CN112724179A - Neutral metal complex iridium-bipyridyl dicarboxylic acid crystal material and preparation method thereof - Google Patents
Neutral metal complex iridium-bipyridyl dicarboxylic acid crystal material and preparation method thereof Download PDFInfo
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- 239000000126 substance Substances 0.000 claims abstract description 7
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- KVQMUHHSWICEIH-UHFFFAOYSA-N 6-(5-carboxypyridin-2-yl)pyridine-3-carboxylic acid Chemical compound N1=CC(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C=N1 KVQMUHHSWICEIH-UHFFFAOYSA-N 0.000 claims abstract description 6
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- 239000012046 mixed solvent Substances 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
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- 229910052741 iridium Inorganic materials 0.000 claims description 4
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 4
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- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 0.000 abstract description 2
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/0033—Iridium compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/13—Crystalline forms, e.g. polymorphs
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Abstract
The invention belongs to the field of chemical sensors and the field of laser protection, and discloses a neutral metal complex iridium-bipyridyl dicarboxylic acid crystal material and a preparation method thereof. According to the invention, from the structure and performance of the complex, a 1-phenylpyrazole chelating ligand with better phosphorescence performance is selected to form phenylpyrazole cyclometaliridium dimer with trihydrate and iridium trichloride, and then the phenylpyrazole cyclometaliridium dimer is combined with an auxiliary ligand 2, 2-bipyridyl-5, 5' dicarboxylic acid by means of dichloro bridge breakage under a certain reaction condition to form the iridium-bipyridyl dicarboxylic acid metal complex. And then applying the principle of crystal engineering, adopting a high-temperature high-pressure reaction kettle method, namely hydro-thermal synthesis, and obtaining the crystal material by the iridium-bipyridyl dicarboxylic acid metal complex through the processes of crystal nucleus precipitation, crystal growth and the like under the conditions of high temperature and high pressure.
Description
Technical Field
The invention belongs to the field of chemical sensors and the field of laser protection, and particularly relates to a neutral metal complex iridium-bipyridyl dicarboxylic acid crystal material and a preparation method thereof.
Background
In recent years, metal organic compounds represented by cyclometalated ir (iii) complexes have been a research hotspot in the field of photoelectric functional materials and devices due to their potential application values in the fields of Organic Light Emitting Diodes (OLEDs), light emitting electrochemical cells (LECs), nonlinear optics (NLO), biological imaging, chemical sensing, photocatalysis, and the like. Compared with the traditional complex, the metal organic compound has the advantages of fast reaction time, low dielectric constant, flexible structure and the like. For example, metal-organic compounds have advantages over traditional complexes in the transfer of various forms of charge, such as low energy metal-to-ligand charge transfer (MLCT), ligand-to-metal charge transfer (LMCT), and ligand-to-ligand charge transfer (LLCT), among others. These properties have a very important influence on the properties of metal organic compounds, such as nonlinear optics (NLO) and chemical sensing. In addition, the structure and the performance of the cyclometalated Ir (III) complex can be effectively adjusted by changing the types of cyclometalated precursors, auxiliary ligands, counter ions and solvents. Therefore, the ring metal Ir (III) complex with a novel structure is synthesized by a simple and convenient preparation method explored by a molecular engineering technology, the photoelectric property of the complex is researched, and the corresponding crystal material is applied to the fields of chemical sensors and laser protection, so that the method has very important significance.
Disclosure of Invention
The conventional synthesis method of the cyclometalated Ir (III) complex is mainly divided into the following steps: firstly, introducing a proper chelating ligand to synthesize a ring metal iridium dimer, then utilizing the vacant coordination point on the iridium dimer to coordinate with the nitrogen atom of an auxiliary ligand, finally preparing a ring metal iridium complex, and finally carrying out diffusion culture on the ring metal iridium complex to obtain the crystal material of the metal complex. However, the conventional crystal material cultivation method has more steps, takes longer time and has relatively higher cost. The invention provides a simple synthesis method of a cyclometalated Ir (III) complex and a culture method of a crystal material thereof. The crystal cultivation method mainly comprises the steps of adding raw materials into an autoclave in proportion by utilizing a solvothermal method, preparing a solvent, adjusting the pH value of the solution, setting the temperature and time of an oven according to the boiling point of a solvent system, and finally obtaining the target crystal material.
The invention firstly provides a neutral metal complex iridium-bipyridyl dicarboxylic acid crystal material, wherein a vacant coordination point of phenylpyrazole ring metal iridium in the crystal material is coordinated with a nitrogen atom on an auxiliary ligand 2, 2-bipyridyl-5, 5' -dicarboxylic acid (bipyridyl dicarboxylic acid for short), and the structural formula of the crystal material is shown as the following formula:
in order to solve the problems, the invention also provides a preparation method of the neutral metal complex iridium-bipyridyl dicarboxylic acid crystal material, which comprises the following steps:
step 1: phenylpyrazole Cyclometalated Iridium dimer [ Ir (ppz)2(μ-Cl)]2The synthesis of (2):
dissolving iridium trichloride hydrate and 1-phenylpyrazole ligand in a molar ratio of 1:2 in a mixed solvent of ethylene glycol ethyl ether and deionized water, heating and refluxing for 24 hours at 135 ℃ in a nitrogen environment after fixation, and monitoring the reaction progress degree by TLC in the reaction process. Cooling to room temperature after the reflux is finished, performing suction filtration on the formed crude product by using a small Buchner funnel, washing the obtained precipitate by using a mixed solvent of petroleum ether and ethanol to remove impurities, extracting the precipitate for a plurality of times by using a mixed solvent of dichloromethane and deionized water, and finally drying the precipitate in vacuum to obtain a yellow target product [ Ir (ppz)2(μ-Cl)]2。
Step 2: synthesis of 2, 2-bipyridine-5, 5' -dicarboxylic acid (bipyridine dicarboxylic acid):
adding 5,5 '-dimethyl-2, 2' -bipyridine into the solution containing H2SO4Then the K is added in 20 minutes2Cr2O7Slowly adding while stirring. When the temperature rises above 80 ℃, cooling is started. The temperature was reduced to 35 ℃ with continuous stirring and the solution was poured into excess ice water with external cooling. The off-white solid product was isolated from the solution by centrifugation and washed with copious amounts of deionized water until the water no longer discolored and then acetone. The product was dried under vacuum at 60 ℃.
And step 3: synthesis of metal complex iridium-bipyridine dicarboxylic acid:
sodium carbonate, 2-bipyridine-5, 5' -dicarboxylic acid and [ Ir (ppz)2(μ-Cl)]2Added to a mixed solution of methanol and methylene chloride in a molar ratio of 1:4:2, and then the reaction mixture was heated under reflux at 80 ℃ for 3 hours. Cooling the mixture to room temperature after the reflux is finished, and adopting a rotary evaporation methodThe solvent was removed under reduced pressure. Adding deionized water, stirring to dissolve the precipitate, adding an HCl solution, adjusting the pH value of the solution to be 5, and finally filtering and drying in air to obtain the metal complex iridium-bipyridyl dicarboxylic acid.
And 4, step 4: hydrothermal culture of the iridium-biphenyldicarboxylic acid crystal material:
adding the metal complex iridium-bipyridyl dicarboxylic acid obtained in the step 3 into the inner liner of a polytetrafluoroethylene stainless steel container, adding sodium hydroxide and deionized water, and adjusting the pH value of the solution to 11; then the container is put under autogenous pressure, and crystals are precipitated at 180 ℃ according to the processes of temperature rise, heat preservation, temperature reduction and the like. The reaction mixture was cooled to room temperature and filtered over H2O washed several times and dried in air to give bright red crystals.
All solvents and reagents were analytically pure and used without further purification.
Further, in the step 1, the dosage ratio of the iridium trichloride hydrate to the mixed solvent of ethylene glycol ethyl ether and deionized water is 1mmol:50 ml; wherein, in the mixed solvent of ethylene glycol ethyl ether and deionized water, VEthylene glycol Ether:VDeionized water＝4:1。
In a mixed solvent of petroleum ether and ethanol, VPetroleum ether:VEthanol1: 1; in a mixed solvent of dichloromethane and deionized water, VMethylene dichloride:VDeionized water＝1:1。
Further, in step 2, the 5,5 '-dimethyl-2, 2' -bipyridine and K2Cr2O7In a molar ratio of 1: 3.
Further, in step 2, 5,5 '-dimethyl-2, 2' -bipyridine is reacted with H2SO4The dosage ratio of (A) to (B) is 1mmol to 20ml, wherein, H2SO4The mass percentage concentration of (2) is 95%.
Further, in the step 3, the using ratio of the sodium carbonate to the methanol/dichloromethane mixed solution is 1mmol:120 ml; wherein, in the mixed solution of methanol and dichloromethane, the molar ratio of the methanol to the dichloromethane is 1: 1.
Further, in the step 4, the heating, heat preservation and cooling time is respectively 24 hours, 48-72 hours and 12-24 hours.
The neutral metal complex iridium-bipyridyl dicarboxylic acid crystal material prepared by the invention is used in the field of chemical sensors or laser protection.
The principle of the invention is as follows:
according to the invention, from the structure and performance of the complex, a 1-phenylpyrazole chelating ligand with better phosphorescence performance is selected to form phenylpyrazole cyclometaliridium dimer with trihydrate and iridium trichloride, and then the phenylpyrazole cyclometaliridium dimer is combined with an auxiliary ligand 2, 2-bipyridyl-5, 5' dicarboxylic acid by means of dichloro bridge breakage under a certain reaction condition to form the iridium-bipyridyl dicarboxylic acid metal complex. And then applying the principle of crystal engineering, adopting a high-temperature high-pressure reaction kettle method, namely hydro-thermal synthesis, and obtaining the crystal material by the iridium-bipyridyl dicarboxylic acid metal complex through the processes of crystal nucleus precipitation, crystal growth and the like under the conditions of high temperature and high pressure.
The invention has the beneficial effects that:
(1) firstly, the invention changes the reaction conditions (the conventional reaction conditions are that the iridium-bipyridyl dicarboxylic acid is shaded and oxygen-free and is heated to 85 ℃ for refluxing for 24 hours, and the improved reaction conditions are that the iridium-bipyridyl dicarboxylic acid is heated to 80 ℃ for refluxing for 3 hours in the air) when preparing the iridium-bipyridyl dicarboxylic acid metal complex, greatly shortens the reaction time from the original time consumption of 24 hours to 3 hours, and obviously improves the synthesis efficiency.
(2) Secondly, when the iridium-bipyridyl dicarboxylic acid metal complex crystal is cultured, the raw materials are put into a high-pressure kettle in proportion by adopting a high-pressure reaction kettle method, a solvent is selected, the pH value is adjusted, the temperature of a system is selected by utilizing the boiling point of the solvent, and the time is set to obtain the target crystal material. Compared with the normal temperature solvent diffusion method, the method has simple operation and is easy to synthesize high-quality crystals.
(3) The crystal cultured by the normal temperature solvent diffusion method is fragile, and along with the volatilization of the solvent, a plurality of cracks appear on the surface of the crystal, thereby influencing the quality of the crystal. The neutral metal complex iridium-bipyridyl dicarboxylic acid crystal material cultured by the invention has good crystal quality and high stability.
Drawings
FIG. 1 is a synthetic route for phenylpyrazole cyclometalated iridium dimers;
FIG. 2 is a scheme for the synthesis of bipyridyldicarboxylic acid co-ligands;
FIG. 3 is a route for the preparation of iridium-bipyridyldicarboxylic acid metal complexes;
FIG. 4 is a crystal structure diagram of an iridium-bipyridyldicarboxylic acid metal complex;
FIG. 5 is a UV-visible absorption spectrum of a phenylpyrazole cyclometalated iridium dimer and an iridium-bipyridyl dicarboxylic acid crystalline material;
FIG. 6 steady state fluorescence emission spectra of phenylpyrazole cyclometalated iridium dimer and iridium-bipyridyl dicarboxylic acid crystalline materials;
FIG. 7 is a thermogravimetric plot of an iridium-bipyridyldicarboxylic acid crystalline material.
Detailed Description
The present invention will be described or further illustrated below with reference to specific examples, which show detailed embodiments and specific procedures for better understanding of the technical spirit of the present invention, but the scope of the present invention is not limited to the following.
Example 1:
step 1: phenylpyrazole Cyclometalated Iridium dimer [ Ir (ppz)2(μ-Cl)]2The synthetic route is shown in figure 1:
iridium trichloride hydrate (353.1mg,1.012mmol) and 1-phenylpyrazole ligand (290.2mg,2.101mmol) were dissolved in 50ml of a mixed solvent of ethylene glycol ethyl ether and deionized water, and after fixation, the mixture was heated under reflux at 135 ℃ for 24 hours under a nitrogen atmosphere, and the degree of progress of the reaction was monitored by TLC during the reaction. Cooling to room temperature after refluxing, suction filtering the yellow precipitate with small Buchner funnel, and collecting the precipitate with petroleum ether and ethanol mixed solvent (V)Petroleum ether:VEthanol1:1) washing to remove impurities, followed by a mixed solvent of dichloromethane and deionized water (V)Methylene dichloride:VDeionized water1:1) and finally dried in vacuo to give the yellow desired product [ ir (ppz)2(μ-Cl)]2. Yield 293mg (56.9%).
Step 2: the synthesis of 2, 2-bipyridine-5, 5' -dicarboxylic acid, the synthetic route is shown in figure 2:
5,5 '-dimethyl-2, 2' -bipyridine (178.7mg,0.971mmol) was added to 20ml of H2SO4(95%), followed by addition of K over 20 minutes2Cr2O7(855.7mg,2.913mmol) was added with stirring. When the temperature rises to 80 ℃ or higher, the heating is stopped. The temperature is continuously reduced to 35 ℃ by stirring, the solution is poured into 800ml of ice water, and is cooled by an ice bath to precipitate an off-white solid. Separating the solid from the solution by centrifugation, washing with a large amount of deionized water until the water no longer changes color, washing with acetone once, and drying the solid at 60 deg.C under vacuum. Yield 161mg (83%).
And step 3: the synthesis route of the iridium-bipyridyl dicarboxylic acid metal complex is shown in figure 3:
sodium carbonate (51.9mg,0.490mmol), 2-bipyridine-5, 5' -dicarboxylic acid (478.3mg,1.960mmol) and [ Ir (ppz)2(μ-Cl)]2(1004.9mg,0.980mmol) was added to a mixed solution of methanol and methylene chloride (60ml), and the reaction mixture was heated under reflux at 80 ℃ for 3 hours. The mixture was cooled to room temperature and the solvent was removed by rotary evaporation under reduced pressure. Deionized water (10ml) was added and the precipitate dissolved with stirring, and the pH adjusted to 5 by addition of HCl (AR,120 ul). Filtration and drying in air gave the iridium-bipyridyldicarboxylic acid metal complex in a yield of 38mg (45%).
And 4, step 4: carrying out hydrothermal reaction crystal culture on iridium-bipyridyl dicarboxylic acid:
adding the iridium-bipyridyl dicarboxylic acid metal complex (22.2mg,0.031mmol) obtained in step 3 into the inner liner of a 25ml polytetrafluoroethylene stainless steel container, and adding sodium hydroxide (20ul,1M) and 2ml H2And O, adjusting the pH value of the solution to 12. And then placing the container under the autogenous pressure, heating for 24 hours at 180 ℃ according to a certain temperature gradient, preserving heat for 72 hours, and cooling for 24 hours to room temperature. The reaction mixture was cooled to room temperature and filtered over H2And washing with O for more than three times, and drying in air to obtain bright red crystals. The yield was 9mg (32%) and the resulting neutral iridium-bipyridinedicarboxylic acid metal complex had a crystal structure as shown in FIG. 4.
FIG. 5 shows the utilization of ultraviolet lightAnd scanning and testing the spectrophotometer at a wave band of 200-800 nm to obtain an ultraviolet visible absorption spectrogram of the phenylpyrazole cyclometalated iridium dimer and the iridium-bipyridyl dicarboxylic acid crystal material in a dichloromethane solution. As can be seen from FIG. 5, the absorption peaks with strong characteristics in the 225-300 nm range are all shown and can be attributed to ligands1Pi-pi transition. The weak absorption from 300nm to the visible region is then due to charge transfer from the metal to the ligand: (3MLCT) and ligand to ligand charge transfer (1LLCT)。
Fig. 6 is an emission spectrum of a phenylpyrazole cyclometalated iridium dimer and an iridium-bipyridyl dicarboxylic acid crystalline material in a dichloromethane solution at room temperature with λ 258nm as an excitation wavelength. At room temperature, the emission wavelength of the phenylpyrazole cyclometaliridium dimer is 349 nm, and the emission wavelength of the iridium-bipyridyl dicarboxylic acid metal complex is 352 nm. The fluorescence emission wavelength of the iridium-bipyridyl dicarboxylic acid crystal material generates weak red shift but generates obvious fluorescence quenching phenomenon. These indicate that the introduction of the ligand has a relatively significant effect on the electron cloud density.
Figure 7 is a thermogravimetric analysis (TGA) of an iridium-bipyridylcarboxylic acid crystalline material performed using a thermobalance of a PerkineElmerPyis1 analyzer. The procedure used was as follows: the temperature of a 3mg sample is raised to 800 ℃ at a heating rate of 10 ℃/min, and the nitrogen flow is 200 mL/min-1. The curves show three successive steps with a mass loss between 30 ℃ and 800 ℃. The temperature of the first stage is slight mass loss at 30-225 ℃, and the weight loss rate is 4.99% due to solvent volatilization. The mass loss from 225 ℃ to 410 ℃ is severe, and the weight loss rate reaches 65 percent, which is attributed to the loss of chelating ligand; the loss of mass continues from 410 ℃ to 800 ℃, but not much, due to the complete loss of ligand. Thermogravimetric analysis shows that the crystal material of the iridium-bipyridyl dicarboxylic acid metal complex has good thermal stability.
Example 2:
and step 3: synthesis of iridium-bipyridyl dicarboxylic acid metal complex:
sodium carbonate (51.4mg,0.471mmol), 2-bipyridine-5, 5' -dicarboxylic acid (459.7mg,1.884mmol) and [ Ir (ppz)2(μ-Cl)]2(970.3mg,0.942mmol) was added to a mixed solution (60ml) of methanol and methylene chloride, and the mixture was heated under reflux at 80 ℃ for 3 hours. After the reaction is finished, the reaction product is cooled to room temperature, and the solvent is removed by adopting a rotary evaporation method under the reduced pressure condition. The precipitate was then dissolved by adding deionized water (10ml) with stirring, and the pH was adjusted to 5 by adding HCl (AR,120 ul). Filtration and drying in air gave the iridium-bipyridyldicarboxylic acid metal complex in a yield of 43mg (46%).
And 4, step 4: carrying out hydrothermal reaction crystal culture on iridium-bipyridyl dicarboxylic acid:
the iridium-bipyridyldicarboxylic acid metal complex (25.3mg,0.035mmol) obtained in step 3 was added to a 25ml polytetrafluoroethylene stainless steel container liner, and sodium hydroxide (21ul,1M) and 2.5ml H were added2And O, adjusting the pH value of the solution to 12. And then placing the container under the autogenous pressure, heating for 24 hours at 180 ℃ according to a certain temperature gradient, preserving heat for 48 hours, and cooling for 24 hours to room temperature. The reaction mixture was cooled to room temperature and filtered over H2O washed three times and dried in air to give bright red crystals. Yield 10mg (33%).
Example 3:
and step 3: synthesis of metal complex iridium-bipyridine dicarboxylic acid:
sodium carbonate (53.1mg,0.491mmol), 2-bipyridine-5, 5' -dicarboxylic acid (497.2mg,1.964mmol) and [ Ir (ppz)2(μ-Cl)]2(1011.5mg,0.982mmol) was added to a mixed solution of methanol and methylene chloride (60ml), and the reaction mixture was heated under reflux at 80 ℃ for 3 hours. After the reaction, the mixture was cooled to room temperature, and the solvent was removed by rotary evaporation under reduced pressure. The precipitate was then dissolved by adding deionized water (10ml) with stirring, and the pH was adjusted to 5 by adding HCl (AR,120 ul). Filtering and drying in the air to obtain the iridium-bipyridyl dicarboxylic acid metal complex. Yield 42mg (48%).
And 4, step 4: culturing the iridium-bipyridyl dicarboxylic acid hydrothermal reaction crystal:
the iridium-bipyridyl dicarboxylic acid metal complex (23.1 m) obtained in step 3g,0.032mmol) was added to the 25ml Teflon stainless steel vessel liner and sodium hydroxide (20ul,1M) and 2.8ml H were added2And O, adjusting the pH value of the solution to 12. And then placing the container under the autogenous pressure, heating for 24 hours at 180 ℃ according to a certain temperature gradient, preserving heat for 72 hours, and cooling for 12 hours to room temperature. The reaction mixture was cooled to room temperature and filtered over H2O washed three times and dried in air to give bright red crystals. Yield 8.8mg (29%).
Tables 1 to 3 show the crystallographic data, partial bond length data and partial bond angle data of the iridium-bipyridylium dicarboxylic acid crystal material prepared in example 1 of the present invention, respectively.
Table 1 shows the crystallographic data of the iridium-bipyridyldicarboxylic acid crystalline material prepared in example 1 of the present invention
Table 2 shows partial bond length data of the iridium-bipyridyl dicarboxylic acid crystalline material prepared in example 1 of the present invention
Table 3 shows data of partial bond angles of the iridium-bipyridyl dicarboxylic acid crystalline material prepared in example 1 of the present invention
Claims (10)
1. A neutral metal complex iridium-bipyridyl dicarboxylic acid crystal material is characterized in that a vacant coordination point of phenylpyrazole ring metal iridium in the crystal material is coordinated with a nitrogen atom on an auxiliary ligand 2, 2-bipyridyl-5, 5' -dicarboxylic acid, and the structural formula of the crystal material is as follows:
2. a preparation method of a neutral metal complex iridium-bipyridyl dicarboxylic acid crystal material is characterized by comprising the following steps:
step 1: phenylpyrazole Cyclometalated Iridium dimer [ Ir (ppz)2(μ-Cl)]2The synthesis of (2):
dissolving iridium trichloride hydrate and 1-phenylpyrazole ligand in a mixed solvent of ethylene glycol ethyl ether and deionized water according to a proportion, heating and refluxing in a nitrogen environment after fixation, monitoring the reaction progress by TLC in the reaction process, cooling to room temperature after the reflux is finished, carrying out suction filtration, washing the obtained precipitate by using a mixed solvent of petroleum ether and ethanol to remove impurities, extracting and purifying by using a mixed solvent of dichloromethane and deionized water, and finally drying in vacuum to obtain a yellow target product [ Ir (ppz) ]2(μ-Cl)]2；
Step 2: synthesis of 2, 2-bipyridine-5, 5' -dicarboxylic acid:
adding 5,5 '-dimethyl-2, 2' -bipyridine into the solution containing H2SO4Then the K is added in 20 minutes2Cr2O7Slowly adding while stirring, and cooling when the temperature rises to above 80 ℃; continuously stirring and cooling to 35 ℃, pouring the solution into excessive ice water, and externally cooling; the off-white solid product was isolated from the solution by centrifugation and washed with copious amounts of deionized water until the water was no longer presentChanging color, cleaning with acetone, and vacuum drying;
and step 3: synthesis of metal complex iridium-bipyridine dicarboxylic acid:
proportionally mixing sodium carbonate, 2-dipyridyl-5, 5' -dicarboxylic acid and [ Ir (ppz)2(μ-Cl)]2Adding into mixed solution of methanol and dichloromethane, and heating and refluxing the reaction mixture at 80 deg.C for 3 hr; after the reflux is finished, cooling the mixture to room temperature, and removing the solvent by adopting a rotary evaporation method under the reduced pressure condition; adding deionized water, stirring to dissolve the precipitate, adding HCl solution, adjusting the pH value of the solution, and finally filtering and drying in the air to obtain a metal complex iridium-bipyridyl dicarboxylic acid;
and 4, step 4: hydrothermal culture of the iridium-biphenyldicarboxylic acid crystal material:
adding the metal complex iridium-bipyridyl dicarboxylic acid obtained in the step 3 into the inner liner of a polytetrafluoroethylene stainless steel container, adding sodium hydroxide and deionized water, and adjusting the pH value of the solution; then putting the container under autogenous pressure, and separating out crystals at 180 ℃ according to the processes of heating, heat preservation, cooling and the like; the reaction mixture was cooled to room temperature and filtered over H2O washed several times and dried in air to give bright red crystals.
3. The method according to claim 2, wherein in step 1, the molar ratio of iridium trichloride hydrate to 1-phenylpyrazole ligand is 1: 2; the dosage ratio of the iridium trichloride hydrate to the mixed solvent of ethylene glycol ethyl ether and deionized water is 1mmol:50 mL; wherein, in the mixed solvent of ethylene glycol ethyl ether and deionized water, VEthylene glycol Ether:VDeionized water＝4:1。
4. The method according to claim 2, wherein in step 1, the temperature of the heating reflux is 135 ℃ for 24 hours; the filtration is carried out by a small Buchner funnel, and V is carried out in a mixed solvent of petroleum ether and ethanolPetroleum ether:VEthanol1: 1; in a mixed solvent of dichloromethane and deionized water, VMethylene dichloride:VDeionized water＝1:1。
5. The method according to claim 2, wherein in step 2, the 5,5 '-dimethyl-2, 2' -bipyridine and K are2Cr2O7In a molar ratio of 1: 3.
6. The method of claim 2, wherein in step 2, 5,5 '-dimethyl-2, 2' -bipyridine is reacted with H2SO4The dosage ratio of (A) to (B) is 1mmol to 20ml, wherein, H2SO4The mass percentage concentration of (A) is 95%; the temperature for vacuum drying was 60 ℃.
7. The method according to claim 2, wherein in step 3, sodium carbonate, 2-bipyridine-5, 5' -dicarboxylic acid and [ Ir (ppz)2(μ-Cl)]2In a molar ratio of 1:4: 2; the dosage ratio of the sodium carbonate to the methanol/dichloromethane mixed solution is 1mmol to 120 ml; wherein, in the mixed solution of methanol and dichloromethane, the molar ratio of the methanol to the dichloromethane is 1: 1.
8. The method of claim 2, wherein in step 3, the solution pH is adjusted to 5 using HCl solution.
9. The method of claim 2, wherein in step 4, the pH of the solution is adjusted to 11 using sodium hydroxide and deionized water; the temperature is raised, kept warm and lowered for 24 hours, 48-72 hours and 12-24 hours respectively.
10. The neutral metal complex iridium-bipyridyl dicarboxylic acid crystal material according to claim 1 is used in the field of chemical sensors or in the field of laser protection.
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