Triazine compound-based metal main chain polymer and synthesis method thereof

Abstract

The invention belongs to the technical field of high polymer material synthesis, and particularly relates to a metal main chain high polymer based on triazine compounds and a synthesis method of the metal main chain high polymer. By means of efficient reaction activity, excellent coordination capability and effective electronic regulation and control characteristics of the triazine compound, efficient and accurate synthesis of the auxiliary ligand framework is realized; then, a ligand-assisted synthesis strategy is utilized, the ligand is used as a template to be subjected to a coordination reaction with a metal ion compound under the heating condition, ordered polymerization of metal ions is achieved, and finally the triazine nickel metal main chain macromolecule with the molecular weight being 11.14 KDa is synthesized. The metal main chain polymer with the molecular weight reaching a ten thousand threshold value is synthesized for the first time, the metal main chain polymer has the advantages that the molecular structure is accurate and controllable, and the metal-metal bond interaction force is high, and meanwhile, the molecular weight is improved to bring visible light absorption capacity, semiconductor electrical band gap and solution processability to the metal main chain polymer; further development of a synthesis technology of a metal main chain high polymer material is promoted.

Description

Technical Field

[0001] The present invention belongs to the technical field of polymer material synthesis, and specifically relates to a metal main-chain polymer based on triazine compounds and a synthesis method thereof. Background Art

[0002] The polymer backbone plays an important role in determining the molecular structure and properties of polymers. The transformation of polymers from non-conjugated backbones to conjugated backbones has promoted the development of conductive polymers (J Chem Soc, Chem Commun 1977; 578-580.). At present, a completely new molecular structure of metal main-chain polymers has been reported (Angew Chem Int Ed 2023; 62: e202216060.), whose molecular backbone is entirely composed of metal ions interconnected by metal-metal bonds. This new type of polymer has excellent optical and electrical properties and shows good application prospects in optoelectronic devices, flexible electronics, and microwave absorption materials. The length and complexity of polymer macromolecular chains make them different from low-molecular-weight compounds in terms of physical and chemical properties. Compounds with a molecular weight exceeding 10 kDa are generally considered the threshold for exhibiting polymer characteristics. Therefore, it is crucial to achieve the synthesis of metal main-chain polymers with a molecular weight above the threshold.

[0003] So far, in the synthesis process of metal main-chain polymers, the low reactivity of organic reactions reduces the efficiency of synthesizing long-chain ligands; moreover, the existing ligand templates have high flexibility and poor electron regulation ability, resulting in their lack of the ability to coordinate with metals in sequence and making it difficult to form stable and continuous metal-metal bonds. Therefore, metal main-chain polymers with a molecular weight exceeding the threshold are still unable to be achieved, hindering the further development and application of metal main-chain polymers. Summary of the Invention

[0004] The purpose of the present invention is to provide a metal main-chain polymer based on triazine compounds with a high molecular weight, precisely controllable structure, and strong metal-metal bond interaction force, and a synthesis method thereof.

[0005] The present invention synthesizes metal main-chain polymers by virtue of the high reactivity, excellent coordination ability, and effective electron regulation of triazine compounds. For the first time, the molecular weight of the synthesized metal main-chain polymers breaks through the ten-thousand threshold, and the structure is precisely controllable, and the metal-metal bond interaction force is strong. At the same time, the increase in molecular weight brings new optoelectronic properties to metal main-chain polymers.

[0006] The triazine-based metal main-chain polymer provided by the present invention is denoted as PT-MBP, and its structural general formula is as follows:

[0007]

[0008] In the formula, M is a metal ion; wherein, (1) the main chain skeleton is completely formed by the mutual stable bonding between metal ions; (2) the triazine compound ligand stabilizes the spatial structure of the main chain skeleton through coordination interaction.

[0009] The present invention also provides a method for synthesizing the above-mentioned metal main-chain polymer based on triazine compounds. By virtue of the high reaction activity, excellent coordination ability and effective electron regulation of triazine compounds, a metal main-chain polymer is synthesized. The synthesis route is as follows:

[0010]

[0011] wherein, n is the number of repeating units, n is greater than or equal to 1; B n is a terminal protection intermediate, L n is a ligand; M is a metal ion; PT-MBP is a triazine-based metal main-chain polymer; the protected polymer side-chain monomer has the following structure:

[0012]

[0013] In the formula, R is an amino protecting group.

[0014] The specific synthesis steps are as follows:

[0015] Step (i): Connect the polymer side-chain monomer with the precursor binding molecule through Buchwald coupling reaction and protecting group strategy to obtain a terminal protection intermediate (B ni ); the specific process is: (1) Dissolve bromopyridine calixarene and diaminopyridine in an organic solvent, and under nitrogen protection, heat and couple under the catalysis of a palladium catalyst, an organic phosphorus ligand and a base to obtain a precursor binding molecule; (2) Dissolve the polymer side-chain monomer and the precursor binding molecule in an organic solvent, and under nitrogen protection, heat and couple under the catalysis of a palladium catalyst, an organic phosphorus ligand and a base to obtain the corresponding terminal protection intermediate (B ni ). Among them:

[0016] The calixarene is selected from one of calix[4]arene, 4-alkylcalix[4]arene, thiacalix[4]arene, 4-hydroxycalix[4]arene, tert-butylcalix[4]arene. Preferably, it is tert-butylcalix[4]arene.

[0017] The organic solvent is selected from toluene, pyridine, methylpyridine, 1,4-dioxane, dichloromethane, tetrahydrofuran, N,N-dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone or xylene. Preferably, it is xylene, dimethyl sulfoxide or pyridine.

[0018] The palladium catalyst is selected from tetrakis(triphenylphosphine)palladium, tris(dibenzylideneacetone)dipalladium, palladium acetate, bis(benzonitrile)palladium dichloride, bis(dibenzylideneacetone)palladium, bis(tricyclohexylphosphine)palladium dichloride, palladium di(acetylacetonate), or palladium tetrakis(4-carboxyphenyl)porphyrin. Preferably, it is tris(dibenzylideneacetone)dipalladium or bis(benzonitrile)palladium dichloride.

[0019] The organic phosphorus ligand is selected from 1,3-bis(diphenylphosphino)propane, 1,1'-binaphthalene-2,2'-bis(diphenylphosphine), 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl, or dicyclohexyl[3,6-dimethoxy-2',4',6'-triisopropyl[1,1'-biphenyl]-2-yl]phosphine. Preferably, it is 1,3-bis(diphenylphosphino)propane or 1,1'-binaphthalene-2,2'-bis(diphenylphosphine).

[0020] The base is selected from sodium hydroxide, potassium hydroxide, potassium tert-butoxide, sodium tert-butoxide, diisopropylethylamine, cesium carbonate, or potassium carbonate. Preferably, it is sodium tert-butoxide.

[0021] The polymerizable side chain monomer is a halogenated amino triazine chain with a protected amino group.

[0022] Furthermore, the triazine compound is selected from melamine, benzoguanamine, 6-methyl-1,3,5-triazine-2,4-diamine, 2,4-diamino-1,3,5-triazine, 2,4-diamino-6-(4-methylphenyl)-1,3,5-triazine, 2,4-diamino-6-(4-chlorophenyl)-1,3,5-triazine, cyanuric chloride, 2,4-dichloro-1,3,5-triazine, 2,4-dichloro-6-phenyl-1,3,5-triazine, 2,4-dichloro-6-methoxy-1,3,5-triazine, or 2,4-dichloro-6-ethyltriazine. Preferably, it is benzoguanamine or 2,4-dichloro-6-phenyl-1,3,5-triazine.

[0023] The triazine compound contains melamine, benzoguanamine, 6-methyl-1,3,5-triazine-2,4-diamine, 2,4-diamino-1,3,5-triazine, 2,4-diamino-6-(4-methylphenyl)-1,3,5-triazine, 2,4-diamino-6-(4-chlorophenyl)-1,3,5-triazine, cyanuric chloride, 2,4-dichloro-1,3,5-triazine, 2,4-dichloro-6-phenyl-1,3,5-triazine, 2,4-dichloro-6-methoxy-1,3,5-triazine, or 2,4-dichloro-6-ethyltriazine.

[0024] Preferably, the triazine compound contains 2,4-dichloro-6-phenyl-1,3,5-triazine or benzoguanamine.

[0025] Furthermore, the amino protecting group is selected from acetyl, trimethylsilylethoxycarbonyl, phthaloyl, tert-butoxycarbonyl, p-methoxybenzyl, p-toluenesulfonyl or 2,4-dimethoxybenzyl. Preferably, it is 2,4-dimethoxybenzyl.

[0026] The protecting group contains acetyl, trimethylsilylethoxycarbonyl, phthaloyl, tert-butoxycarbonyl, p-methoxybenzyl, p-toluenesulfonyl or 2,4-dimethoxybenzyl.

[0027] Preferably, the protecting group contains 2,4-dimethoxybenzyl.

[0028] Step (ii): Perform a deprotection reaction on the terminal protected intermediate (B ni ). Specifically, dissolve the terminal protected intermediate (B ni ) in an organic solvent, and under heating conditions, under the action of a strong acid, remove the protecting group to activate the functional group; repeat the above step (i) and step (ii) (the number of repetition cycles is greater than or equal to 1) to obtain a ligand (L n ) with precise controllability; where:

[0029] The acid is selected from glacial acetic acid, dilute hydrochloric acid, trifluoroacetic acid, trichloroacetic acid or dilute sulfuric acid. Preferably, it is trifluoroacetic acid.

[0030] The organic solvent is selected from dichloromethane, chloroform, acetonitrile, acetone, methanol or tetrahydrofuran. Preferably, it is acetonitrile.

[0031] The heating temperature is 75 - 80 °C, and the time is 10 - 12 h:

[0032] The ligand contains one or more groups of triazinyl, pyridyl, phenyl, alkyl, nitro, amino, hydroxyl or conjugated olefin;

[0033] More preferably, the ligand contains triazinyl, phenyl or amino groups.

[0034] Step (iii): Perform a metal coordination reaction on the ligand (L n ) obtained in step (ii) with a metal ion compound under heating conditions to achieve the orderly polymerization of metal ions and obtain the corresponding triazine-based metal main-chain polymer (PT-MBP).

[0035] The specific conditions for the metal coordination reaction are: dissolve the ligand (L n ) and the metal ion compound in an organic solvent, and heat under nitrogen protection for metallization to obtain a metal main-chain polymer. Where:

[0036] The metal is selected from one or more of transition metals.

[0037] The metal ion compound is selected from acetate salts, halide salts, triphenylphosphine-substituted salts or acetonitrile-substituted salts of alkali metals. Preferably, it is an acetate salt.

[0038] The organic solvent is selected from N,N-dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, xylene or naphthalene. Preferably, it is naphthalene.

[0039] For the metallization by heating, the heating temperature is 200 - 210 °C and the time is 5 - 6 h.

[0040] Compared with the prior art, the present invention has the following technical effects:

[0041] 1. The present invention creatively proposes a preparation method of a metal main-chain polymer based on triazine compounds. By virtue of the high reaction activity, excellent coordination ability and effective electron regulation of triazine compounds, the efficient and precise synthesis of the auxiliary ligand framework is realized; then, using the ligand-assisted synthesis strategy, the ligand is used as a template to carry out a coordination reaction with the metal ion compound under heating conditions, enabling the orderly polymerization of metal ions and realizing the controllable polymerization of triazine-based nickel metal main-chain polymers. This synthesis method is simple and efficient.

[0042] 2. Through the high reaction activity and electron regulation ability of triazine compounds, the present invention regulates the degree of polymerization, electron conjugation degree and metal coordination ability of the ligand template, and obtains a metal main-chain polymer with a molecular weight of 11.14 KDa, achieving a breakthrough in the molecular weight of metal main-chain polymers beyond the ten-thousand threshold for the first time.

[0043] 3. The electrical band gap of the triazine-based metal main-chain polymer prepared by the present invention is 2.66 eV, showing the electrical band gap properties of a semiconductor. Its thermal decomposition temperature is 261 °C, indicating high thermal stability. At the same time, this polymer has good solubility in various solvents and is suitable for solution processing methods. Therefore, this novel polymer is expected to be applied in semiconductors, optoelectronic materials or single-molecule devices. BRIEF DESCRIPTION OF THE DRAWINGS

[0044] Figure 1 It is the matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF MS) diagram of the triazine-based metal main-chain polymer in the present invention.

[0045] Figure 2 It is the ultraviolet-visible absorption spectrum diagram of the triazine-based metal main-chain polymer in the present invention.

[0046] Figure 3 It is the reflection electron energy loss spectrum of the triazine-based metal main-chain polymer in the present invention.

[0047] Figure 4 It is the thermogravimetric analysis diagram of the triazine-based metal main-chain polymer in the present invention.

[0048] Figure 5 This is the solubility experiment diagram of the triazine-based metal main-chain polymer in the present invention. Detailed implementation manners

[0049] The present invention will be further introduced below through embodiments in conjunction with the accompanying drawings. The embodiments give detailed operation procedures, but the protection scope of the present invention is not limited to the following embodiments.

[0050] In the following embodiments:

[0051] The precursor binding molecule A is synthesized by the method described in the literature (Angew Chem Int Ed 2023; 62: e202216060.).

[0052] The synthesis method of the precursor compound is as follows:

[0053]

[0054] Dissolve bromopyridine calixarene (1.0 g, 0.079 mmol) and 2,6-diaminopyridine (1.72 g, 0.016 mol) in xylene (20 mL). Quickly add bis(dibenzylideneacetone)palladium(0) (72.00 mg, 0.079 mmol), 1,3-bis(diphenylphosphino)propane (65.00 mg, 0.157 mmol) and potassium tert-butoxide (706 mg, 6.29 mmol) under nitrogen protection, and then reflux for 2 h. After the solution is cooled, pour the reaction solution into petroleum ether, filter and wash the filter cake with deionized water. Then dissolve the filter cake in tetrahydrofuran and filter to remove insoluble impurities. Distill off the solvent under reduced pressure to obtain 1.01 g of brown solid powder A with a yield of 91%. The data of its nuclear magnetic resonance hydrogen spectrum, carbon spectrum and infrared spectrum are as follows:

[0055] 1 H NMR(400MHz,DMSO-d6,ppm):δ8.80(s,4H),7.55(t,J=7.9Hz,4H),7.14(s,8H),6.94(t,J=8.0Hz,4H),6.78(d,J=7.9Hz,4H),6.73(d,J=8.0Hz,4H),6.64(d,J=8.0Hz,4H),5.87(d,J=7.8Hz,4H),5.43(s,8H),3.98(d,J=12.5Hz,4H),3.11(d,J=12.7Hz,4H),1.18(s,36H).

[0056] 1313C NMR (100 MHz, DMSO-d6, ppm): δ 163.5, 158.4, 153.5, 152.6, 147.3, 146.1, 139.8, 138.6, 134.8, 125.3, 104.3, 101.5, 100.4, 99.6, 34.3, 31.7, 31.5.

[0057] FTIR (KBr, cm -1 ): 3487, 3197, 3122, 3055, 2960, 2925, 2865, 1611, 1574, 1520, 1448, 1436, 1395, 1361, 1317, 1277, 1249, 1215, 1191, 1152, 1120, 1079, 1032, 870, 784, 726.

[0058] The high-resolution mass spectrometry data are as follows: Theoretical value of high-resolution mass spectrometry for C 84 H 88 N 16 NaO4 [M + Na] + : 1407.97; Measured value: 1408.02.

[0059] Example 1: Synthesis of a metal main-chain polymer based on a triazine compound:

[0060] The specific synthesis steps are as follows:

[0061] Step (i) Synthesis of the side-chain compound

[0062] a. Synthesis of side-chain compound 1

[0063] The synthesis reaction equation is as follows:

[0064]

[0065] Dissolve 2,4-dichloro-6-phenyl-1,3,5-triazine (11.03 g, 48.77 mmol) and bis(2,4-dimethoxybenzyl)amine (10.00 g, 32.51 mmol) in xylene (150 mL). Subsequently, add N,N-diisopropylethylamine (8.41 g, 65.02 mmol) to the system, and then reflux for 24 h. After the reaction is completed, remove the solvent by distillation under reduced pressure, and purify by column chromatography (ethyl acetate:petroleum ether = 1:10) to obtain 14.6 g of a white solid powder compound 1, with a yield of 89%. The nuclear magnetic resonance hydrogen spectrum, carbon spectrum, and infrared spectrum data are as follows:

[0066] 11H NMR (400 MHz, DMSO-d6, ppm): δ 8.55 - 8.14 (m, 2H), 7.63 (t, J = 7.3 Hz, 1H), 7.54 (t, J = 7.7 Hz, 2H), 7.07 (dd, J = 10.2, 8.4 Hz, 2H), 6.57 (t, J = 7.5 Hz, 2H), 6.46 - 6.43 (m, 2H), 4.85 (s, 2H), 4.70 (s, 2H), 3.82 - 3.69 (m, 12H).

[0067] 13 13C NMR (100 MHz, DMSO-d6, ppm): δ 171.7, 170.3, 165.9, 160.5, 160.4, 158.6, 135.0, 133.3, 129.4, 129.2, 129.2, 128.9, 116.9, 116.5, 105.0, 104.9, 98.8, 98.8, 55.8, 55.6, 55.6, 44.9, 44.8.

[0068] FT-IR (KBr, cm -1 ): 3393, 3266, 3169, 3053, 3004, 2952, 3926, 2851, 2361, 2327, 1573, 1551, 1505, 1462, 1370, 1462, 1370, 1318, 1255, 1207, 1157, 1121, 1074, 1036, 981, 934, 826, 778, 737, 702, 642, 539, 513, 457.

[0069] The mass spectrometry data are as follows:

[0070] Mass spectrometry (MALDI-TOF, m / z) theoretical value: C 27 H 27 ClN4O4Na [M+Na] + : 529.16; measured value: 529.22.

[0071] b. Synthesis of side chain compound 2

[0072] The synthesis reaction equation is as follows:

[0073]

[0074] The side chain compound 1 (10.00 g, 19.76 mmol) and melamine (7.40 g, 39.52 mmol) were dissolved in tetrahydrofuran (150 mL). Under nitrogen protection, tris(dibenzylideneacetone)dipalladium (347.7 mg, 0.38 mmol), 1,1'-binaphthalene-2,2'-bis(diphenylphosphine) (479.5 mg, 0.76 mmol) and sodium tert-butoxide (3.80 g, 39.52 mmol) were quickly added, and the mixture was refluxed for 12 h. After the reaction was completed, the solvent was removed by distillation under reduced pressure, and the product was purified by column chromatography (methanol:dichloromethane = 1:80) to obtain 10.7 g of yellow solid powder compound 2 with a yield of 85%. The 1H NMR, 13C NMR and IR spectral data are as follows:

[0075] 1 1H NMR (400 MHz, DMSO-d6, ppm): δ 10.01 (s, 1H), 8.55 - 8.18 (m, 4H), 7.62 - 7.46 (m, 4H), 7.38 (t, J = 7.7 Hz, 3H), 7.20 (d, J = 8.4 Hz, 1H), 7.14 (s, 1H), 7.07 (d, J = 8.4 Hz, 1H), 6.56 (dd, J = 7.4, 2.3 Hz, 2H), 6.45 - 6.42 (m, 2H), 4.86 (d, J = 6.6 Hz, 4H), 3.78 (s, 3H), 3.72 (d, J = 3.6 Hz, 9H).

[0076] 13 13C NMR (100 MHz, DMSO-d6, ppm): δ 171.2, 170.8, 168.0, 166.5, 165.2, 164.8, 160.2, 160.1, 158.6, 158.5, 136.8, 136.8, 132.3, 132.2, 129.7, 128.9, 128.8, 128.6, 128.6, 128.4, 118.0, 117.9, 105.1, 98.7, 98.7, 55.8, 55.7, 55.6, 43.8, 43.7.

[0077] FT-IR (KBr, cm -1 ): 3665, 3472, 3314, 3154, 2970, 2903, 1592, 1547, 1500, 1459, 1379, 1339, 1287, 1256, 1206, 1155, 1112, 1043, 980, 917, 826, 779, 732, 700, 641, 594, 529, 508, 456, 434.

[0078] The mass spectrometry data are as follows:

[0079] Theoretical value of mass spectrometry (MALDI-TOF, m / z): C 36 H 35 N9O4Na [M+Na] + : 680.27; Measured value: 680.32.

[0080] c. Synthesis of side chain compound 3

[0081] The synthesis reaction equation is as follows:

[0082]

[0083] Dissolve side chain compound 2 (10.00 g, 15.22 mmol) and 2,4-dichloro-6-phenyl-1,3,5-triazine (6.88 g, 30.44 mmol) in xylene (150 mL). Under nitrogen protection, quickly add tris(dibenzylideneacetone)dipalladium (557.7 mg, 0.61 mmol), 1,1'-binaphthalene-2,2'-bis(diphenylphosphine) (759.7 mg, 1.22 mmol) and sodium tert-butoxide (2.93 g, 30.44 mmol), and reflux for 12 h. After the reaction is completed, remove the solvent by distillation under reduced pressure, and purify by column chromatography (methanol:dichloromethane = 1:200) to obtain 8.3 g of white solid powder compound 3, with a yield of 64%. The data of its 1H NMR, 13C NMR and IR spectra are as follows:

[0084] 1 1H NMR (400 MHz, DMSO-d6, ppm): δ 10.74 (s, 1H), 8.53 (d, J = 7.2 Hz, 2H), 8.41 (dd, J = 9.2, 7.2 Hz, 4H), 7.69 - 7.59 (m, 2H), 7.58 - 7.42 (m, 7H), 7.15 (d, J = 8.5 Hz, 1H), 7.01 (d, J = 8.4 Hz, 1H), 6.54 (d, J = 8.2 Hz, 2H), 6.41 (d, J = 8.4 Hz, 2H), 4.82 (d, J = 7.0 Hz, 4H), 3.77 - 3.66 (m, 12H).

[0085] 1313C NMR (100 MHz, DMSO-d6, ppm): δ 173.2, 172.2, 171.1, 170.9, 166.6, 165.8, 165.5, 165.2, 164.7, 160.2, 160.1, 158.6, 158.5, 136.7, 135.9, 134.5, 134.0, 133.2, 132.4, 129.5, 129.3, 129.2, 129.0, 128.9, 128.8, 128.6, 117.8, 117.7, 105.0, 98.7, 55.8, 55.7, 55.6, 43.8, 43.8.

[0086] FT-IR (KBr, cm -1 ): 3409, 3270, 3161, 3061, 2998, 2932, 2834, 1607, 1578, 1510, 1463, 1374, 1330, 1256, 1207, 1156, 1121, 1072, 1035, 980, 932, 845, 825, 778, 702, 641, 532, 511, 456, 406.

[0087] The mass spectrometry data are as follows:

[0088] Mass spectrometry (MALDI-TOF, m / z) theoretical value: C 45 H 39 ClN 12 O4Na [M+Na] + : 869.28; measured value: 869.41.

[0089] Synthesis of the ligand in step (ii)

[0090] The synthesis reaction equation is as follows:

[0091]

[0092] ①Dissolve the precursor compound A (414.7 mg, 0.30 mmol) and the compound 3 polymerization monomer (2.00 g, 2.36 mmol) in ultradry xylene (50 mL). Quickly add bis(dibenzylideneacetone)palladium(0) (165.3 mg, 0.18 mmol), 1,1'-binaphthalene-2,2'-bis(diphenylphosphine) (224.2 mg, 0.36 mmol), and sodium tert-butoxide (230.4 mg, 2.40 mmol) under nitrogen protection, and then reflux for 12 h. After the reaction is completed, remove the solvent by distillation under reduced pressure, wash with tetrahydrofuran, filter, add cold methanol (200 mL), and collect the resulting precipitate by vacuum filtration. Recrystallize the filter cake with tetrahydrofuran and diethyl ether, filter, and collect the solid to obtain B1. Subsequently, dissolve the intermediate B1 (1.00 g, 0.22 mmol) in acetonitrile (30 mL), slowly add trifluoroacetic acid (251.3 mg, 2.20 mmol) to the system, and reflux for 12 h. After the reaction is completed, remove the solvent by distillation under reduced pressure, dissolve in methanol (30 mL) and filter, add an aqueous sodium bicarbonate solution (20 mL) to the filtrate, filter, wash with deionized water (100 mL), and dry to obtain a brown powder solid product L1, 630.0 mg, with a yield of 83%. The proton nuclear magnetic resonance, carbon nuclear magnetic resonance, and infrared spectrum data are as follows:

[0093] 1 H NMR (400 MHz, DMSO-d6, ppm): δ 10.87 (s, 4H), 10.36 (s, 4H), 9.61 (s, 4H), 9.05 (s, 4H), 8.55 (s, 8H), 8.45 (s, 8H), 8.38 (s, 12H), 8.25 (s, 8H), 8.02 (s, 4H), 7.53 - 7.48 (m, 52H), 7.07 - 7.03 (m, 8H), 3.96 (d, J = 8.4 Hz, 4H), 3.08 (d, J = 8.6 Hz, 4H), 1.09 (s, 36H).

[0094] 13 C NMR (100 MHz, DMSO-d6, ppm): δ 173.1, 172.2, 172.0, 171.5, 171.1, 168.8, 168.5, 168.2, 164.9, 164.5, 163.4, 158.7, 156.9, 136.3, 135.8, 135.3, 133.5, 133.4, 133.0, 132.5, 132.3, 129.3, 129.3, 129.1, 129.0, 128.9, 128.6, 128.5, 31.7.

[0095] FT-IR (KBr, cm -1): 3490, 3419, 3314, 3202, 2965, 2860, 2324, 1680, 1562, 1510, 1429, 1320, 1242, 1179, 1153, 1059, 982, 902, 825, 776, 698, 640, 595, 455。

[0096] Its mass spectrometry data are as follows:

[0097] Theoretical value of mass spectrometry (MALDI-TOF, m / z) C 192 H 160 N 64 NaO4: [M + Na] + : 3450.34; Measured value: 3449.60.

[0098] ② Dissolve compound L1 (518.1 mg, 0.15 mmol) and compound 3 polymerization monomer (1.00 g, 1.18 mmol) in ultradry xylene (50 mL). Quickly add bis(dibenzylideneacetone)palladium(0) (82.3 mg, 0.09 mmol), 1,1'-binaphthalene-2,2'-bis(diphenylphosphine) (112.0 mg, 0.18 mmol) and sodium tert-butoxide (115.3 mg, 1.20 mmol) under nitrogen protection, and then reflux for 12 h. After the reaction is completed, remove the solvent by distillation under reduced pressure, wash with tetrahydrofuran, filter, add cold methanol (200 mL), and collect the resulting precipitate by vacuum filtration. Recrystallize the filter cake with tetrahydrofuran and ether, filter, and collect the solid to obtain B2. Subsequently, dissolve the intermediate B2 (600.0 mg, 0.09 mmol) in acetonitrile (30 mL), slowly add trifluoroacetic acid (102.6 mg, 0.90 mmol) to the system, and reflux for 12 h. After the reaction is completed, remove the solvent by distillation under reduced pressure, dissolve in methanol (30 mL) and filter, add aqueous sodium bicarbonate solution (20 mL) to the filtrate, filter, wash with deionized water (100 mL), and dry to obtain a brown powder solid product L2, 422.4 mg, with a yield of 86%. The nuclear magnetic resonance hydrogen spectrum, carbon spectrum and infrared spectrum data are as follows:

[0099] 11H NMR (400 MHz, DMSO-d6, ppm): δ 11.26 (s, 8H), 10.91 (s, 8H), 10.51 (s, 12H), 8.59 - 8.53 (m, 12H), 8.50 - 8.45 (m, 8H), 8.44 - 8.30 (m, 36H), 8.25 - 8.20 (m, 12H), 7.91 - 7.77 (m, 12H), 7.60 - 7.43 (m, 72H), 6.94 (s, 8H), 3.72 (d, J = 8.1 Hz, 4H), 3.20 (d, J = 8.5 Hz, 4H), 1.08 (s, 36H).

[0100] 13 13C NMR (100 MHz, DMSO-d6, ppm): δ 173.0, 172.2, 171.5, 168.8, 168.2, 166.1, 165.4, 165.2, 157.8, 153.1, 136.8, 136.1, 133.4, 133.0, 132.6, 132.3, 129.0, 128.8, 128.6, 128.5, 31.9, 31.8, 31.6.

[0101] FT-IR (KBr, cm -1 ): 3494, 3322, 3187, 2969, 2858, 2361, 2080, 1962, 1685, 1581, 1540, 1511, 1437, 1365, 1310, 1200, 1171, 1062, 904, 827, 778, 699, 643, 456.

[0102] The mass spectrometry data are as follows:

[0103] Mass spectrometry (MALDI-TOF, m / z) theoretical value for C 300 H 232 N 112 NaO4: [M + Na] + : 5492.79; measured value: 5493.37.

[0104] ③ Dissolve compound L2 (400.0 mg, 0.12 mmol) and compound 3 polymerization monomer (813.1 mg, 0.96 mmol) in ultradry xylene (50 mL). Quickly add bis(dibenzylideneacetone)palladium(0) (65.9 mg, 0.07 mmol), 1,1'-binaphthalene-2,2'-bis(diphenylphosphine) (89.6 mg, 0.14 mmol) and sodium tert-butoxide (92.3 mg, 0.96 mmol) under nitrogen protection, and then reflux the reaction for 12 h. After the reaction is completed, remove the solvent by distillation under reduced pressure, wash with tetrahydrofuran, filter, add cold methanol (200 mL), and collect the obtained precipitate by vacuum filtration. Recrystallize the filter cake with tetrahydrofuran and diethyl ether, filter, and collect the solid to obtain B3. Subsequently, dissolve intermediate B3 (600.0 mg, 0.07 mmol) in acetonitrile (30 mL), slowly add trifluoroacetic acid (79.8 mg, 0.70 mmol) to the system, and reflux the reaction for 12 h. After the reaction is completed, remove the solvent by distillation under reduced pressure, dissolve with methanol (30 mL) and filter, add aqueous sodium bicarbonate solution (20 mL) to the filtrate, filter, wash with deionized water (100 mL), and dry to obtain a brown powder solid product L3, 446.9 mg, with a yield of 85%. The 1H NMR, 13C NMR and IR spectral data are as follows:

[0105] 1 1H NMR (400 MHz, DMSO-d6, ppm): δ 11.22 (s, 12H), 10.95 (s, 12H), 10.36 (s, 16H), 8.59 - 8.56 (m, 16H), 8.50 - 8.48 (m, 16H), 8.43 - 8.38 (m, 48H), 8.25 - 8.23 (m, 12H), 7.86 - 7.81 (m, 12H), 7.62 - 7.58 (m, 36H), 7.51 - 7.48 (m, 60H), 7.35 - 7.31 (m, 12H), 6.91 (s, 8H), 3.97 (d, J = 8.0 Hz, 4H), 3.30 (d, J = 8.2 Hz, 4H), 1.09 (s, 36H).

[0106] 1313C NMR (100 MHz, DMSO-d6, ppm): δ 173.3, 173.1, 173.1, 172.9, 172.8, 172.4, 172.4, 172.3, 172.1, 171.9, 168.7, 168.7, 168.5, 168.4, 168.3, 168.1, 166.3, 166.1, 166.0, 165.8, 165.7, 165.4, 165.1, 164.8, 164.6, 164.4, 158.5, 156.8, 136.4, 136.1, 135.9, 135.8, 135.6, 135.3, 135.2, 135.1, 135.1, 133.8, 133.6, 133.5, 133.4, 133.2, 133.0, 132.9, 132.5, 132.4, 129.2, 129.0, 128.9, 128.8, 128.8, 31.9, 31.9, 31.7, 31.6。

[0107] FT-IR (KBr, cm -1 ): 3493, 3424, 3326, 3200, 3059, 2970, 2859, 2361, 2330, 1684, 1577, 1555, 1510, 1436, 1365, 1307, 1203, 1174, 1062, 904, 828, 778, 699, 644, 457。

[0108] The mass spectrometry data are as follows:

[0109] Mass spectrometry (MALDI-TOF, m / z) theoretical value C 408 H 304 N 160 NaO4: [M + Na] + : 7535.03; measured value: 7534.91.

[0110] ④ Dissolve compound L3 (400.0 mg, 0.05 mmol) and compound 3 polymerization monomer (338.8 mg, 0.4 mmol) in ultradry xylene (50 mL). Quickly add bis(dibenzylideneacetone)palladium(0) (27.5 mg, 0.03 mmol), 1,1'-binaphthalene-2,2'-bis(diphenylphosphine) (37.3 mg, 0.06 mmol) and sodium tert-butoxide (38.4 mg, 0.4 mmol) under nitrogen protection, and then reflux the reaction for 12 h. After the reaction is completed, remove the solvent by distillation under reduced pressure, wash with tetrahydrofuran, filter, add cold methanol (200 mL), and collect the resulting precipitate by vacuum filtration. Recrystallize the filter cake with tetrahydrofuran and diethyl ether, filter, and collect the solid to obtain B4. Subsequently, dissolve intermediate B4 (600.0 mg, 0.06 mmol) in acetonitrile (30 mL), slowly add trifluoroacetic acid (68.4 mg, 0.60 mmol) to the system, and reflux the reaction for 12 h. After the reaction is completed, remove the solvent by distillation under reduced pressure, dissolve with methanol (30 mL) and filter, add aqueous sodium bicarbonate solution (20 mL) to the filtrate, filter, wash with deionized water (100 mL), and dry to obtain a brown powder solid product L4, 441.4 mg, with a yield of 77%. The 1H NMR, 13C NMR and IR spectral data are as follows:

[0111] 1 1H NMR (400 MHz, DMSO-d6, ppm): δ 11.24 (s, 16H), 10.89 (s, 16H), 10.33 (s, 20H), 8.57 - 8.56 (m, 20H), 8.50 - 8.49 (m, 20H), 8.42 - 8.41 (m, 48H), 8.24 - 8.23 (m, 36H), 7.67 (m, 16H), 7.62 (m, 24H), 7.59 (m, 16H), 7.57 - 7.53 (m, 20H), 7.51 - 7.46 (m, 72H), 7.21 (s, 8H), 3.36 (d, J = 8.5 Hz, 4H), 3.18 (d, J = 8.6 Hz, 4H), 1.09 (s, 36H).

[0112] 1313C NMR (100 MHz, DMSO-d6, ppm): δ 173.1, 173.0, 172.8, 172.3, 172.2, 172.2, 172.2, 172.0, 171.5, 171.1, 168.7, 168.5, 168.3, 168.2, 168.1, 166.1, 165.9, 165.8, 165.6, 165.5, 165.4, 165.0, 164.9, 164.7, 164.5, 163.4, 158.7, 156.8, 136.8, 136.7, 136.7, 136.3, 136.2, 136.1, 136.0, 135.9, 135.8, 135.5, 135.2, 135.1, 133.5, 133.5, 133.4, 133.4, 133.2, 133.1, 133.0, 132.9, 132.5, 132.3, 132.3, 129.4, 129.3, 129.2, 129.0, 129.0, 128.9, 128.6, 128.5, 32.0, 32.0, 31.9, 31.9, 31.8, 31.7, 31.7, 31.6.

[0113] FT-IR (KBr, cm -1 ): 3732, 3502, 3420, 3322, 3208, 2968, 2861, 2361, 2334, 1687, 1636, 1596, 1529, 1434, 1386, 1357, 1305, 1277, 1226, 1184, 1153, 1063, 904, 827, 764, 702, 658, 595, 432.

[0114] The mass spectrometry data are as follows:

[0115] Mass spectrometry (MALDI-TOF, m / z) theoretical value C 516 H 376 N 208 NaO4: [M+Na] + : 9577.89; measured value: 9578.32.

[0116] (iii) Synthesis of metal main chain polymers

[0117] The synthesis reaction equation is as follows:

[0118]

[0119] The synthesized ligand L4 (143.7 mg, 0.015 mmol) and nickel acetate tetrahydrate (156.8 mg, 0.63 mmol) were dissolved in naphthalene (20 g), and under nitrogen protection, the mixture was stirred at 210 °C for 6 h. Then, the temperature was lowered to 180 °C, and n-butanol (5 mL) was added dropwise to the reaction mixture until the n-butanol evaporated completely to terminate the reaction. After the reaction was completed, the mixture was cooled to about 80 °C, and the dark black solution was treated with petroleum ether, followed by filtration. Then, the filtrate was dissolved in dichloromethane, and the solvent was removed to obtain a dark green metal main-chain polymer solid powder, 15 mg, with a yield of 9%.

[0120] The data of its infrared spectrum are as follows:

[0121] FT-IR (KBr, cm -1 ): 3634, 3310, 3061, 2952, 2917, 2849, 2360, 2322, 2086, 1736, 1663, 1587, 1510, 1457, 1433, 1373, 1257, 1203, 1152, 1090, 1022, 875, 799, 765, 738, 694, 651, 563, 500, 459, 422.

[0122] The data of its mass spectrum are as follows: Mass spectrum (MALDI-TOF, m / z) theoretical value for C 516 H 320 N 208 Ni 28 O4[M + H] + : 11142.10; measured value: 11142.87.

[0123] Example 2: Synthesis of a metal main-chain polymer based on triazine compounds;

[0124] The specific synthesis steps are as follows:

[0125] (i) Synthesis of the side-chain compound

[0126] The preparation process is the same as the synthesis method of the side-chain compound in step (i) of Example 1.

[0127] (ii) Synthesis of the ligand

[0128] The preparation process is the same as the synthesis method of ligand L n in step (ii) of Example 1.

[0129] (iii) Synthesis of the metal main-chain polymer

[0130] (a). Synthesis of PT-MBM1

[0131] The synthesis reaction equation is as follows:

[0132]

[0133] The synthesized ligand L1 (342.7 mg, 0.10 mmol) and nickel acetate tetrahydrate (373.3 mg , 1.5 mmol) were dissolved in naphthalene (20 g), and under nitrogen protection, the mixture was stirred at 210 °C for 6 h. Then, the temperature was lowered to 180 °C, and n-butanol (5 mL) was added dropwise to the reaction mixture until the n-butanol had evaporated completely to terminate the reaction. After the reaction was completed, the mixture was cooled to about 80 °C, and the dark black solution was treated with petroleum ether, followed by filtration. The filtrate was dissolved in dichloromethane and filtered again. After removing the solvent, a dark green metal backbone polymer solid powder, 84 mg, with a yield of 21% was obtained.

[0134] The data of its infrared spectrum are as follows:

[0135] FT-IR (KBr, cm -1 ): 3411, 3308, 2973, 2902, 2852, 2671, 1610, 1522, 1502, 1455, 1361, 1264, 1197, 1143, 1078, 1023, 968, 920, 803, 791, 702, 653, 525, 452.

[0136] The data of its mass spectrum are as follows: Mass spectrum (MALDI-TOF, m / z) theoretical value C 192 H 141 N 64 Ni 10 O4 [M + H] + : 3995.91; measured value: 3996.31.

[0137] (b). Synthesis of PT-MBM2

[0138] The synthesis reaction equation is as follows:

[0139]

[0140] The synthesized ligand L2 (547.2 mg, 0.10 mmol) and nickel acetate tetrahydrate (597.2 mg , 2.4 mmol) were dissolved in naphthalene (20 g), and under nitrogen protection, the mixture was stirred at 210 °C for 6 h. Then, the temperature was lowered to 180 °C, and n-butanol (5 mL) was added dropwise to the reaction mixture until the n-butanol had evaporated completely to terminate the reaction. After the reaction was completed, the mixture was cooled to about 80 °C, and the dark black solution was treated with petroleum ether, followed by filtration. The filtrate was dissolved in dichloromethane and filtered again. After removing the solvent, a dark green metal backbone polymer solid powder, 89 mg, with a yield of 14% was obtained.

[0141] The infrared spectrum data are as follows:

[0142] FT-IR(KBr, cm -1 ): 3464, 3423, 3318, 2983, 2921, 2844, 2659, 1636, 1517, 1500, 1451, 1322, 1257, 1186, 1142, 1111, 1069, 1011, 951, 932, 811, 783, 701, 662, 535, 473.

[0143] The mass spectrometry data are as follows: Mass spectrometry (MALDI-TOF, m / z) theoretical value C 300 H 201 N 112 Ni 16 O4[M + H] + : 6377.64; measured value: 6376.91.

[0144] (c) Synthesis of PT-MBM3

[0145] The synthesis reaction equation is as follows:

[0146]

[0147] Dissolve the synthesized ligand L3 (751.2 mg, 0.10 mmol) and nickel acetate tetrahydrate (821.2 mg , 3.3 mmol) in naphthalene (20 g), and under nitrogen protection, stir and react at 210 °C for 6 h. Then, lower the temperature to 180 °C, and gradually add n-butanol (5 mL) dropwise to the reaction mixture until the n-butanol evaporates completely to terminate the reaction. After the reaction is completed, cool to about 80 °C, treat the dark black solution with petroleum ether, then filter, and dissolve the filter cake with dichloromethane. After removing the solvent, a dark green metal main-chain polymer solid powder is obtained, 96 mg, with a yield of 11%.

[0148] The infrared spectrum data are as follows:

[0149] FT-IR(KBr, cm -1 ): 3492, 3434, 3323, 2943, 2922, 2872, 2661, 1607, 1511, 1496, 1443, 1342, 1258, 1188, 1130, 1069, 1017, 938, 907, 826, 771, 712, 683, 505, 492.

[0150] The mass spectrometry data are as follows: Mass spectrometry (MALDI-TOF, m / z) theoretical value C 408 H 261 N160 Ni 22 O4[M+H] + : 8759.75; Measured value: 8759.31.

[0151] Example 3: Synthesis of a Metal-Main Chain Polymer Based on Triazine Compounds

[0152] The specific synthesis steps are as follows:

[0153] (i) Synthesis of the side-chain compound

[0154] The preparation process is the same as the synthesis method of a. side-chain compound 1 in step (i) of Example 1.

[0155] (ii) Synthesis of the ligand

[0156] The synthesis reaction equation is as follows:

[0157]

[0158] Dissolve the precursor compound A (683.8 mg, 0.49 mmol) and the compound 1 polymerization monomer (2.00 g, 3.95 mmol) in ultradry xylene (50 mL). Quickly add bis(dibenzylideneacetone)palladium(0) (134.6 mg, 0.15 mmol), 1,1'-binaphthalene-2,2'-bis(diphenylphosphine) (186.6 mg, 0.30 mmol) and sodium tert-butoxide (376.7 mg, 3.92 mmol) under nitrogen protection, and then reflux for 12 h. After the reaction is completed, remove the solvent by distillation under reduced pressure, wash with tetrahydrofuran, filter, add cold methanol (200 mL), and collect the obtained precipitate by vacuum filtration. Recrystallize the filter cake with tetrahydrofuran and ether, filter, and collect the solid to obtain B5. Subsequently, dissolve the intermediate B5 (1.00 g, 0.31 mmol) in acetonitrile (30 mL), slowly add trifluoroacetic acid (353.4 mg, 3.10 mmol) to the system, and reflux for 12 h. After the reaction is completed, remove the solvent by distillation under reduced pressure, dissolve in methanol (30 mL) and filter, add an aqueous sodium bicarbonate solution (20 mL) to the filtrate, filter, wash with deionized water (100 mL), and dry to obtain a brown powder solid product L5, 557.2 mg, with a yield of 87%. The nuclear magnetic resonance hydrogen spectrum, carbon spectrum and infrared spectrum data are as follows:

[0159] 11H NMR (400 MHz, DMSO-d6, ppm): δ 9.11 (s, 4H), 8.85 (s, 4H), 8.31 (d, J = 7.7 Hz, 8H), 7.75 (d, J = 7.9 Hz, 4H), 7.57 - 7.53 (m, 8H), 7.50 (t, J = 7.5 Hz, 12H), 7.36 - 7.32 (m, 4H), 7.21 (s, 12H), 7.10 (d, J = 8.2 Hz, 4H), 7.03 (s, 8H), 4.03 (d, J = 11.2 Hz, 4H), 3.20 (d, J = 11.4 Hz, 4H), 1.17 (s, 36H).

[0160] 13 13C NMR (100 MHz, DMSO-d6, ppm): δ 174.3, 170.8, 167.6, 164.7, 163.5, 159.1, 158.9, 158.7, 158.5, 153.1, 152.7, 150.7, 137.0, 136.8, 134.8, 132.1, 129.1, 128.8, 128.5, 128.4, 125.5, 125.4, 31.8, 30.9.

[0161] FT-IR (KBr, cm -1 ): 3485, 3408, 3214, 3128, 3061, 2957, 2863, 1599, 1534, 1433, 1308, 1283, 1242, 1190, 1152, 1116, 1063, 919, 873, 826, 783, 699, 636, 602, 459.

[0162] The mass spectrometry data are as follows:

[0163] Mass spectrometry (MALDI-TOF, m / z) theoretical value for C 120 H 112 N 32 NaO4: [M + Na] + : 2088.94; measured value: 2088.53.

[0164] (iii) Synthesis of metal main chain polymers

[0165] The synthesis reaction equation is as follows:

[0166]

[0167] The synthesized ligand L5 (206.6 mg, 0.10 mmol) and nickel acetate tetrahydrate (223.9 mg ,0.9 mmol) was dissolved in naphthalene (20 g), and under nitrogen protection, the mixture was stirred and reacted at 210 °C for 6 h. Then, the temperature was lowered to 180 °C, and n-butanol (5 mL) was added dropwise to the reaction mixture until the evaporation of n-butanol was complete to terminate the reaction. After the reaction, the mixture was cooled to about 80 °C, and the dark black solution was treated with petroleum ether, followed by filtration. Then, the filtrate was dissolved in dichloromethane and the solvent was removed to obtain a dark green metal main-chain polymer solid powder, 103 mg, with a yield of 43%.

[0168] The infrared spectrum data are as follows:

[0169] FT-IR (KBr, cm -1 ): 3404, 2950, 2920, 2854, 1605, 1531, 1429, 1387, 1270, 1191, 1157, 1111, 1032, 974, 819, 780, 700, 646, 595, 467.

[0170] The mass spectrum data are as follows: Mass spectrum (MALDI-TOF, m / z) theoretical value C 120 H 101 N 32 Ni6O4[M + H] + : 2407.50; measured value: 2407.11.

[0171] The test results show that through the above ligand-assisted synthesis method, a triazine-based metal main-chain polymer was prepared, and the highest molecular weight can reach more than 11.14 KDa ( Figure 1 , Example 1). Its ultraviolet-visible absorption wavelength was tested in dichloromethane. Due to the formation of nickel-nitrogen coordination bonds, the triazine-based metal main-chain polymer has an absorption peak of π-π* electronic transition at 373 nm, and due to the influence of metal-metal bonds, it has an absorption peak of d-orbital electronic transition at 588 nm in visible light ( Figure 2 ). At the same time, through reflection electron energy loss spectroscopy test, it was found that the electrical band gap of the triazine-based metal main-chain polymer is 2.66 eV, showing the electrical band gap properties of a semiconductor ( Figure 3 ). At the same time, its thermal decomposition temperature is 261 °C, showing high thermal stability ( Figure 4 ). Moreover, the synthesized triazine-based metal main-chain polymer has good solubility in dichloromethane, chloroform, tetrahydrofuran, 1,4-dioxane, acetone, N,N-dimethylformamide, and dimethyl sulfoxide, and is suitable for spin coating or solution processing.

[0172] Among them, the nuclear magnetic data was obtained by testing with a Bruker AVANCE III HD 400M nuclear magnetic resonance spectrometer, using deuterated dimethyl sulfoxide as the solvent; the molecular weight was obtained by testing with an AB SCIEX 5800 matrix-assisted laser desorption ionization time-of-flight mass spectrometer, using trans-2-[3-(4-tert-butylphenyl)-2-methyl-2-propenylidene] malononitrile as the matrix and sodium trifluoroacetate as the sodium salt; the infrared signal was obtained by testing with a Thermofisher Nicolet 6700 infrared spectrometer, and the sample was prepared by pressing tablets with potassium bromide powder as the diluent; the ultraviolet-visible absorption spectrum was obtained by testing with a Perkin-Elmer Lambda 750 ultraviolet-visible spectrophotometer; the reflection electron energy loss spectrum was measured on a Thermo Scientific ESCALAB 250Xi using a primary electron beam of about 1 keV in the high-energy mode, and the data was recorded with a constant pass energy of 5 eV and a beam spot size of about 1 mm; the thermogravimetric temperature test was carried out on a Mettler Toledo TGA1 and SDT Q600 TG-DTA analyzer under nitrogen atmosphere protection, with a temperature range of 50 to 800 °C and a heating rate of 10 °C min -1 .

[0173] Based on triazine compounds, the present invention realizes the ordered polymerization of metal ions by adopting a ligand-assisted synthesis strategy. The obtained triazine-based metal main-chain polymer has the advantages of precise controllability of molecular structure, molecular weight exceeding the ten-thousand threshold, and strong metal-metal interaction, providing an effective way for the design and synthesis of future new metal main-chain polymers.

[0174] The triazine-based metal main-chain polymer synthesized in the present invention has achieved a breakthrough in the molecular weight ten-thousand threshold for the first time, showing the ability to absorb visible light, the electrical band gap of a semiconductor in terms of optical and electrical properties, and at the same time having good solubility, suitable for spin coating or solution processing. This material is expected to be widely used in semiconductors, optoelectronic materials and single-molecule devices.

Claims

1. A metal main chain polymer based on triazine compounds, denoted as PT-MBP, has the following general structural formula: Wherein, M is a metal ion; The main chain skeleton is completely composed of mutually stable bonds between metal ions; the triazine compound ligands use coordination interactions to stabilize the spatial structure of the main chain skeleton.

2. The method for preparing a metal main chain polymer based on triazine compounds according to claim 1, characterized in that: With the help of triazine compounds' high reactivity, excellent coordination ability and effective electronic regulation, metal main chain polymers are synthesized. The synthesis route is as follows: Where n is the number of repeating units, n is greater than or equal to 1; B n For terminal protection intermediate, L n is a ligand; M is a metal ion; PT-MBP is a triazine metal main chain polymer; the protected polymer side chain monomer has the following structure: In the formula, R is an amino protecting group; The specific steps of synthesis are: Step (i): Connect the polymerized side chain monomer to the precursor tethered molecule through a Buchwald coupling reaction and a protecting group strategy to obtain a terminal protected intermediate (B ni ); the specific process is as follows: (1) dissolving bromopyridine calixarene and diaminopyridine in an organic solvent, and heating and coupling them under nitrogen protection in the presence of a palladium catalyst, an organic phosphorus ligand and a base to obtain a precursor tethered molecule; (2) dissolving the polymerizable side chain monomer and the precursor tethered molecule in an organic solvent, and heating and coupling them under nitrogen protection in the presence of a palladium catalyst, an organic phosphorus ligand and a base to obtain the corresponding terminal protected intermediate (B ni ); Step (ii): The terminal protected intermediate (B ni ) is subjected to a deprotection reaction, specifically, the terminal protected intermediate (B ni ) is dissolved in an organic solvent, and under heating conditions, the protective group is removed by a strong acid to activate the functional group; the above steps (i) and (ii) are repeated for a number of cycles greater than or equal to 1 to obtain a ligand (L n ); Step (iii): The ligand (L n ) undergoes a metal coordination reaction with a metal ion compound under heating conditions to achieve ordered polymerization of metal ions and obtain the corresponding triazine metal main chain polymer (PT-MBP).

3. The synthesis method according to claim 2, characterized in that In step (i): The calixarene is selected from the group consisting of calix[4]arene, 4-alkylcalix[4]arene, thiacalix[4]arene, 4-hydroxycalix[4]arene, and tert-butylcalix[4]arene; The organic solvent is selected from toluene, pyridine, picoline, 1,4-dioxane, dichloromethane, tetrahydrofuran, N,N-dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone or xylene; preferably xylene, dimethyl sulfoxide or pyridine; The palladium catalyst is selected from tetrakis(triphenylphosphine)palladium, tris(dibenzylideneacetone)dipalladium, palladium acetate, bis(benzonitrile)palladium chloride, bis(dibenzylideneacetone)palladium, bis(tricyclohexylphosphine)palladium dichloride, bis(acetylacetonate)palladium or tetrakis(4-carboxyphenyl)porphyrin palladium; The organophosphorus ligand is selected from 1,3-bis(diphenylphosphino)propane, 1,1'-binaphthyl-2,2'-bisdiphenylphosphine, 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl or dicyclohexyl[3,6-dimethoxy-2',4',6'-triisopropyl[1,1'-biphenyl]-2-yl]phosphine; The base is selected from sodium hydroxide, potassium hydroxide, potassium tert-butoxide, sodium tert-butoxide, diisopropylethylamine, cesium carbonate or potassium carbonate.

4. The synthesis method according to claim 2, characterized in that In step (i): The polymerizable side chain monomer is a halogenated amino triazine chain with protected amino groups; The triazine compound is selected from melamine, benzoguanamine, 6-methyl-1,3,5-triazine-2,4-diamine, 2,4-diamino-1,3,5-triazine, 2,4-diamino-6-(4-methylphenyl)-1,3,5-triazine, 2,4-diamino-6-(4-chlorophenyl)-1,3,5-triazine, cyanuric chloride, 2,4-dichloro-1,3,5-triazine, 2,4-dichloro-6-phenyl-1,3,5-triazine, 2,4-dichloro-6-methoxy-1,3,5-triazine or 2,4-dichloro-6-ethyltriazine; The amino protecting group is selected from acetyl, trimethylsilylethoxycarbonyl, phthaloyl, tert-butyloxycarbonyl, p-methoxybenzyl, p-toluenesulfonyl or 2,4-dimethoxybenzyl.

5. The synthesis method according to claim 2, characterized in that In step (ii): The acid is selected from glacial acetic acid, dilute hydrochloric acid, trifluoroacetic acid, trichloroacetic acid or dilute sulfuric acid; The organic solvent is selected from dichloromethane, chloroform, acetonitrile, acetone, methanol or tetrahydrofuran; The heating temperature is 75-80°C and the heating time is 10-12h.

6. The synthesis method according to claim 2, characterized in that In step (ii), the ligand contains one or more groups selected from the group consisting of triazine, pyridyl, phenyl, alkyl, nitro, amino, hydroxyl or conjugated olefin.

7. The synthesis method according to claim 2, characterized in that In step (iii): The specific conditions of the metal coordination reaction are: n ) and a metal ion compound are dissolved in an organic solvent, and heated under nitrogen protection for metallization to obtain a metal main chain polymer; wherein: The metal is selected from one or more transition metals; The metal ion compound is selected from alkali metal acetate, halide salt, triphenylphosphine substituted salt or acetonitrile substituted salt; The organic solvent is selected from N,N-dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, xylene or naphthalene; The heating is performed for metallization at a temperature of 200-210° C. for 5-6 hours.

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