by connecting with each other. In addition, the non-covalent interactions between the molecules connecting these 2D skeletons give a 3D framework ( Figure 2 Such a compact and interesting microporous framework encourages us to further explore its photophysical properties and potential applications.

[0024] The technical problem to be solved by the present invention is to solve the short decay lifetime of Cu(I)-MOF under ambient conditions and its limited application in RTP / LPL, etc., and provide a metal-organic framework coordination compound SUST-WZ3 based on D-π-A-π-D ligands. The coordination compound shows dual phosphorescence emission of Cu-based MLCT and RTP inherited from the ligands. Their phosphorescence emission peaks are in the range of 450-505nm and 705nm, with lifetimes of 1-5us and 1.85ms, respectively. White light is obtained by adjusting the relative intensity of the double peaks. In addition, deep red LPL is observed with the naked eye under low temperature conditions. The ultra-long RTP can be attributed to the increase in SOC induced by the Cu(I) network and the strong intermolecular / intramolecular interactions and the suppression of molecular vibrations by the dense skeleton structure.

[0025] The present invention has the following beneficial effects:

[0026] (1) The metal-organic framework coordination compound SUST-WZ3 based on D-π-A-π-D ligands provided by the present invention;

[0027] (2) The coordination compound SUST-WZ3 exhibits an ultralong NIR lifetime of 1.85 ms at ambient temperature and achieves deep red LPL at 77 K. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] Figure 1 This is the hydrogen nuclear magnetic resonance spectrum of the organic ligand 1,4-bis(4-(1H-tetrazol-5-yl)phenyl)naphthalene (Tz-Nap) prepared in Example 1.

[0029] Figure 2 Crystal structure of SUST-WZ3. a) Asymmetric unit; b) Cu network formed by Cu(I) and tetrazolyl groups; c) 2D framework; d, e) 3D framework assembled through intermolecular interactions and simplified 3D networks.

[0030] Figure 3 This is the infrared spectrum of SUST-WZ3.

[0031] Figure 4 PXRD spectra of simulated and synthesized SUST-WZ3.

[0032] Figure 5 This is the TGA diagram of SUST-WZ3.

[0033] Figure 6 a) Excitation and emission spectra, and b) decay curves of H2DTzDphNap in solid and air.

[0034] Figure 7Room-temperature photoluminescence characteristics of SUST-WZ3: a) Prompt and delayed (1 ms) emission spectra under 365 nm excitation; b) Decay curves at 450 nm, 475 nm, and 505 nm at room temperature.

[0035] Figure 8 Excitation and emission spectra of SUST-WZ3.

[0036] Figure 9 These are the time-resolved emission spectra of SUST-WZ3 from microseconds to milliseconds.

[0037] Figure 10 Figure 5 is the excitation-related emission spectrum of SUST-WZ3 from 270 nm to 450 nm at 300 K and the corresponding CIE.

[0038] Figure 11 Emission spectra of SUST-WZ3 in air and vacuum. a) Normalized spectrum and b) original spectrum.

[0039] Figure 12 Figure 3 shows the temperature-dependent emission spectrum of SUST-WZ3 from 77 to 300 K and the corresponding CIE coordinates.

[0040] Figure 13 Attenuation curves of SUST-WZ3 at 600, 650, and 705 nm at RT and 77 K.

[0041] Figure 14 The emission spectra of SUST-WZ3 at different grinding times and the corresponding CIE (inset: luminescence image under a 365nm flashlight).

[0042] Figure 15 The emission spectra of SUST-WZ3 after milling at different times.

[0043] Figure 16 This is the energy transfer mechanism of SUST-WZ3. DETAILED DESCRIPTION

[0044] The present invention will be further described below with reference to the accompanying drawings and specific examples, but the examples do not limit the present invention in any way. Unless otherwise specified, the reagents, methods and equipment used in the present invention are conventional reagents, methods and equipment in the art.

[0045] Unless otherwise specified, the reagents and materials used in the following examples were commercially available.

[0046] The instrument used is: single crystal data with copper target The IR data were measured using a Nicolet / Nexus-670 Fourier transform infrared spectrometer at 4000-400 cm -1 The samples were collected using the potassium bromide pellet method and compressed using a Specac mini-pill press. Powder X-ray diffraction (PXRD) was measured using a Rigaku SmartLab diffractometer (Bragg-Brentano geometry, Cu kα1 radiation, λ = 1.54056A). Thermogravimetry was performed under nitrogen and 1 atm pressure at a temperature of 10 °C min -1 Thermogravimetric analysis (TGA) of the heating rates was performed on a NETZSCH TG209 system; UV-visible absorption spectra were recorded using a Shimadzu UV-2450 spectrophotometer; and fluorescence spectra were measured using an Edinburgh FLS 980 and Horiba spectrometers. Long-lasting luminescence was measured using an EQ65 Pro instrument; photos and videos of the LPL were recorded using a smartphone.

[0047] Example 1 Preparation of coordination compound SUST-WZ3

[0048] Preparation of coordination compound SUST-WZ3:

[0049] A mixture of Tz-Nap (41.7 mg, 0.1 mmol) and cuprous iodide (38.0 mg, 0.2 mmol) was added to a 25 mL polytetrafluoroethylene liner, and 6 mL of N,N-dimethylformamide, 4 mL of distilled water, and 2 mL (1 mol / L) of hydrochloric acid aqueous solution were added. The mixture was placed in a matching stainless steel high-temperature reactor, and then the reactor was placed in an electric blast drying oven. The temperature was raised to 110°C for 2 h, maintained at this temperature for 48 h, and cooled to room temperature for 12 h. Finally, the resulting mixture was filtered and washed to obtain pink block single crystals.

[0050] Example 2 Crystal structure determination of coordination compound SUST-WZ3

[0051] Equipped with a copper target Single-crystal X-ray diffraction data of SUST-WZ3 were collected on a Rigaku-Oxford Supernova X-ray diffractometer system at 50 kV and 0.80 mA.

[0052] The structure was solved using a direct method and refined using the full-matrix least-squares method with the SHELXL-2014 package. All hydrogen atoms were obtained using theoretical hydrogenation and refined along the anisotropic direction. The crystallographic data for SUST-WZ3 are shown in Table 1.

[0053] Table 1 is the crystallographic data of the coordination compound SUST-WZ3

[0054]

[0055]

[0056] from Figure 2 It can be seen that SUST-WZ3 is a 3D network structure of multi-core clusters. There is a strong accumulation of Cu(I)-clusters in the Cu network, which greatly rigidifies the ligand and is conducive to molecular luminescence.

[0057] Example 3 Optical Properties of SUST-WZ3

[0058] The diffraction peaks measured by X-ray powder diffraction (PXRD) experiments of the coordination compound SUST-WZ3 are basically consistent with the peaks simulated by single crystal data, indicating that SUST-WZ3 has a high phase purity ( Figure 4 The TGA curves show that from room temperature (RT) to 250 °C, the weight loss of SUST-WZ3 is about 8.2% attributed to the release of free guest molecules; from 250 to 350 °C, the weight is almost constant, indicating good framework stability ( Figure 5 ).

[0059] When Tz-Nap is excited at 350nm, its maximum peak is at 425nm ( Figure 6 ). Under 365nm excitation, SUST-WZ3 has four emission peaks at 450, 475, 505 and 705nm, respectively. In order to assign all emission peaks, time-gated and transient spectra were studied. Time-gated spectra showed that the peak near 705nm belongs to phosphorescence emission, which may come from T1 of Tz-Nap. At the same time, the decay curves of the peaks at 450, 475 and 505nm were further measured, which showed long microsecond lifetimes with values ​​of 1.07, 2.29 and 5.38μs, respectively, so the emission peaks at 450, 475 and 505nm are attributed to MLCT( Figure 7 and Figure 9 Time-resolved emission spectroscopy (TRES) confirmed that SUST-WZ3 is a dual phosphorescent emitter. Due to the coexistence of emission peaks at 450-505nm and 705nm, the luminescence color of the solid powder tends to be purple-red under the excitation of a 365nm UV flashlight. This study studied the excitation spectra of the two emission bands (MLCT and RTP) ( Figure 8 ), we found that there was a certain difference in its maximum excitation wavelength, which inspired us to adjust the color of the luminescence by changing the excitation wavelength. As the excitation wavelength shifted from 270nm to 450nm, the emission peak intensity at 705nm first increased and then weakened, and the luminescence color gradually changed from pink to green. When excited at 410nm, cold white light emission was observed ( Figure 10 ).like Figure 11As shown in Figure 2, the emission spectrum profile in air is almost unchanged compared to the emission spectrum in vacuum conditions, except that the near-infrared emission intensity in the latter is significantly enhanced. In order to further explore the RTP characteristics, the temperature-dependent spectrum was measured. Figure 12 As shown in the figure, as the temperature decreases, the emission intensity and phosphorescence lifetime of the sample gradually increase, further indicating the phosphorescence properties of the material. The corresponding color change can be obtained from CIE. At the same time, the lifetimes of the two peaks at 600nm and 650nm at 77K are calculated to be 32.01 and 31.83ms respectively ( Figure 13 ). It can be seen during the grinding process that the near-infrared triplet state is more susceptible to external influences. As the grinding time increases, MLCT dominates, so the overall photoluminescence gradually turns to blue light ( Figure 14 The RT oxygen reaction of SUST-WZ-3 was studied and it was found that MLCT and NIRRTP reacted to oxygen to different degrees. In a pure oxygen environment, the emission intensity of near-infrared RTP decreased rapidly with increasing oxygen pressure, while that of MLCT decreased slowly ( Figure 15 ). Based on the above experimental and theoretical results, the energy transfer mechanism of SUST-WZ3 is as follows Figure 16 As shown: First, the UV light energy is absorbed by Cu(I)-MOF and transferred to the excited singlet S n , which is converted to the singlet lowest excited state S1. Afterwards, energy is transferred from the S1 state to the high energy (HE) MLCT state (T HE ), emitting blue phosphorescence, and at the same time transitioning to the low energy (LE) state, emitting NIR phosphorescence (T LE ). After stopping the light irradiation, T LE The state can also be further relaxed to a lower energy T LE state, resulting in the unique NIR LPL phenomenon triggered by ultraviolet light in SUST-WZ3 at 77K.

[0060] The PXRD spectra of SUST-WZ3 simulation and synthesis are shown in Figure 2. Figure 4 shown.

[0061] The TGA chart of SUST-WZ3 is as follows Figure 5 shown.

[0062] The immediate and delayed (1ms) emission spectra of SUST-WZ3 under 365nm excitation and the decay curves at 450nm, 475nm and 505nm at room temperature are shown in Figure 2. Figure 7 shown.

[0063] The time-resolved emission spectra of SUST-WZ3 from microseconds to milliseconds are as follows: Figure 9 shown.

[0064] The excitation-related emission spectrum of SUST-WZ3 from 270nm to 450nm at 300K and the corresponding CIE Figure 10 shown.

[0065] The temperature-dependent emission spectrum of SUST-WZ3 from 77 to 300 K and the corresponding CIE coordinates are shown in Figure 2. Figure 12 shown.

[0066] The emission spectra of SUST-WZ3 at different grinding times and the corresponding CIE (inset: luminescence image under a 365nm flashlight) are shown in Figure 2. Figure 14 shown.

Claims

1. A Cu(I)-MOF coordination compound SUST-WZ3 that achieves ultra-long near-infrared room temperature phosphorescence, characterized in that: The molecular formula is: C 48 H 28 Cu4N 16 , molecular weight is 1083.02; belongs to the triclinic system, and the space group of the triclinic system is P -1, the asymmetric unit consists of two Tz-Nap 2- The ligand is composed of four Cu(I) and some lattice solvent molecules. All Cu(I) are tri-coordinated, and the coordinated N atoms come from three Tz-Nap 2- Ligands, in SUST-WZ3, there are four Cu(I) centers bridged by four tetrazole groups in a short range to form a tetranuclear Cu(I)-cluster, Cu1 bridges the tetranuclear clusters over a long distance to form a one-dimensional Cu ribbon, and Cu4 further connects the Cu ribbon to form a double-layer Cu network, in which Cu(I)-clusters accumulate, and all Tz-Nap 2- All adopt six teeth (μ6-η 1 :η 1 :η 1 :η 0 :η 1 :η 1 :η 1 :η 0 ) coordination mode connecting the six Cu + Atoms form a two-dimensional (2D) framework structure by connecting with each other, and the non-covalent interactions between the molecules connecting these 2D skeletons give a 3D framework; the coordination compound SUST-WZ3 is obtained by hydrothermal reaction using 1,4-bis(4-(1H-tetrazol-5-yl)phenyl)naphthalene as organic ligand and cuprous iodide as metal salt.

2. The Cu(I)-MOF coordination compound SUST-WZ3 for achieving ultra-long near-infrared room temperature phosphorescence according to claim 1, characterized in that: The preparation method of the coordination compound SUST-WZ3 comprises the following steps: Step 1. Cuprous iodide and Tz-Nap (1,4-bis(4-(1H-tetrazol-5-yl)phenyl)naphthalene) are mixed in a molar mass ratio of 1 to 5:1, and the mixture is placed in a stainless steel autoclave. N,N-dimethylformamide, water, and hydrochloric acid aqueous solution are added to the reactor in a molar mass ratio of 5 to 10:3 to 6:1 to 3, and the mixture is stirred evenly. The amount ratio of N,N-dimethylformamide and Tz-Nap (1,4-bis(4-(1H-tetrazol-5-yl)phenyl)naphthalene) is 5 to 10 mL: 0.1 mmol, the amount ratio of water to Tz-Nap is 3 to 6 mL: 0.1 mmol, and the amount ratio of hydrochloric acid aqueous solution to Tz-Nap is 1 to 6 mL: 0.1 mmol. Step 2: heating the mixture in a sealed pressure-resistant reactor from room temperature to 120-140°C for 1-3 hours, maintaining this temperature for 40-60 hours, and then cooling it to room temperature for 8-12 hours; Step 3: After cooling to room temperature, pink block crystals are obtained, which are filtered and washed with N,N-dimethylformamide to obtain pure crystals as the coordination compound SUST-WZ3.

3. The method for preparing the Cu(I)-MOF coordination compound SUST-WZ3 that realizes ultra-long near-infrared room temperature phosphorescence according to claim 2, characterized in that: In the step 1, the molar ratio of cuprous iodide to Tz-Nap is 2:1, the volume ratio of N,N-dimethylformamide, water and aqueous hydrochloric acid is 6:4:2, the amount ratio of N,N-dimethylformamide and Tz-Nap (1,4-bis(4-(1H-tetrazol-5-yl)phenyl)naphthalene) is 6 mL:0.1 mmol, and the amount ratio of water to Tz-Nap (1,4-bis(4-(1H-tetrazol-5-yl)phenyl)naphthalene) is 1 to 5 mL: The amount ratio of the hydrochloric acid aqueous solution and Tz-Nap (1,4-bis(4-(1H-tetrazol-5-yl)phenyl)naphthalene) is 2 mL:0.1 mmol.

4. The method for preparing the Cu(I)-MOF coordination compound SUST-WZ3 for achieving ultra-long near-infrared room temperature phosphorescence according to claim 3, characterized in that: In step 2, the temperature is raised to 140° C. for 2 h, maintained at this temperature for 48 h, and then cooled to room temperature for 10 h.

5. The method for preparing the Cu(I)-MOF coordination compound SUST-WZ3 that realizes ultra-long near-infrared room temperature phosphorescence according to claim 3, characterized in that: The preparation method of the coordination compound SUST-WZ3 single crystal is as follows: a mixture of Tz-Nap (1,4-bis(4-(1H-tetrazol-5-yl)phenyl)naphthalene) and cuprous iodide is added to a polytetrafluoroethylene-lined 25 mL reactor, followed by the addition of 6 mL of N,N-dimethylformamide, 4 mL of water, and 2 mL of (1 mol / L) hydrochloric acid aqueous solution. The mixture is stirred evenly and placed in a matching stainless steel high-temperature reactor. The reactor is then placed in an electric blast drying oven, the temperature is programmed to rise to 140°C over 2 hours, the temperature is maintained at this temperature for 48 hours, and then the temperature is cooled to room temperature over 10 hours. Finally, the reaction mixture is filtered and washed to obtain a pink block single crystal of SUST-WZ3.

6. The method for preparing the Cu(I)-MOF coordination compound SUST-WZ3 that realizes ultra-long near-infrared room temperature phosphorescence according to claim 2, characterized in that: The preparation process of Tz-Nap (1,4-bis(4-(1H-tetrazol-5-yl)phenyl)naphthalene) is as follows: Step 1, preparation of 4,4'-(naphthalene-1,4-diyl)dibenzonitrile: Under a nitrogen atmosphere, 1,4-dibromonaphthalene, 4-cyanophenylboronic acid, tetrakis(triphenylphosphine)palladium, and potassium carbonate in a molar mass ratio of 15-25:45-65:0.5-0.7:95-115 are added to a round-bottom flask containing toluene, mixed evenly, heated under reflux, and cooled to room temperature after the reaction is complete, and the intermediate product 4,4'-(naphthalene-1,4-diyl)dibenzonitrile is obtained through separation. Step 2, preparation of 1,4-bis(4-(1H-tetrazol-5-yl)phenyl)naphthalene: The intermediate product 4,4'-(naphthalene-1,4-diyl)dibenzonitrile obtained in step S1 is dissolved in a round-bottom flask containing a DMF solution, and then an excess of sodium azide and ammonium chloride are added, wherein the molar mass ratio of the 4,4'-(naphthalene-1,4-diyl)dibenzonitrile, sodium azide, and ammonium chloride is 15-25:15-35:15-35. The mixture is mixed evenly and heated to reflux. After the reaction is complete, the reaction mixture is poured into an ice water / hydrochloric acid aqueous solution to precipitate, and the precipitate is filtered to obtain the target product 1,4-bis(4-(1H-tetrazol-5-yl)phenyl)naphthalene.

7. The method for preparing the Cu(I)-MOF coordination compound SUST-WZ3 for achieving ultra-long near-infrared room temperature phosphorescence according to claim 6, characterized in that: In step 1, the reflux temperature is 100-120° C. and the reaction time is 40-60 h. In step 2, the reflux temperature is 110-130° C. and the reaction time is 40-60 h.

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