A kind of multidentate organic ligand containing triphenylamine-tripyridine structure, metal supramolecular polymer, polymer film and preparation method

Abstract

The application provides a kind of polychaete organic ligand containing triphenylamine-tripyridine structure, metal supramolecular polymer, polymer film and preparation method, belong to organic luminescent material technical field.The application designs and synthesizes a kind of novel polychaete organic ligand containing "triphenylamine-tripyridine" structure, by introducing electron-donating group in benzene ring para position, can effectively reduce oxidation-reduction potential, enhance the efficiency of electrochromic, promote the entry and extraction of ion and electron, and it is driven to synthesize a series of metal supramolecular polymer by coordination with metal ion, and the prepared metal-supramolecular polymer film has short color change response time and high electrochromic performance.

Description

Technical Field

[0001] This invention relates to the field of organic light-emitting materials technology, and in particular to a multidentate organic ligand containing a triphenylamine-terpyridine structure, a metal supramolecular polymer, a polymer film, and a preparation method thereof. Background Technology

[0002] Metal supramolecular polymers are a novel type of electrochromic material, prepared by coordination polymerization of small organic molecules or polymers with metal ions. They exhibit electrochromic properties primarily based on metal-ligand charge transfer. The metal center of these polymers is bonded to the polymer backbone or side chains, complementing and combining the advantages of both organic and inorganic materials. Coordination polymer electrochromic films prepared based on molecular assembly not only possess excellent coloring efficiency and redox stability, but also allow for a wide range of color changes by modifying organic ligands or altering the type of metal ions.

[0003] Triphenylamine is an excellent electroactive group. The most significant characteristics of triphenylamine-based electrochromic materials are their short conjugated structure and high band gap; they are colorless in the neutral state and exhibit a noticeable color change during oxidation. These properties perfectly match the energy-saving requirements for electrochromic materials. Simultaneously, the three-dimensional, large-volume twisted structure of triphenylamine reduces the solid-state π-π packing effect of the material. In summary, introducing triphenylamine structures into metal supramolecular polymers can prepare intermediate-state colorless, solution-processable electrochromic materials.

[0004] Pyridine and its derivatives, as heterocyclic organic luminescent molecules, can be used not only as luminescent materials themselves but also as starting materials to explore the synthesis of better luminescent materials. 2,2':6',2"-terpyridine (TPY), as a common tripentate ligand, can coordinate with metals to form stable motifs... <tpy-M 2+ -tpyridine metal complexes possess a large π-conjugated structure, giving them strong σ-electron-donating and π-electron-accepting capabilities. This endows terpyridine metal complexes with rich photophysical and electrochemical properties. Most terpyridine metal complexes exhibit tunable emission wavelengths, long emission lifetimes, large Stokes shifts, and good optical stability, and have been widely applied in photoluminescence, catalysts, self-assembly, sensing, and bioimaging.

[0005] Guoming Wang et al. (Organic Electronics. 2014, 15, 622-630) synthesized a series of novel single-molecule electrochromic materials, 2,4,6-trisubstituted pyridine derivatives, and studied their electrochromic properties. They found that the electrochromic devices had long response times and poor stability. Fu She Han et al. (J. Am. Chem. Soc. 2008, 130, 6, 2073-2081) designed a series of organic ligands containing bidentate terpyridine ligands. Experiments showed that terpyridine-based organic ligands have good photoelectric properties, but also suffer from long response times. To address these issues, this invention combines a triphenylamine structure and terpyridine into the same compound via Ullmann coupling, and then introduces other modifying groups to enrich the structure of the organic ligand, aiming to optimize the electrochromic properties of metal supramolecular polymers. Summary of the Invention

[0006] In view of this, the present invention aims to provide a multidentate organic ligand containing a triphenylamine-terpyridine structure, a metal supramolecular polymer, a polymer film, and a preparation method thereof. The multidentate organic ligand provided by the present invention can be used to synthesize a series of metal-supramolecular polymer films through coordination with metal ions, which have the advantages of short color change response time and high electrochromic performance.

[0007] To achieve the above objectives, the present invention provides the following technical solution:

[0008] This invention provides a multidentate organic ligand containing a triphenylamine-terpyridine structure, having the structure shown in Formula I:

[0009]

[0010] In the formula, R1 is selected from one of the following structures:

[0011]

[0012] R2 is selected from one of the following structures:

[0013]

[0014] The present invention also provides a method for preparing the multidentate organic ligand described in the above technical solution, comprising the following steps:

[0015] (1) Under alkaline conditions, 4'-(4-nitrophenyl)-2,2':6',2"-terpyridine was synthesized in a one-pot process using 4-nitrobenzaldehyde and 2-acetylpyridine as raw materials;

[0016] (2) Under an inert atmosphere, the 4'-(4-nitrophenyl)-2,2':6',2"-terpyridine obtained in step (1) was reduced with hydrazine hydrate under the condition of catalyst Pd / C to obtain 4'-(4-aminophenyl)-2,2':6',2"-terpyridine;

[0017] (3) Under alkaline conditions, the 4'-(4-aminophenyl)-2,2':6',2"-terpyridine obtained in step (2) and the iodobenzene compound undergo the Ullmann reaction with 18-crown ether-6 in the presence of copper powder catalyst to obtain terpyridine aniline compounds;

[0018] (4) Under alkaline conditions, the tripyridine aniline compound obtained in step (3) and the dibromo compound undergo a Ullmann reaction with 18-crown ether-6 in the presence of copper powder as a catalyst to obtain the target product.

[0019] Preferably, the alkali in step (1) is potassium hydroxide and ammonium hydroxide; the molar ratio of 4-nitrobenzaldehyde, 2-acetylpyridine, potassium hydroxide and ammonium hydroxide is 1:(1.5~4):(1.5~4):(1~5); the one-pot reaction temperature is room temperature and the reaction time is 72~96h.

[0020] Preferably, the mass fraction of hydrazine hydrate in step (2) is 65% to 85%; the molar ratio of 4'-(4-nitrophenyl)-2,2':6',2"-terpyridine to hydrazine hydrate is 1:(5 to 15); the reduction reaction temperature is 70 to 80°C, and the reaction time is 8 to 15 h.

[0021] Preferably, the base in step (3) is potassium carbonate; the molar ratio of 4'-(4-aminophenyl)-2,2':6',2"-terpyridine:iodobenzene compound:copper:potassium carbonate:18-crown ether-6 is 1:(1~3):(1~3):(1~3):(0.4~0.6); the reaction temperature of the Ullmann reaction is 140~175℃, and the reaction time is 12~20h.

[0022] Preferably, the base in step (4) is potassium carbonate; the molar ratio of the terpyridine aniline compound: dibromo compound: copper: potassium carbonate: 18-crown ether-6 is 1:(0.5~1.5):(1~3):(1~3):(0.4~0.6); the reaction temperature of the Ullmann reaction is 140~175℃, and the reaction time is 10~40h.

[0023] The present invention also provides a metal supramolecular polymer, which is synthesized by coordination-driven synthesis of the polydentate organic ligand and metal ions as described in the above technical solution.

[0024] Preferably, the molar ratio of the polydentate organic ligand to the metal ion is 1:(1-2).

[0025] Preferably, the metal ions are selected from Fe(BF4)2·6H2O, Cu(ClO4)2·6H2O, Zn(BF4)2·6H2O, and RuCl2(DMSO)4.

[0026] The present invention also provides a metal ion-ligand supramolecular polymer film, which is obtained by dissolving the metal supramolecular polymer described in the above technical solution in methanol, then spraying it onto the surface of ITO conductive glass, and drying it.

[0027] Compared with the prior art, the present invention has the following beneficial technical effects:

[0028] 1. This invention designs and synthesizes a novel multidentate organic ligand containing a "triphenylamine-terpyridine" structure, and synthesizes a series of metal supramolecular polymers through coordination with metal ions. The resulting metal-supramolecular polymer films have short color-changing response times and high electrochromic properties.

[0029] 2. By introducing an electron-donating group at the para position of the benzene ring, this invention can effectively reduce the redox potential, enhance the efficiency of electrochromism, and promote the entry and extraction of ions and electrons.

[0030] 3. The "one-pot method" for preparing terpyridine used in this invention is simple to operate and has low overall cost. Attached Figure Description

[0031] Figure 1 The target product N described in Example 1 1 N 4 -bis(4-([2,2'-:6'-,2”-bipyridine]-4'-yl)phenyl)-N 1 N 4 -Diphenylbenzene-1,4-diamine proton NMR spectrum;

[0032] Figure 2 The target product N described in Example 1 1 N 4 -bis(4-([2,2'-:6'-,2”-bipyridine]-4'-yl)phenyl)-N 1 N 4 Fourier transform infrared spectrum of 1,4-diphenylphenyl-1,4-diamine;

[0033] Figure 3 The electrochromatogram of the metal supramolecular polymer labeled as film 1 in Example 11;

[0034] Figure 4The cyclic voltammogram of the metal supramolecular polymer labeled as film 1 in Example 11;

[0035] Figure 5 The electrochromic response time spectrum at 910 nm is shown for the metal supramolecular polymer labeled as film 1 in Example 11.

[0036] Figure 6 The electrochromic response time spectrum of the metal supramolecular polymer labeled as film 1 in Example 11 is shown at 680 nm. Detailed Implementation

[0037] This invention provides a multidentate organic ligand containing a triphenylamine-terpyridine structure, having the structure shown in Formula I:

[0038]

[0039] In the formula, R1 is selected from one of the following structures:

[0040]

[0041] R2 is selected from one of the following structures:

[0042]

[0043] The present invention also provides a method for preparing the multidentate organic ligand described in the above technical solution, comprising the following steps:

[0044] (1) Under alkaline conditions, 4'-(4-nitrophenyl)-2,2':6',2"-terpyridine was synthesized in a one-pot process using 4-nitrobenzaldehyde and 2-acetylpyridine as raw materials;

[0045] (2) Under an inert atmosphere, the 4'-(4-nitrophenyl)-2,2':6',2"-terpyridine obtained in step (1) was reduced with hydrazine hydrate under the condition of catalyst Pd / C to obtain 4'-(4-aminophenyl)-2,2':6',2"-terpyridine;

[0046] (3) Under alkaline conditions, the 4'-(4-aminophenyl)-2,2':6',2"-terpyridine obtained in step (2) and the iodobenzene compound undergo the Ullmann reaction with 18-crown ether-6 in the presence of copper powder catalyst to obtain terpyridine aniline compounds;

[0047] (4) Under alkaline conditions, the tripyridine aniline compound obtained in step (3) and the dibromo compound undergo a Ullmann reaction with 18-crown ether-6 in the presence of copper powder as a catalyst to obtain the target product.

[0048] This invention first synthesizes 4'-(4-nitrophenyl)-2,2':6',2"-terpyridine in a one-pot reaction under alkaline conditions using 4-nitrobenzaldehyde and 2-acetylpyridine as raw materials. The general reaction formula is:

[0049]

[0050] In this invention, the alkali is preferably potassium hydroxide and ammonium hydroxide; the molar ratio of 4-nitrobenzaldehyde, 2-acetylpyridine, potassium hydroxide and ammonium hydroxide is preferably 1:(1.5-4):(1.5-4):(1-5).

[0051] In this invention, the one-pot reaction further includes the addition of a solvent, preferably methanol, wherein the amount of methanol added is 1 mmol of 4-nitrobenzaldehyde monomer per 6-10 mL of solvent. In this invention, the one-pot reaction is carried out at room temperature for 72-96 hours.

[0052] In this invention, after the one-pot reaction is completed, the product is further purified. The purification specifically involves dissolving the product obtained from the one-pot reaction in dichloromethane, repeatedly extracting and washing the product with a 1-5% sodium bicarbonate solution (V dichloromethane:V sodium bicarbonate solution = 2:(2-1)), combining the organic phases and drying with anhydrous magnesium sulfate, filtering, and removing the filtrate by rotary evaporation to obtain the product 4'-(4-nitrophenyl)-2,2':6',2"-terpyridine.

[0053] After obtaining 4'-(4-nitrophenyl)-2,2':6',2"-terpyridine, this invention, under an inert atmosphere, reduces the 4'-(4-nitrophenyl)-2,2':6',2"-terpyridine obtained in step (1) with hydrazine hydrate under the condition of Pd / C catalyst to obtain 4'-(4-aminophenyl)-2,2':6',2"-terpyridine. The general reaction formula is:

[0054]

[0055] In this invention, the inert atmosphere is preferably N2; the mass fraction of Pd / C is preferably 10%; the molar ratio of 4'-(4-nitrophenyl)-2,2':6',2"-terpyridine to Pd / C is preferably 1:(1.5-4); the mass fraction of hydrazine hydrate is preferably 65%-85%; and the molar ratio of 4'-(4-nitrophenyl)-2,2':6',2"-terpyridine to hydrazine hydrate is preferably 1:(5-15).

[0056] In this invention, the reduction reaction further includes the addition of a solvent; the solvent is preferably ethanol; the amount of ethanol added is preferably 1 mmol of 4'-(4-nitrophenyl)-2,2':6',2"-terpyridine per 30-50 mL of solvent. In this invention, the reduction reaction temperature is preferably 70-80°C, and the reaction time is preferably 8-15 h.

[0057] In this invention, after the reaction is completed, the product is purified; the purification specifically involves: after the reaction is complete, the reaction solution is filtered while hot to remove Pd / C, the obtained filtrate is washed with deionized water, the organic phases are combined and dried with anhydrous magnesium sulfate, filtered, and the filtrate is removed by rotary evaporation to obtain the product 4'-(4-aminophenyl)-2,2':6',2"-terpyridine.

[0058] After obtaining 4'-(4-aminophenyl)-2,2':6',2"-terpyridine, under alkaline conditions, the present invention reacts the 4'-(4-aminophenyl)-2,2':6',2"-terpyridine obtained in step (2) with an iodobenzene compound in the presence of copper powder catalyst, and then reacts with 18-crown ether-6 to obtain terpyridine aniline compounds. The general reaction formula is:

[0059]

[0060] In this invention, the alkali is preferably potassium carbonate; the molar ratio of 4'-(4-aminophenyl)-2,2':6',2"-terpyridine:iodobenzene compound:copper:potassium carbonate:18-crown ether-6 is 1:(1~3):(1~3):(1~3):(0.4~0.6).

[0061] In this invention, the Ullmann reaction is carried out under an inert atmosphere, preferably nitrogen; the Ullmann reaction also includes the addition of a solvent, preferably o-dichlorobenzene, wherein the amount of o-dichlorobenzene added is 1 mmol of tripyridine monomer per 5-10 ml of solvent; the reaction temperature of the Ullmann reaction is 140-175°C, and the reaction time is 12-20 h.

[0062] In this invention, after the Ullmann reaction is completed, the product is further purified. Specifically, the purification involves: after the reaction is complete, hot filtration is performed, and the organic solvent o-dichlorobenzene is removed from the filtrate by vacuum distillation. The crude product is then dissolved in a minimal amount of N,N-dimethylacetamide. After the reaction is complete, the product is discharged into brine, filtered, dried, and eluent is obtained using dichloromethane / methanol (V...). 二氯甲烷 V 甲醇 =5:1), the crude product was purified by column chromatography to obtain tripyridine aniline compounds.

[0063] After obtaining the terpyridine aniline compound, the present invention, under alkaline conditions, reacts the terpyridine aniline compound obtained in step (3) with a dibromo compound in the presence of copper powder as a catalyst, and then reacts with 18-crown ether-6 to obtain the target product. The general reaction formula is:

[0064]

[0065] In this invention, the alkali is preferably potassium carbonate, and the molar ratio of the terpyridine aniline compound: dibromo compound: copper: potassium carbonate: 18-crown ether-6 is 1:(0.5~1.5):(1~3):(1~3):(0.4~0.6).

[0066] In this invention, the Ullmann reaction is preferably carried out under an inert atmosphere, preferably N2; the Ullmann reaction also includes the addition of a solvent, preferably o-dichlorobenzene, wherein the amount of o-dichlorobenzene added is 1 mmol of tripyridine monomer per 5-10 ml of solvent; the reaction temperature of the Ullmann reaction is 140-175°C, and the reaction time is 10-40 h.

[0067] In this invention, after the Ullmann reaction is completed, the product is further purified. Specifically, the purification involves: after the reaction is complete, hot filtration is performed, and the organic solvent o-dichlorobenzene is removed from the filtrate by vacuum distillation. The crude product is then dissolved in a minimal amount of N,N-dimethylacetamide. After the reaction is complete, the product is discharged into brine, filtered, dried, and eluent is obtained using dichloromethane / methanol (V...). 二氯甲烷 V 甲醇 =2~5:1), the crude product was purified by chromatography to obtain the target product.

[0068] The present invention also provides a metal supramolecular polymer, which is synthesized by coordination-driven synthesis of the polydentate organic ligand and metal ions as described in the above technical solution.

[0069] In this invention, the molar ratio of the multidentate organic ligand to the metal ion is preferably 1:(1-2); the metal ion is preferably Fe(BF4)2·6H2O, Cu(ClO4)2·6H2O, Zn(BF4)2·6H2O, or RuCl2(DMSO)4; the reaction temperature for the coordination-driven synthesis of the multidentate organic ligand and the metal ion is 40℃-100℃, and the reaction time is 10h-50h.

[0070] In some embodiments, the reaction is specifically performed as follows: the multidentate organic ligand and metal ions are dissolved in glacial acetic acid, and reacted at 50°C to 90°C for 12 to 48 hours to allow the ligand and metal ions to completely complex. After the reaction, the mixture is filtered, and the filtrate is evaporated under reduced pressure. The product is washed multiple times with ethanol and then dried under vacuum to obtain a solid metal supramolecular polymer. In this invention, the amount of glacial acetic acid added is 0.1 mmol of multidentate organic ligand per 100 ml of glacial acetic acid.

[0071] The present invention also provides a metal ion-ligand supramolecular polymer film, which is obtained by dissolving the metal supramolecular polymer described in the above technical solution in methanol, then spraying it onto the surface of ITO conductive glass, and drying it.

[0072] In some embodiments, the specific operation is as follows: the above-mentioned solid metal supramolecular polymer is dissolved in methanol, insoluble matter is filtered out to obtain a metal ion-ligand supramolecular polymer solution, 5 ml to 40 ml of the solution is added to the spray bottle of a pneumatic spray gun, and then sprayed onto the surface of ITO conductive glass. The glass is then placed in an oven and dried at 25°C to 50°C for 10 to 40 hours to obtain a uniform metal ion-ligand supramolecular polymer film. In this invention, the amount of methanol added is controlled to be 50 mg of metal supramolecular polymer per 100 ml of methanol.

[0073] To better understand the present invention, the following embodiments further illustrate the content of the present invention, but the content of the present invention is not limited to the following embodiments.

[0074] Example 1

[0075] The structure of the multidentate organic ligand is shown below:

[0076]

[0077] (1) Add 5 g (33.0 mmol) of 4-nitrobenzaldehyde, 6.05 g (50.0 mmol) of 2-acetylpyridine, 2.81 g (50.0 mmol) of potassium hydroxide and 1.16 g (33.0 mmol) of ammonium hydroxide to a three-necked flask containing a magnetic inlet. After stirring, add 198 ml of methanol as a solvent and stir at room temperature for 72 h. Filter the mixture and dissolve the precipitate in 40 ml of dichloromethane. Extract and wash the product with 20 ml of 1% sodium bicarbonate solution. Combine the organic phases and dry them with anhydrous magnesium sulfate. Filter the mixture and remove the filtrate by rotary evaporation to obtain 2.46 g of the product 4'-(4-nitrophenyl)-2,2':6',2"-terpyridine, with a yield of 21%.

[0078] (2) Add 2.46 g (7.0 mmol) of 4'-(4-nitrophenyl)-2,2':6',2"-terpyridine and 1.12 g (10.5 mmol) of 10% Pd / C to a three-necked flask equipped with a magnetic stirrer, a condenser, and a spherical drying tube. Purge the flask with nitrogen gas through one end. After 3 min, add 210 ml of ethanol as a solvent and stir. Nitrogen gas is continuously purged throughout the reaction. After heating to reflux, stop the reaction. Stop heating and slowly add 2.69 g (35.0 mmol) of 65% hydrazine hydrate. Then, allow the system to react at 70 °C for 8 h under a nitrogen atmosphere. After the reaction is complete, filter the reaction solution while hot to remove Pd / C. Wash the filtrate with deionized water, combine the organic phases and dry them with anhydrous magnesium sulfate. Filter under vacuum and remove the filtrate by rotary evaporation to obtain 1.82 g of product 4'-(4-aminophenyl)-2,2':6',2"-terpyridine, with a yield of 80%.

[0079] (3) Add 1.82 g (5.6 mmol) of 4'-(4-aminophenyl)-2,2':6',2"-terpyridine, 1.14 g (5.6 mmol) of iodobenzene, 0.36 g (5.6 mmol) of copper powder, 0.72 g (5.6 mmol) of potassium carbonate and 0.59 g (2.24 mmol) of 18-crown ether-6 to a Schrank flask, and then apply three nitrogen-vacuum cycles (using a double-row tube, first fill the Schrank flask with nitrogen, then evacuate until the vacuum level reaches below 0.1 MPa). Repeat this process three times, ensuring the reaction is carried out under a nitrogen atmosphere. After the solid reactants are thoroughly mixed and impregnated in the nitrogen atmosphere, add 28 ml of o-dichlorobenzene solvent using a syringe, and apply three more nitrogen-vacuum cycles to the system, allowing the system to react at 140°C for 12 hours. After the reaction is complete, filter while hot, remove the o-dichlorobenzene organic solvent from the filtrate by vacuum distillation, and then dissolve the crude product in a minimal amount of N,N-dimethylacetamide. After the reaction is complete, discharge the product into brine, filter, dry, and use dichloromethane / methanol as the eluent (V... 二氯甲烷 V 甲醇 =5:1), the crude product was purified by column chromatography to obtain 0.76 g of tripyridine aniline compounds, with a yield of 34%;

[0080] (4) Add 0.76 g (1.9 mmol) of terpyridine aniline compound, 0.22 g (0.95 mmol) of p-dibromobenzene, 0.12 g (1.9 mmol) of copper powder, 0.24 g (1.9 mmol) of potassium carbonate, and 0.20 g (0.76 mmol) of 18-crown ether-6 to a Schrank flask. Then apply three nitrogen-vacuum cycles. After the solid reactants are fully mixed and impregnated in the nitrogen atmosphere, add 9.5 ml of o-dichlorobenzene solvent using a syringe. Apply three more nitrogen-vacuum cycles to the system and allow the system to react at 140 °C for 12 h. After the reaction is complete, filter while hot and remove the organic solvent o-dichlorobenzene from the filtrate by vacuum distillation. Then dissolve the crude product in a minimum amount of N,N-dimethylacetamide. After the reaction is complete, discharge the product into brine, filter, dry, and use dichloromethane / methanol as the eluent (V 二氯甲烷 V 甲醇 The crude product was purified by column chromatography (r = 2:1) to obtain 0.48 g of the target product, a multidentate organic ligand compound containing the "triphenylamine-terpyridine" structure, with a yield of 29%.

[0081] Figure 1 The target product N described in Example 1 1 N 4 -bis(4-([2,2'-:6'-,2”-bipyridine]-4'-yl)phenyl)-N 1 N 4 -Diphenylbenzene-1,4-diamine proton NMR spectrum; 1 ¹H NMR (400MHz, DMSO-d⁶) δ 9.16 (d, J = 20.0Hz, 4H), 9.12–8.96 (m, 4H), 8.55 (s, 4H), 7.74 (s, 4H), 7.55 (s, 4H), 7.37 (s, 4H), 7.24 (d, J = 5.0Hz, 8H), 7.14 (s, 4H), 7.08 (s, 4H), 7.00 (s, 2H). The peak positions and integrated peak areas are consistent with the structure, indicating the successful preparation of the target organic ligand.

[0082] Figure 2 The target product N described in Example 1 1 N 4 -bis(4-([2,2'-:6'-,2”-bipyridine]-4'-yl)phenyl)-N 1 N 4 Fourier transform infrared spectrum of 1,4-diphenylbenzene; the target product of Example 1 has absorption peaks with characteristic functional group structures, such as 1598 cm⁻¹. -1 The C=N absorption peak at that location;

[0083] Example 2

[0084] The structure of the multidentate organic ligand is shown below:

[0085]

[0086] (1) Add 5 g (33.0 mmol) of 4-nitrobenzaldehyde, 6.05 g (50.0 mmol) of 2-acetylpyridine, 2.81 g (50.0 mmol) of potassium hydroxide and 1.16 g (33.0 mmol) of ammonium hydroxide to a three-necked flask containing a magnetic inlet. After stirring, add 198 ml of methanol as a solvent. The remaining operations and conditions of this step are the same as in step (1) of Example 1, to obtain 2.92 g of product 4'-(4-nitrophenyl)-2,2':6',2"-terpyridine, with a yield of 25%.

[0087] (2) 2.92 g (8.25 mmol) of 4'-(4-nitrophenyl)-2,2':6',2"-terpyridine and 1.32 g (12.38 mmol) of 10% Pd / C were added to a three-necked flask equipped with a magnetic stirrer, a condenser, and a spherical drying tube. Nitrogen gas was purged through one end of the flask. After 3 min, 248 ml of ethanol was added as a solvent and the mixture was stirred. Nitrogen gas was continuously purged throughout the reaction. After heating to reflux, heating was stopped, and 3.17 g (41.25 mmol) of 65% hydrazine hydrate was slowly added dropwise. The remaining operations and conditions of this step were the same as in step (2) of Example 1. 2.34 g of 4'-(4-aminophenyl)-2,2':6',2"-terpyridine was obtained, with a yield of 87%.

[0088] (3) Add 2.34 g (7.21 mmol) of 4'-(4-aminophenyl)-2,2':6',2"-terpyridine, 1.69 g (7.21 mmol) of p-iodoanisole, 0.46 g (7.21 mmol) of copper powder, 0.92 g (7.21 mmol) of potassium carbonate and 0.73 g (2.88 mmol) of 18-crown ether-6 to a Schrank flask, and then apply three nitrogen-vacuum cycles. After the solid reactants are fully mixed and impregnated in the nitrogen atmosphere, add 36 ml of o-dichlorobenzene solvent using a syringe. The remaining operations and conditions of this step are the same as in step (3) of Example 1, to obtain 0.87 g of terpyridine aniline compound with a yield of 28%.

[0089] (4) In a Schrank flask, add 0.87 g (2.02 mmol) of a terpyridine aniline compound, 0.32 g (1.01 mmol) of 4,4'-dibromobiphenyl, 0.13 g (2.02 mmol) of copper powder, 0.26 g (2.02 mmol) of potassium carbonate, and 0.21 g (0.81 mmol) of 18-crown ether-6. Then apply three nitrogen-vacuum cycles until the solid reactants are fully mixed and impregnated in the nitrogen atmosphere. Then, add 10 ml of o-dichlorobenzene solvent using a syringe. The remaining operations and conditions of this step are the same as in step (4) of Example 1. 0.65 g of the target product, a multidentate organic ligand compound containing a "triphenylamine-terpyridine" structure, was obtained, with a yield of 32%.

[0090] Example 3

[0091] The structure of the multidentate organic ligand is shown below:

[0092]

[0093] (1) Add 5 g (33.0 mmol) of 4-nitrobenzaldehyde, 6.05 g (50.0 mmol) of 2-acetylpyridine, 2.81 g (50.0 mmol) of potassium hydroxide and 1.16 g (33.0 mmol) of ammonium hydroxide to a three-necked flask containing a magnetic inlet. After stirring, add 198 ml of methanol as a solvent. The remaining operations and conditions of this step are the same as in step (1) of Example 1, to obtain 3.6 g of product 4'-(4-nitrophenyl)-2,2':6',2"-terpyridine, with a yield of 31%.

[0094] (2) 3.6 g (10.23 mmol) of 4'-(4-nitrophenyl)-2,2':6',2"-terpyridine and 1.63 g (15.35 mmol) of 10% Pd / C were added to a three-necked flask equipped with a magnetic stirrer, a condenser, and a spherical drying tube. Nitrogen gas was purged through one end of the flask. After 3 min, 300 ml of ethanol was added as a solvent and the mixture was stirred. Nitrogen gas was continuously purged throughout the reaction. After heating to reflux, heating was stopped, and 3.93 g (51.15 mmol) of 65% hydrazine hydrate was slowly added dropwise. The remaining operations and conditions of this step were the same as in step (2) of Example 1, yielding 2.79 g of 4'-(4-aminophenyl)-2,2':6',2"-terpyridine, with a yield of 84%.

[0095] (3) 2.79 g (8.6 mmol) of 4'-(4-aminophenyl)-2,2':6',2"-terpyridine, 2.24 g (8.6 mmol) of p-iodoanisole, 0.55 g (8.6 mmol) of copper powder, 1.10 g (8.6 mmol) of potassium carbonate and 0.91 g (3.44 mmol) of 18-crown ether-6 were added to a Schrank flask, and then three nitrogen-vacuum cycles were applied. After the solid reactants were thoroughly mixed and impregnated in the nitrogen atmosphere, 45 ml of o-dichlorobenzene solvent was added using a syringe. The remaining operations and conditions of this step were the same as in step (3) of Example 1, yielding 1.41 g of terpyridine aniline compounds, with a yield of 36%.

[0096] (4) In a Schrank flask, add 1.37 g (3.0 mmol) of a triphenylpyridine aniline compound, 0.35 g (1.5 mmol) of p-dibromobenzene, 0.19 g (3.0 mmol) of copper powder, 0.38 g (3.0 mmol) of potassium carbonate, and 0.32 g (1.2 mmol) of 18-crown ether-6. Then apply three nitrogen-vacuum cycles until the solid reactants are fully mixed and impregnated in the nitrogen atmosphere. Then, add 15 ml of o-dichlorobenzene solvent using a syringe. The remaining operations and conditions of this step are the same as in step (4) of Example 1. 1.01 g of the target product, a multidentate organic ligand compound containing a "triphenylamine-triphenylpyridine" structure, was obtained, with a yield of 34%.

[0097] Example 4

[0098] The structure of the multidentate organic ligand is shown below:

[0099]

[0100] (1) Add 5 g (33.0 mmol) of 4-nitrobenzaldehyde, 7.99 g (66.0 mmol) of 2-acetylpyridine, 5.55 g (99.0 mmol) of potassium hydroxide and 3.47 g (99.0 mmol) of ammonium hydroxide to a three-necked flask containing a magnetic inlet. Stir well and add 264 ml of methanol as a solvent. Stir at room temperature for 84 h and filter. Dissolve the precipitate in 40 ml of dichloromethane and extract and wash the product with 30 ml of 3% sodium bicarbonate solution. Combine the organic phases and dry with anhydrous magnesium sulfate. Filter and remove the filtrate by rotary evaporation to obtain 3.98 g of product 4'-(4-nitrophenyl)-2,2':6',2"-terpyridine, with a yield of 34%.

[0101] (2) Add 3.98 g (11.22 mmol) of 4'-(4-nitrophenyl)-2,2':6',2"-terpyridine and 2.39 g (22.44 mmol) of 10% Pd / C to a three-necked flask equipped with a magnetic stirrer, a condenser, and a spherical drying tube. Purge the flask with nitrogen through one end. After 4 min, add 440 ml of ethanol as a solvent and stir. Nitrogen gas is continuously purged throughout the reaction. After heating to reflux, stop the reaction. Heating was stopped, and 7.48 g (112.2 mmol) of 75% hydrazine hydrate was slowly added dropwise. The system was then allowed to react at 75 °C for 11 h under a nitrogen atmosphere. After the reaction was complete, the reaction solution was filtered while hot to remove Pd / C. The filtrate was washed with deionized water, and the organic phases were combined and dried over anhydrous magnesium sulfate. After filtration and rotary evaporation to remove the filtrate, 3.13 g of the product 4'-(4-aminophenyl)-2,2':6',2"-terpyridine was obtained, with a yield of 86%.

[0102] (3) Add 3.13 g (9.65 mmol) of 4'-(4-aminophenyl)-2,2':6',2"-terpyridine, 4.21 g (19.3 mmol) of p-methyliodobenzene, 1.23 g (19.3 mmol) of copper powder, 2.47 g (19.3 mmol) of potassium carbonate and 1.28 g (4.83 mmol) of 18-crown ether-6 to a Schrank flask, and then apply three nitrogen-vacuum cycles. After the solid reactants are fully mixed and impregnated in the nitrogen atmosphere, add 80 ml of o-dichlorobenzene solvent using a syringe, and apply three nitrogen-vacuum cycles to the system again. Let the system react at 155 °C for 16 h. After the reaction is complete, filter while hot, remove the organic solvent o-dichlorobenzene from the filtrate by vacuum distillation, and then dissolve the crude product in a minimum amount of N,N-dimethylacetamide. After the reaction is complete, discharge into brine, filter, and dry. Use dichloromethane / methanol as the eluent (V 二氯甲烷 V 甲醇 The crude product was purified by column chromatography (ratio = 5:1) to obtain 1.68 g of tripyridine aniline compounds, with a yield of 42%.

[0103] (4) Add 1.68 g (4.05 mmol) of terpyridine aniline compound, 1.33 g (4.05 mmol) of 4,4'-dibromodiphenyl ether, 0.51 g (8.10 mmol) of copper powder, 1.04 g (8.10 mmol) of potassium carbonate, and 0.54 g (2.03 mmol) of 18-crown ether-6 to a Schrank flask, and then apply three nitrogen-vacuum cycles. After the solid reactants are fully mixed and impregnated in the nitrogen atmosphere, add 32 ml of o-dichlorobenzene solvent using a syringe, and apply three nitrogen-vacuum cycles to the system again. Let the system react at 155 °C for 16 h. After the reaction is complete, filter while hot, remove the organic solvent o-dichlorobenzene from the filtrate by vacuum distillation, and then dissolve the crude product in a minimum amount of N,N-dimethylacetamide. After the reaction is complete, discharge into brine, filter, and dry. Use dichloromethane / methanol as the eluent (V 二氯甲烷 V 甲醇 =3.5:1), the crude product was purified by column chromatography to obtain 1.81 g of the target product, a multidentate organic ligand compound containing the "triphenylamine-terpyridine" structure, with a yield of 45%.

[0104] Example 5

[0105] The structure of the multidentate organic ligand is shown below:

[0106]

[0107] (1) Add 5 g (33.0 mmol) of 4-nitrobenzaldehyde, 7.99 g (66.0 mmol) of 2-acetylpyridine, 5.55 g (99.0 mmol) of potassium hydroxide and 3.47 g (99.0 mmol) of ammonium hydroxide to a three-necked flask containing a magnetic inlet. After stirring, add 264 ml of methanol as a solvent. The remaining operations and conditions of this step are the same as in step (1) of Example 4, to obtain 4.79 g of product 4'-(4-nitrophenyl)-2,2':6',2"-terpyridine, with a yield of 41%.

[0108] (2) 4.68 g (13.2 mmol) of 4'-(4-nitrophenyl)-2,2':6',2"-terpyridine and 2.81 g (26.4 mmol) of 10% Pd / C were added to a three-necked flask equipped with a magnetic stirrer, a condenser, and a spherical drying tube. Nitrogen gas was purged through one end of the flask. After 4 min, 528 ml of ethanol was added as a solvent and the mixture was stirred. Nitrogen gas was continuously purged throughout the reaction. After heating to reflux, heating was stopped, and 8.8 g (132 mmol) of 75% hydrazine hydrate was slowly added dropwise. The remaining operations and conditions of this step were the same as in step (2) of Example 4, yielding 3.51 g of 4'-(4-aminophenyl)-2,2':6',2"-terpyridine, with a yield of 82%.

[0109] (3) Add 3.51 g (9.65 mmol) of 4'-(4-aminophenyl)-2,2':6',2"-terpyridine, 5.01 g (21.6 mmol) of p-ethyliodobenzene, 1.37 g (21.6 mmol) of copper powder, 2.77 g (21.6 mmol) of potassium carbonate and 1.43 g (5.4 mmol) of 18-crown ether-6 to a Schrank flask, and then apply three nitrogen-vacuum cycles. After the solid reactants are fully mixed and impregnated in the nitrogen atmosphere, add 88 ml of o-dichlorobenzene solvent using a syringe. The remaining operations and conditions of this step are the same as in step (3) of Example 4, to obtain 1.85 g of terpyridine aniline compound with a yield of 40%.

[0110] (4) In a Schrank flask, add 1.85 g (4.32 mmol) of a tripyridine aniline compound, 2.00 g (4.32 mmol) of 2,2-bis(4-bromophenyl)hexafluoropropane, 0.55 g (8.64 mmol) of copper powder, 1.11 g (8.64 mmol) of potassium carbonate, and 0.57 g (2.16 mmol) of 18-crown ether-6, and then apply three nitrogen-vacuum cycles. After the solid reactants are thoroughly mixed and impregnated in the nitrogen atmosphere, add 32 ml of o-dichlorobenzene solvent using a syringe. The remaining operations and conditions of this step are the same as in step (4) of Example 4, yielding 2.15 g of the target product, a multidentate organic ligand compound containing a "triphenylamine-terpyridine" structure, with a yield of 43%.

[0111] Example 6

[0112] The structure of the multidentate organic ligand is shown below:

[0113]

[0114] (1) Add 5 g (33.0 mmol) of 4-nitrobenzaldehyde, 7.99 g (66.0 mmol) of 2-acetylpyridine, 5.55 g (99.0 mmol) of potassium hydroxide and 3.47 g (99.0 mmol) of ammonium hydroxide to a three-necked flask containing a magnetic inlet. After stirring, add 264 ml of methanol as a solvent. The remaining operations and conditions of this step are the same as in step (1) of Example 4, to obtain 5.26 g of product 4'-(4-nitrophenyl)-2,2':6',2"-terpyridine, with a yield of 45%.

[0115] (2) 4.96 g (14 mmol) of 4'-(4-nitrophenyl)-2,2':6',2"-terpyridine and 2.98 g (28 mmol) of 10% Pd / C were added to a three-necked flask equipped with a magnetic stirrer, a condenser, and a spherical drying tube. Nitrogen gas was purged through one end of the flask. After 4 min, 560 ml of ethanol was added as a solvent and the mixture was stirred. Nitrogen gas was continuously purged throughout the reaction. After heating to reflux, heating was stopped, and 9.33 g (140 mmol) of 75% hydrazine hydrate was slowly added dropwise. The remaining operations and conditions of this step were the same as in step (2) of Example 4, yielding 3.81 g of 4'-(4-aminophenyl)-2,2':6',2"-terpyridine, with a yield of 84%.

[0116] (3) Add 3.24 g (10 mmol) of 4'-(4-aminophenyl)-2,2':6',2"-terpyridine, 4.92 g (20 mmol) of p-n-propyl iodobenzene, 1.27 g (20 mmol) of copper powder, 2.56 g (20 mmol) of potassium carbonate and 1.32 g (5 mmol) of 18-crown ether-6 to a Schrank flask, and then apply three nitrogen-vacuum cycles. After the solid reactants are thoroughly mixed and impregnated in the nitrogen atmosphere, add 80 ml of o-dichlorobenzene solvent using a syringe. The remaining operations and conditions of this step are the same as in step (3) of Example 4, to obtain 2.21 g of terpyridine aniline compound, with a yield of 50%;

[0117] (4) In a Schrank flask, 2.21 g (5 mmol) of a terpyridine aniline compound, 1.76 g (5 mmol) of 2,7-dibromo-9,9-dimethylfluorene, 0.64 g (10 mmol) of copper powder, 1.28 g (10 mmol) of potassium carbonate, and 0.66 g (2.5 mmol) of 18-crown ether-6 were added, followed by three nitrogen-vacuum cycles. After the solid reactants were thoroughly mixed and impregnated in the nitrogen atmosphere, 40 ml of o-dichlorobenzene solvent was added using a syringe. The remaining operations and conditions of this step were the same as in step (4) of Example 4, yielding 2.53 g of the target product, a multidentate organic ligand compound containing a "triphenylamine-terpyridine" structure, with a yield of 47%.

[0118] Example 7

[0119] The structure of the multidentate organic ligand is shown below:

[0120]

[0121] (1) Add 5 g (33.0 mmol) of 4-nitrobenzaldehyde, 7.99 g (66.0 mmol) of 2-acetylpyridine, 5.55 g (99.0 mmol) of potassium hydroxide and 3.47 g (99.0 mmol) of ammonium hydroxide to a three-necked flask containing a magnetic inlet. After stirring, add 264 ml of methanol as a solvent. The remaining operations and conditions of this step are the same as in step (1) of Example 4, to obtain 4.91 g of product 4'-(4-nitrophenyl)-2,2':6',2"-terpyridine, with a yield of 42%.

[0122] (2) 4.25 g (12 mmol) of 4'-(4-nitrophenyl)-2,2':6',2"-terpyridine and 2.55 g (24 mmol) of 10% Pd / C were added to a three-necked flask equipped with a magnetic stirrer, a condenser, and a spherical drying tube. Nitrogen gas was purged through one end of the flask. After 4 min, 480 ml of ethanol was added as a solvent and the mixture was stirred. Nitrogen gas was continuously purged throughout the reaction. After heating to reflux, heating was stopped, and 8.00 g (120 mmol) of 75% hydrazine hydrate was slowly added dropwise. The remaining operations and conditions of this step were the same as in step (2) of Example 4, yielding 3.08 g of 4'-(4-aminophenyl)-2,2':6',2"-terpyridine, with a yield of 79%.

[0123] (3) 2.60 g (8 mmol) of 4'-(4-aminophenyl)-2,2':6',2"-terpyridine, 4.16 g (16 mmol) of p-n-butyliodobenzene, 1.02 g (16 mmol) of copper powder, 2.05 g (16 mmol) of potassium carbonate and 1.06 g (4 mmol) of 18-crown ether-6 were added to a Schrank flask, and then three nitrogen-vacuum cycles were applied. After the solid reactants were thoroughly mixed and impregnated in the nitrogen atmosphere, 64 ml of o-dichlorobenzene solvent was added using a syringe. The remaining operations and conditions of this step were the same as in step (3) of Example 4, yielding 1.75 g of terpyridine aniline compounds with a yield of 48%.

[0124] (4) In a Schrank flask, add 0.91 g (2 mmol) of a terpyridine aniline compound, 0.95 g (2 mmol) of 2,7-dibromo-9,9-diphenylfluorene, 0.13 g (4 mmol) of copper powder, 0.26 g (4 mmol) of potassium carbonate, and 0.26 g (1 mmol) of 18-crown ether-6, and then apply three nitrogen-vacuum cycles. After the solid reactants are thoroughly mixed and impregnated in the nitrogen atmosphere, add 40 ml of o-dichlorobenzene solvent using a syringe. The remaining operations and conditions of this step are the same as in step (4) of Example 4, yielding 1.06 g of the target product, a multidentate organic ligand compound containing a "triphenylamine-terpyridine" structure, with a yield of 43%.

[0125] Example 8

[0126] The structure of the multidentate organic ligand is shown below:

[0127]

[0128] (1) Add 5 g (33.0 mmol) of 4-nitrobenzaldehyde, 15.98 g (132.0 mmol) of 2-acetylpyridine, 7.41 g (132.0 mmol) of potassium hydroxide and 5.78 g (156.0 mmol) of ammonium hydroxide to a three-necked flask containing a magnetic inlet. After stirring, add 330 ml of methanol as a solvent. Stir at room temperature for 96 h and filter. Dissolve the precipitate in 40 ml of dichloromethane, and extract and wash the product with 40 ml of 5% sodium bicarbonate solution. Combine the organic phases and dry with anhydrous magnesium sulfate. Filter under vacuum, remove the filtrate by rotary evaporation to obtain 3.51 g of product 4'-(4-nitrophenyl)-2,2':6',2"-terpyridine, with a yield of 30%.

[0129] (2) Add 3.19 g (9 mmol) of 4'-(4-nitrophenyl)-2,2':6',2"-terpyridine and 3.83 g (36 mmol) of 10% Pd / C to a three-necked flask equipped with a magnetic stirrer, a condenser, and a spherical drying tube. Purge the flask with nitrogen through one end. After 5 min, add 450 ml of ethanol as a solvent and stir. Nitrogen gas is continuously purged throughout the reaction. After heating to reflux, stop adding nitrogen. 7.94 g (135 mmol) of 85% hydrazine hydrate was slowly added dropwise under heat. The system was then allowed to react at 80 °C for 15 h under a nitrogen atmosphere. After the reaction was complete, the reaction solution was filtered while hot to remove Pd / C. The filtrate was washed with deionized water, the organic phases were combined and dried over anhydrous magnesium sulfate. After filtration and rotary evaporation to remove the filtrate, 2.28 g of the product 4'-(4-aminophenyl)-2,2':6',2"-terpyridine was obtained, with a yield of 78%.

[0130] (3) Add 2.27 g (7 mmol) of 4'-(4-aminophenyl)-2,2':6',2"-terpyridine, 5.17 g (21 mmol) of p-isopropyl iodobenzene, 1.33 g (21 mmol) of copper powder, 2.69 g (21 mmol) of potassium carbonate, and 1.11 g (4.2 mmol) of 18-crown ether-6 to a Schrank flask, and then apply three nitrogen-vacuum cycles. After the solid reactants are thoroughly mixed and impregnated in the nitrogen atmosphere, add 70 ml of o-dichlorobenzene solvent using a syringe, and apply three nitrogen-vacuum cycles to the system again. Let the system react at 175 °C for 20 h. After the reaction is complete, filter while hot, remove the organic solvent o-dichlorobenzene from the filtrate by vacuum distillation, and then dissolve the crude product in a minimum amount of N,N-dimethylacetamide. After the reaction is complete, discharge into brine, filter, and dry. Use dichloromethane / methanol as the eluent (V 二氯甲烷 V 甲醇 =5:1), the crude product was purified by column chromatography to obtain 0.99 g of tripyridine aniline compounds, with a yield of 32%;

[0131] (4) Add 0.91 g (2 mmol) of terpyridine aniline compound, 1.42 g (3 mmol) of 2,7-dibromo-9,9'-spirodifluorene, 0.38 g (6 mmol) of copper powder, 0.77 g (6 mmol) of potassium carbonate, and 0.32 g (1.2 mmol) of 18-crown ether-6 to a Schrank flask, and then apply three nitrogen-vacuum cycles. After the solid reactants are fully mixed and impregnated in the nitrogen atmosphere, add 20 ml of o-dichlorobenzene solvent using a syringe, and apply three nitrogen-vacuum cycles to the system again. Let the system react at 175 °C for 20 h. After the reaction is complete, filter while hot, remove the organic solvent o-dichlorobenzene from the filtrate by vacuum distillation, and then dissolve the crude product in a minimum amount of N,N-dimethylacetamide. After the reaction is complete, discharge into brine, filter, and dry. Use dichloromethane / methanol as the eluent (V 二氯甲烷 V 甲醇 =5:1), the crude product was purified by column chromatography to obtain 0.67 g of the target product, a multidentate organic ligand compound containing the "triphenylamine-terpyridine" structure, with a yield of 28%.

[0132] Example 9

[0133] The structure of the multidentate organic ligand is shown below:

[0134]

[0135] (1) Add 5 g (33.0 mmol) of 4-nitrobenzaldehyde, 7.99 g (66.0 mmol) of 2-acetylpyridine, 5.55 g (99.0 mmol) of potassium hydroxide and 3.47 g (99.0 mmol) of ammonium hydroxide to a three-necked flask containing a magnetic inlet. After stirring, add 330 ml of methanol as a solvent. The remaining operations and conditions of this step are the same as in step (1) of Example 8, to obtain 2.92 g of product 4'-(4-nitrophenyl)-2,2':6',2"-terpyridine, with a yield of 25%.

[0136] (2) 2.83 g (8 mmol) of 4'-(4-nitrophenyl)-2,2':6',2"-terpyridine and 3.41 g (32 mmol) of 10% Pd / C were added to a three-necked flask equipped with a magnetic stirrer, a condenser, and a spherical drying tube. Nitrogen gas was purged through one end of the flask. After 5 min, 480 ml of ethanol was added as a solvent and the mixture was stirred. Nitrogen gas was continuously purged throughout the reaction. After heating to reflux, heating was stopped, and 7.06 g (120 mmol) of 85% hydrazine hydrate was slowly added dropwise. The remaining operations and conditions of this step were the same as in step (2) of Example 8, yielding 1.97 g of 4'-(4-aminophenyl)-2,2':6',2"-terpyridine, with a yield of 76%.

[0137] (3) Add 1.95 g (6 mmol) of 4'-(4-aminophenyl)-2,2':6',2"-terpyridine, 4.68 g (18 mmol) of 1-(sec-butyl)-4-iodobenzene, 1.14 g (18 mmol) of copper powder, 2.31 g (18 mmol) of potassium carbonate and 0.95 g (3.6 mmol) of 18-crown ether-6 to a Schrank flask, and then apply three nitrogen-vacuum cycles. After the solid reactants are thoroughly mixed and impregnated in the nitrogen atmosphere, add 60 ml of o-dichlorobenzene solvent using a syringe. The remaining operations and conditions of this step are the same as in step (3) of Example 8, to obtain 0.85 g of terpyridine aniline compound, with a yield of 31%.

[0138] (4) In a Schrank flask, add 0.82 g (1.8 mmol) of a terpyridine aniline compound, 1.32 g (2.7 mmol) of 1,2-di(4-bromophenyl)ethylene, 0.34 g (5.4 mmol) of copper powder, 0.69 g (5.4 mmol) of potassium carbonate, and 0.29 g (1.08 mmol) of 18-crown ether-6, and then apply three nitrogen-vacuum cycles. After the solid reactants are thoroughly mixed and impregnated in the nitrogen atmosphere, add 18 ml of o-dichlorobenzene solvent using a syringe. The remaining operations and conditions of this step are the same as in step (4) of Example 8, yielding 0.74 g of the target product, a multidentate organic ligand compound containing a "triphenylamine-terpyridine" structure, in a yield of 33%.

[0139] Example 10

[0140] The structure of the multidentate organic ligand is shown below:

[0141]

[0142] (1) Add 5 g (33.0 mmol) of 4-nitrobenzaldehyde, 7.99 g (66.0 mmol) of 2-acetylpyridine, 5.55 g (99.0 mmol) of potassium hydroxide and 3.47 g (99.0 mmol) of ammonium hydroxide to a three-necked flask containing a magnetic inlet. After stirring, add 330 ml of methanol as a solvent. The remaining operations and conditions of this step are the same as in step (1) of Example 8, to obtain 3.16 g of product 4'-(4-nitrophenyl)-2,2':6',2"-terpyridine, with a yield of 27%.

[0143] (2) Add 3.00 g (8.5 mmol) of 4'-(4-nitrophenyl)-2,2':6',2"-terpyridine and 3.62 g (34 mmol) of 10% Pd / C to a three-necked flask equipped with a magnetic stirrer, a condenser, and a spherical drying tube. Purge the flask with nitrogen through one end. After 5 min, add 425 ml of ethanol as a solvent and stir. Nitrogen gas is continuously purged throughout the reaction. After heating to reflux, stop heating and slowly add 7.50 g (127.5 mmol) of 85% hydrazine hydrate. The remaining operations and conditions of this step are the same as in step (2) of Example 8, to obtain 2.26 g of 4'-(4-aminophenyl)-2,2':6',2"-terpyridine, with a yield of 82%.

[0144] (3) 2.11 g (6.5 mmol) of 4'-(4-aminophenyl)-2,2':6',2"-terpyridine, 5.07 g (19.5 mmol) of 1-iodo-4-isobutylbenzene, 1.24 g (19.5 mmol) of copper powder, 2.50 g (19.5 mmol) of potassium carbonate and 1.03 g (3.9 mmol) of 18-crown ether-6 were added to a Schrank flask, and then three nitrogen-vacuum cycles were applied. After the solid reactants were thoroughly mixed and impregnated in the nitrogen atmosphere, 65 ml of o-dichlorobenzene solvent was added using a syringe. The remaining operations and conditions of this step were the same as in step (3) of Example 8, yielding 1.01 g of terpyridine aniline compound in a yield of 34%.

[0145] (4) In a Schrank flask, add 1.01 g (2.2 mmol) of a triphenylpyridine aniline compound, 1.19 g (3.3 mmol) of 1,6-dibromopyrene, 0.42 g (6.6 mmol) of copper powder, 0.85 g (6.6 mmol) of potassium carbonate, and 0.35 g (1.32 mmol) of 18-crown ether-6, and then apply three nitrogen-vacuum cycles. After the solid reactants are thoroughly mixed and impregnated in the nitrogen atmosphere, add 22 ml of o-dichlorobenzene solvent using a syringe. The remaining operations and conditions of this step are the same as in step (4) of Example 8, yielding 0.71 g of the target product, a multidentate organic ligand compound containing a "triphenylamine-triphenylpyridine" structure, with a yield of 29%.

[0146] Example 11

[0147] The target ligand was polymerized with Fe(BF4)2·6H2O to obtain a metal ion-ligand supramolecular polymer film 1:

[0148] Weigh 87.5 mg (0.1 mmol) of the target ligand and 33.8 mg (0.1 mmol) of Fe(BF4)2·6H2O obtained in Example 1 and dissolve them in 100 ml of glacial acetic acid. Reflux at 40 °C for 10 h to allow the ligand to completely complex with the metal ions. Filter the insoluble substances while hot, distill under reduced pressure, wash several times with ethanol, and dry under vacuum to obtain 50 mg of solid metal supramolecular polymer.

[0149] Dissolve 25 mg of the above solid in 50 ml of methanol, filter out the insoluble matter, add 5 ml of the solution to the spray bottle of a pneumatic spray gun, and then spray it onto the surface of ITO conductive glass. Place it in an oven and dry it at 25°C for 10 h. After the methanol evaporates on the ITO glass surface, a uniform metal ion-ligand supramolecular polymer film is obtained, which is labeled as film 1.

[0150] Figure 3 The image shows the electrochromatogram of the metal supramolecular polymer labeled as film 1 in Example 11. The testing method involved applying voltages of 0V, 1V, and 1.4V to the working electrode using an electrochemical workstation in Amperometric it Curve mode, while simultaneously monitoring the absorbance changes at different wavelengths using a UV-Vis-NIR spectrophotometer. As shown, the film exhibits absorption in both the visible and near-infrared regions. The maximum absorption wavelength of the film changes as the voltage increases from 0V to 1.4V.

[0151] Cyclic voltammetry performance of the metal supramolecular polymer film (labeled 1) prepared in Example 11 was tested as follows: ITO containing the metal supramolecular polymer film from Example 11 was used as the working electrode, platinum wire as the counter electrode, Ag / AgCl as the reference electrode, and 0.1 M tetrabutylammonium perchlorate (TBAP) in acetonitrile solution as the electrolyte. Based on this three-electrode system, cyclic voltammetry performance was tested using an electrochemical workstation at a scan rate of 10. The results are shown below. Figure 4 , Figure 4 The cyclic voltammogram of the metal supramolecular polymer labeled as thin film 1 in Example 11; by Figure 4 It can be seen that the metal supramolecular polymer film marked as 1 has two pairs of reversible redox potentials.

[0152] Figure 5 , 6 The electrochromic response time spectrum of the metal supramolecular polymer labeled as film 1 in Example 11; Figure 5 The test method is as follows: using an electrochemical workstation, a square wave voltage of 0.00 to 1.00 V is applied to the working electrode in Chronoamperometry mode, and the change in its absorption spectrum at 910 nm is monitored using a UV-Vis-NIR spectrophotometer. Figure 6 The testing method was as follows: A square wave voltage of 0.00–1.80 V was applied to the working electrode in Chronoamperometry mode using an electrochemical workstation, while the change in its absorption spectrum at 680 nm was monitored using a UV-Vis-NIR spectrophotometer. Figure 5 , 6 It can be seen that the metal supramolecular polymer film marked as 1 has a faster response speed and excellent cycle stability.

[0153] Example 12

[0154] The target ligand is polymerized with Cu(ClO4)2·6H2O to obtain a metal ion-ligand supramolecular polymer film 2:

[0155] Weigh 87.5 mg (0.1 mmol) of the target ligand and 59.4 mg (0.16 mmol) of Cu(ClO4)2·6H2O obtained in Example 1 and dissolve them in 100 ml of glacial acetic acid. Reflux at 60 °C for 20 h to allow the ligand to completely complex with the metal ions. Filter the insoluble substances while hot, distill under reduced pressure, wash several times with ethanol, and dry under vacuum to obtain 57 mg of solid metal supramolecular polymer.

[0156] Dissolve 25 mg of the above solid in 50 ml of methanol, filter out the insoluble matter, add 15 ml of the solution to the spray bottle of a pneumatic spray gun, and then spray it onto the surface of ITO conductive glass. Place it in an oven and dry it at 35°C for 20 h. After the methanol evaporates on the ITO glass surface, a uniform metal ion-ligand supramolecular polymer film is obtained, which is labeled as film 2.

[0157] The electrochromic properties, cyclic voltammetry properties, and electrochromic response time of the obtained film 2 were tested. The results were similar to those of Example 11. When the voltage changed, the maximum absorption wavelength of the film also changed, which confirmed the successful preparation of the metal supramolecular polymer. Furthermore, the film has two pairs of reversible redox potentials, has a fast response speed to electrochromism, and excellent cyclic stability.

[0158] Example 13

[0159] The target ligand is polymerized with Zn(BF4)2·6H2O to obtain a metal ion-ligand supramolecular polymer film 3:

[0160] Weigh 87.5 mg (0.1 mmol) of the target ligand and 62.5 mg (0.18 mmol) of Zn(BF4)2·6H2O obtained in Example 1 and dissolve them in 100 ml of glacial acetic acid. Reflux at 80 °C for 30 h to allow the ligand to completely complex with the metal ions. Filter the insoluble substances while hot, distill under reduced pressure, wash several times with ethanol, and dry under vacuum to obtain 51 mg of solid metal supramolecular polymer.

[0161] Dissolve 25 mg of the above solid in 50 ml of methanol, filter out the insoluble matter, add 30 ml of the solution to the spray bottle of a pneumatic spray gun, and then spray it onto the surface of ITO conductive glass. Place it in an oven and dry it at 45°C for 30 h. After the methanol evaporates on the ITO glass surface, a uniform metal ion-ligand supramolecular polymer film is obtained, which is labeled as film 3.

[0162] The obtained film 3 was tested for electrochromic properties, cyclic voltammetry, and electrochromic response time. The results were similar to those of Example 11. When the voltage changed, the maximum absorption wavelength of the film also changed, which confirmed the successful preparation of the metal supramolecular polymer. Furthermore, the film has two pairs of reversible redox potentials, has a fast response speed to electrochromism, and excellent cyclic stability.

[0163] Example 14

[0164] The target ligand was polymerized with RuCl2(DMSO)4 to obtain a metal ion-ligand supramolecular polymer film 4:

[0165] Weigh 87.5 mg (0.1 mmol) of the target ligand and 97.7 mg (0.2 mmol) of RuCl2(DMSO)4 obtained in Example 1 and dissolve them in 100 ml of glacial acetic acid. Reflux at 100 °C for 50 h to allow the ligand to completely complex with the metal ions. Filter the insoluble substances while hot, distill under reduced pressure, wash several times with ethanol, and dry under vacuum to obtain 63 mg of solid metal supramolecular polymer.

[0166] Dissolve 25 mg of the above solid in 50 ml of methanol, filter out the insoluble matter, add 40 ml of the solution to the spray bottle of a pneumatic spray gun, and then spray it onto the surface of ITO conductive glass. Place it in an oven and dry it at 50°C for 40 h. After the methanol evaporates on the ITO glass surface, a uniform metal ion-ligand supramolecular polymer film is obtained, which is labeled as film 4.

[0167] The obtained film 4 was tested for electrochromic properties, cyclic voltammetry, and electrochromic response time. The results were similar to those of Example 11. When the voltage changed, the maximum absorption wavelength of the film also changed, which confirmed the successful preparation of the metal supramolecular polymer. Furthermore, the film has two pairs of reversible redox potentials, has a fast response speed to electrochromism, and excellent cyclic stability.

[0168] The solubility of the metal supramolecular polymers prepared in Examples 11-14 was tested. The concentration of the solutions formed by the different metal supramolecular polymers in different solvents was 2 mg / mL. The results are shown in Table 1.

[0169] Table 1. Solubility of the metal supramolecular polymers prepared in Examples 11-14 in six common solvents.

[0170]

[0171] Note: ++: Soluble at room temperature; +: Soluble upon heating; +-: Partially soluble; -: Insoluble upon heating.

[0172] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A multidentate organic ligand containing a triphenylamine-terpyridine structure, characterized in that, It has the structure shown in Equation I: Formula I In the formula, R1 is selected from one of the following structures: ； R2 is selected from one of the following structures: 。 2. The method for preparing the multidentate organic ligand according to claim 1, characterized in that, Includes the following steps: (1) Under alkaline conditions, 4'-(4-nitrophenyl)-2,2':6',2"-terpyridine was synthesized in a one-pot process using 4-nitrobenzaldehyde and 2-acetylpyridine as raw materials; (2) Under an inert atmosphere, the 4'-(4-nitrophenyl)-2,2':6',2"-terpyridine obtained in step (1) was reduced with hydrazine hydrate under the condition of catalyst Pd / C to obtain 4'-(4-aminophenyl)-2,2':6',2"-terpyridine; (3) Under alkaline conditions, the 4'-(4-aminophenyl)-2,2':6',2"-terpyridine obtained in step (2) and the iodobenzene compound undergo the Ullmann reaction with 18-crown ether-6 in the presence of copper powder catalyst to obtain terpyridine aniline compounds; (4) Under alkaline conditions, the tripyridine aniline compound obtained in step (3) and the dibromo compound are reacted with 18-crown ether-6 in the presence of copper powder as a catalyst to obtain the target product; The structural formula of the iodobenzene compound is as follows: ; The structural formula of the dibromo compound is: ; In the iodobenzene compound, R2 is the same as R2 in claim 1, and in the dibromo compound, R1 is the same as R1 in claim 1.

3. The preparation method according to claim 2, characterized in that, The alkali in step (1) is potassium hydroxide and ammonium hydroxide; the molar ratio of 4-nitrobenzaldehyde, 2-acetylpyridine, potassium hydroxide and ammonium hydroxide is 1:(1.5~4):(1.5~4):(1~5); the one-pot reaction temperature is room temperature and the reaction time is 72~96 h.

4. The preparation method according to claim 2, characterized in that, In step (2), the mass fraction of hydrazine hydrate is 65%~85%; the molar ratio of 4'-(4-nitrophenyl)-2,2':6',2"-terpyridine to hydrazine hydrate is 1:(5~15); the reduction reaction temperature is 70~80 ℃, and the reaction time is 8~15 h.

5. The preparation method according to claim 2, characterized in that, The base in step (3) is potassium carbonate; the molar ratio of 4'-(4-aminophenyl)-2,2':6',2"-terpyridine:iodobenzene compound:copper:potassium carbonate:18-crown ether-6 is 1:(1~3):(1~3):(1~3):(0.4~0.6); the reaction temperature of the Ullmann reaction is 140~175 ℃, and the reaction time is 12~20 h.

6. The preparation method according to claim 2, characterized in that, The base in step (4) is potassium carbonate; the molar ratio of the terpyridine aniline compound, dibromo compound, copper, potassium carbonate, and 18-crown ether-6 is 1:(0.5~1.5):(1~3):(1~3):(0.4~0.6); the reaction temperature of the Ullmann reaction is 140~175 ℃, and the reaction time is 10~40 h.

7. A metal supramolecular polymer, characterized in that, Synthesized by coordination between the multidentate organic ligand described in claim 1 and metal ions; The metal ions are selected from Fe(BF4)2·6H2O, Cu(ClO4)2·6H2O, Zn(BF4)2·6H2O, and RuCl2(DMSO)4.

8. The metal supramolecular polymer according to claim 7, characterized in that, The molar ratio of the polydentate organic ligand to the metal ion is 1:(1~2).

9. A metal ion-ligand supramolecular polymer film, characterized in that, The metal supramolecular polymer described in any one of claims 7 to 8 is dissolved in methanol, then sprayed onto the surface of ITO conductive glass, and dried to obtain the final product.

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