A two-dimensional network non-fully conjugated metal-supramolecular polymer and its preparation method and application

Abstract

The present invention proposes a two-dimensional network non-fully conjugated metal-supramolecular polymer and its preparation method and application, which belongs to the technical field of electrochromism, and is used to solve the problem that one-dimensional linear non-fully conjugated metal-supramolecular polymer electrochromic materials have poor cyclic stability, thereby limiting their application in the field of energy-saving devices. The preparation of the two-dimensional network non-fully conjugated metal-supramolecular polymer of the present invention includes the following steps: S1, a terpyridine derivative and 1,3,5-tris(halogenated methyl)benzene react to synthesize a tridentate intermediate having a non-conjugated unit; S2, the tridentate intermediate and metal ions are subjected to a coordination reaction to obtain a two-dimensional network non-fully conjugated metal-supramolecular polymer. The present invention utilizes the tridentate structure to improve the cyclic stability of the material and the introduction of non-conjugated units in the molecular skeleton to limit the transmission of residual electrons and thus improve the optical memory performance of the material. The obtained two-dimensional non-fully conjugated metal-supramolecular polymer electrochromic material has the characteristics of a large optical modulation range, fast response speed, good cyclic stability and excellent optical memory performance.

Description

Technical Field

[0001] The present invention belongs to the technical field of electrochromism, and in particular relates to a two-dimensional network non-fully conjugated metal-supramolecular polymer and a preparation method and application thereof. Background Art

[0002] Electrochromism refers to the phenomenon that the optical properties of a material or device (such as transmittance and reflectance) undergo reversible and lasting changes under the stimulation of an external electric field. Electrochromic devices have broad application prospects in optoelectronic devices such as smart windows, low-power displays, electronic tags, and anti-glare rearview mirrors. Various electrochromic materials, such as transition metal oxides, metal-supramolecular polymers, organic small molecules, and organic conjugated polymers, have been intensively studied. Metal-supramolecular polymers have metal-organic ligand charge transfer (MLCT) and have a faster response speed and higher coloring efficiency, and have attracted widespread attention from researchers. At present, metal-supramolecular polymers with non-fully conjugated structures are synthesized to improve their optical memory properties, but their cyclic stability cannot meet the practical application requirements of smart windows. Therefore, designing and synthesizing metal-supramolecular polymer electrochromic materials with non-fully conjugated structures and high cyclic stability is crucial to promote their practical applications.

[0003] Patent publication number CN 118206774A discloses a non-fully conjugated metal-supramolecular polymer and its preparation method and application. The preparation method comprises the following steps: S1, pyridine-4-boric acid and 4-halogenated aromatic terpyridine are synthesized by Suzuki coupling reaction 4'-(4-(pyridyl-4-phenyl)-2,2':6',2"-terpyridine; S2, 4'-(4-(pyridyl-4-phenyl)-2,2':6',2"-terpyridine synthesized in S1 and 1,4-di(halogenated methyl)benzene are reacted to obtain a terpyridine-2,2':6',2"-terpyridine. Synthesize a linear intermediate 1,1'-(1,4-phenylenebis(methylene))bis(4-([2,2'-:6'-,2"-terpyridine]-4'-yl)phenyl)pyridin-1-ium) having a non-conjugated unit; S3, coordinate the 1,1'-(1,4-phenylenebis(methylene))bis(4-([2,2'-:6'-,2"-terpyridine]-4'-yl)phenyl)pyridin-1-ium) synthesized in S2 with a metal ion to prepare a non-fully conjugated metal-supramolecular polymer. The non-fully conjugated metal-supramolecular polymer prepared in this patent is one-dimensional and linear, and has the problem of poor cyclic stability in electrochromic applications. Summary of the Invention

[0004] In response to the problem that one-dimensional linear non-fully conjugated metal-supramolecular polymer electrochromic materials have poor cyclic stability, which in turn limits their application in the field of energy-saving devices, the present invention proposes a two-dimensional network non-fully conjugated metal-supramolecular polymer and its preparation method and application. The tridentate structure is used to improve the cyclic stability of the material, and the introduction of non-conjugated units in the molecular skeleton is used to limit the transmission of residual electrons and thus improve the optical memory performance of the material. The obtained two-dimensional non-fully conjugated metal-supramolecular polymer electrochromic material has the characteristics of a large optical modulation range, fast response speed, good cyclic stability and excellent optical memory performance.

[0005] In order to achieve the above object, the technical solution of the present invention is achieved as follows:

[0006] A two-dimensional network non-fully conjugated metal-supramolecular polymer, the structural formula of which is shown below:

[0007]

[0008] A method for preparing a two-dimensional network non-fully conjugated metal-supramolecular polymer, the synthesis route is as follows Figure 1 As shown, the following steps are included:

[0009] S1, terpyridine derivatives and 1,3,5-tris(halogenated methyl)benzene react to synthesize a tridentate intermediate with a non-conjugated unit;

[0010] S2. The tridentate intermediate and metal ions are subjected to coordination reaction to prepare a two-dimensional network non-fully conjugated metal-supramolecular polymer.

[0011] Preferably, the terpyridine derivative is 4'-(4-(pyridinyl-4-phenyl)-2,2':6',2"-terpyridine, 4'-(4-(pyridin-4-yl)cyclopentadien-1-yl)-2,2':6',2"-terpyridine, 4'-(5-(pyridin-4-yl)furan-2-yl)-2,2':6',2"-terpyridine or 4'-(5-(pyridin-4-yl)thiophene-2-yl)-2,2':6',2"-terpyridine.

[0012] Preferably, the 1,3,5-tris(halomethyl)benzene is 1,3,5-tris(bromomethyl)benzene, 1,3,5-tris(chloromethyl)benzene or 1,3,5-tris(iodomethyl)benzene.

[0013] Furthermore, the step S1 specifically comprises dissolving the terpyridine derivative and 1,3,5-tris(halogenated methyl)benzene in solvent I to prepare a mixed solution, and reacting at 110-130° C. for 48-72 hours under an inert gas atmosphere.

[0014] The molar ratio of the 1,3,5-tris(halogenated methyl)benzene to the terpyridine derivative is 1:(2-5), and the concentration of 4'-(4-(pyridyl-4-phenyl)-2,2':6',2"-terpyridine in the mixed solution is 0.05-0.5 mol / L.

[0015] The solvent I is one of acetonitrile, N,N-dimethylformamide or N,N-dimethylacetamide.

[0016] Furthermore, step S2 specifically comprises dissolving the tridentate intermediate and a soluble metal salt in solution II to prepare a reaction solution, under an inert gas atmosphere, at 70-110° C., for a reaction time of 12-48 h; and then adding a counteranion solution to replace the anions in the metal-supramolecule.

[0017] The metal ion of the soluble metal salt in step S2 is Fe 2+ , Ru 2+ , Os 2+ , Cu 2+ , Zn 2+ Any one of the following; the molar ratio of the tridentate intermediate to the metal ion is 1:(1.5-4).

[0018] The concentration of the tridentate intermediate in the reaction solution is 0.001-0.1 mol / L, and the solution II is at least one of acetic acid, methanol or chloroform.

[0019] In step S2, the counter anion is any one or more of acetate, acetylacetonate, cyclohexanebutyrate, halide, hexafluorophosphate, hexafluoroacetylacetonate, nitrate, perchlorate, phosphate, sulfate, tetrafluoroborate or fluoromethanesulfonate; the concentration of the prepared counter anion solution is 0.1-3 mol / L, and the mixed solution is stirred for 6-24 hours.

[0020] The invention discloses an application of a two-dimensional network non-fully conjugated metal-supramolecular polymer as an electrochromic material, and adopts the two-dimensional network non-fully conjugated metal-supramolecular polymer to prepare an electrochromic nanofilm.

[0021] The preparation of the electrochromic nanofilm comprises the following steps:

[0022] Y1. dissolving a two-dimensional network non-fully conjugated metal-supramolecular polymer electrochromic nanomaterial in a solvent to obtain a nanomaterial ink;

[0023] Y2. The nanomaterial ink obtained in step Y1 is constructed into a two-dimensional network non-fully conjugated metal-supramolecular polymer electrochromic nanofilm on a transparent conductive substrate through a wet film forming method.

[0024] Furthermore, the solvent in step Y1 is N,N-dimethylformamide (DMF) or an alcohol solvent, and the alcohol solvent includes low-boiling point alcohols such as methanol and ethanol, and the concentration of the two-dimensional network non-fully conjugated metal-supramolecular polymer ink is 0.5-1 mg / mL.

[0025] Furthermore, the wet film forming method in step Y2 is spin coating, spraying, inkjet printing and the like, and the cleaning process of the transparent conductive substrate is to ultrasonically clean the conductive substrate with acetone, deionized water and ethanol respectively and blow dry it with nitrogen. The thickness of the electrochromic nanofilm is 0.4 μm to 1 μm.

[0026] Beneficial effects of the present invention:

[0027] 1. The two-dimensional network non-fully conjugated metal-supramolecular polymer electrochromic film prepared by the present invention exhibits a response time of less than 8s, an optical modulation range of more than 60.8% and a wavelength of more than 1000cm 2 C -1 The coloring efficiency was improved by reacting 4'-(4-bromophenyl)-2,2':6',2"-terpyridine with 1,3,5-tris(bromomethyl)benzene and further with Fe 2+ The two-dimensional network non-fully conjugated metal-supramolecular film obtained by the reaction was placed in an organic electrolyte, and its optical modulation range was 60.8%, the fading time was 7.2s, the coloring time was 1.7s, and the coloring efficiency was 1133.2cm 2 C -1 , the film can be reversibly transformed between purple and transparent states.

[0028] 2. The two-dimensional network-like non-fully conjugated metal-supramolecular film prepared by the present invention exhibits excellent optical memory properties and cyclic stability. Compared to traditional fully conjugated metal-supramolecular materials, the constructed metal-supramolecular with a two-dimensional network structure effectively improves the cyclic stability of polymer materials. Furthermore, the introduction of non-conjugated units effectively limits the effective transmission of residual electrons, allowing the prepared non-fully conjugated metal-supramolecular film to maintain its faded state for a long time after the external voltage is disconnected. The transmittance of the two-dimensional network-like non-fully conjugated metal-supramolecular film decreased by only 9.7% after 5000 redox cycles. In the faded state, the film color returned to its initial state after the external voltage was disconnected for 2500 seconds. This invention is well-suited for applications in fields such as electrochromic and energy-saving displays, and has industrial and promotional value. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the following briefly introduces the drawings required for use in the embodiments or the description of the prior art. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative work.

[0030] Figure 1 A synthetic route for preparing two-dimensional network non-fully conjugated metal-supramolecular polymers.

[0031] Figure 2 This is the synthetic route of the two-dimensional network iron-based non-fully conjugated metal-supramolecular polymer prepared in Example 1.

[0032] Figure 3 Ultraviolet absorption spectra of methanol solutions of tridentate intermediate (solid line) and two-dimensional network iron-based non-fully conjugated metal-supramolecular polymer (dashed line).

[0033] Figure 4 This is the XPS test spectrum of the two-dimensional network iron-based non-fully conjugated metal-supramolecular polymer prepared in Example 1. Figure 4 a is full spectrum scan; Figure 4 b is Figure 4 Locally enlarged high-resolution spectrum of a.

[0034] Figure 5 This is a flow chart of the nanofilm preparation process according to Example 1 of the present invention.

[0035] Figure 6 a is the film at 20 mV s -1 The cyclic voltammetry curve below, Figure 6 b is the current density and corresponding optical density change curve of the polymer film at 576 nm.

[0036] Figure 7 This is the test curve of the film memory performance: the transmittance change of the polymer film at 576nm after applying 1.5V for 100s and then disconnecting the potential for 2500s.

[0037] Figure 8 The film was subjected to a cyclic stability test under a square wave voltage of 0.5 V and 1.5 V (relative to silver wire) with an interval of 50 s. DETAILED DESCRIPTION

[0038] The following will clearly and completely describe the technical solutions in the embodiments of the present invention in conjunction with the accompanying drawings. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. All other embodiments obtained by ordinary technicians in this field based on the embodiments of the present invention without creative work are within the scope of protection of the present invention.

[0039] Unless otherwise specified, the experimental methods used in the examples of the present invention are conventional methods.

[0040] Unless otherwise specified, the materials, reagents, etc. used in the examples of the present invention can be obtained from commercial sources.

[0041] Example 1

[0042] A method for synthesizing a two-dimensional network iron-based non-fully conjugated metal-supramolecular polymer electrochromic nanomaterial, the synthesis route is as follows Figure 2 As shown, the following steps are included:

[0043] S1. Prepare a tridentate intermediate having a non-conjugated unit by reacting 4'-(4-(pyridyl-4-phenyl)-2,2':6',2"-terpyridine with 1,3,5-tris(bromomethyl)benzene: Specifically, first, (0.36 g, 0.90 mmol) of 4'-(4-(pyridyl-4-phenyl)-2,2':6',2"-terpyridine and (0.11 g, 0.30 mmol) of 1,3,5-tris(bromomethyl)benzene were added. The reaction mixture was placed in a 25 mL Schlenk flask and evacuated three times. Under a nitrogen stream, 10 mL of DMF was added. The solution was refluxed at 125°C for 72 h. After cooling to room temperature, the reaction solution was added dropwise to 50 mL of vigorously stirred acetone solution. After thorough stirring, the solution was filtered to obtain an off-white solid. The precipitate was washed with ether and dried to obtain a white powder (182.5 mg, yield: 75.2%).

[0044] Proton spectrum: 1 H NMR (500MHz, DMSO-d6, δ)9.21(d,J=6.5Hz,6H),8.66(d,J=5.5Hz,18H),8.54(d,J=7.9Hz,6H),8.23( d,J=8.2Hz,6H),8.12(d,J=8.1Hz,6H),7.99(td,J=7.7,1.8Hz,6H),7.50-7.46(m,9H),5.97(s,6H).

[0045] Carbon spectrum: 13C NMR (126MHz, DMSO-d6, δ)156.12,155.03,149.65,145.84,129.59,128.63,124.99,121.35,118.31.

[0046] S2. The 1,1',1"-(benzene-1,3,5-tris(methylene))tris(4-([2,2':6'-2"-bipyridyl]-4'-yl)phenyl)pyridin-1-ium) obtained in step S1 is reacted with ferrous acetate to obtain a two-dimensional network iron-based non-fully conjugated metal-supramolecular polymer electrochromic nanomaterial. Specifically, 1,1',1"-(benzene-1,3,5-tris(methylene))tris(4-([2,2':6'-2"-bipyridyl]-4'-yl)phenyl)pyridin-1-ium) (45.5 mg, 0.03 mmol) and Fe(OAc)2 (17.4 mg, 0.1 mmol) are added to a 50 mL round-bottom flask. After evacuation and degassing three times, 30 mL of CH3OH solution is slowly added under N2 protection. The above solution is refluxed at 80°C for 24 hours. After cooling to room temperature, the solution was evaporated to dryness using a rotary evaporator, followed by addition of 30 mL of ACN solution for ultrasonic washing, and filtered and dried to obtain a dark purple solid (53.33 mg, yield: 94.7%).

[0047] The spectral properties of the tridentate intermediate and the two-dimensional network iron-based non-fully conjugated metal-supramolecular polymer prepared in Example 1 were tested.

[0048] Figure 3 Ultraviolet absorption spectra of methanol solutions of tridentate intermediate (solid line) and two-dimensional network iron-based non-fully conjugated metal-supramolecular polymer (dashed line).

[0049] Depend on Figure 3 It can be seen that the two-dimensional network iron-based non-fully conjugated metal-supramolecular polymer exhibits a typical metal-supramolecular intramolecular charge transfer (MLCT) absorption peak at 580nm.

[0050] Figure 4 This is the XPS test spectrum of the two-dimensional network iron-based non-fully conjugated metal-supramolecular polymer prepared in Example 1.

[0051] Depend on Figure 4 The XPS spectrum shows characteristic peaks for Fe 2p, O 1s, N 1s, C 1s, and Br 3d. Due to spin-orbit splitting of Fe atoms, the elemental ratio of Fe to N, estimated from the integrated intensity, is 1:7.9, nearly consistent with the theoretical atomic ratio of 1:8, indicating the successful synthesis of a two-dimensional network-like iron-based non-fully conjugated metal-supramolecular polymer material.

[0052] Application Example 1

[0053] This embodiment provides a method for preparing a two-dimensional network iron-based non-fully conjugated metal-supramolecular polymer electrochromic nanomaterial film, comprising the following steps: Figure 5 As shown:

[0054] Y1. Disperse the iron-based non-fully conjugated metal-supramolecular polymer electrochromic nanomaterial prepared in Example 1 in a solvent to obtain a nanomaterial ink. Specifically, the two-dimensional network iron-based non-fully conjugated metal-supramolecular polymer electrochromic nanomaterial is diluted in a mixed solvent of DMF and ethanol to prepare a 0.5 mg / mL solution, i.e., the nanomaterial ink.

[0055] Y2. The nanomaterial ink obtained in step Y1 is constructed into a two-dimensional mesh iron-based non-fully conjugated metal-supramolecular polymer electrochromic nanofilm on a cleaned transparent conductive substrate by a wet film forming method. Specifically, first, the nanomaterial ink prepared in step Y1 is injected into a syringe with a metal needle, which is installed in a microinjection pump and the propulsion speed is set to 1.2 mL / h; secondly, the FTO conductive glass is ultrasonically cleaned with acetone, deionized water, and ethanol for 15 minutes, respectively, and blown clean with nitrogen to obtain a clean FTO conductive glass; thirdly, the distance between the metal needle and the FTO conductive glass is fixed at 10 cm, and a high voltage of 20 kV is applied between the metal needle and the FTO conductive glass. The precursor solution is atomized into an aerogel, and the iron-based non-fully conjugated metal-supramolecular polymer is deposited on the surface of the FTO conductive glass under the action of electrostatic attraction; after spraying, an electrochromic nanofilm with a thickness of about 0.24 μm is obtained.

[0056] The electrochromic performance of the two-dimensional network iron-based non-fully conjugated metal-supramolecular polymer film prepared in Example 1 was tested.

[0057] Figure 6 a and b are the film at 20 mV s -1 The cyclic voltammetry curve under the condition of 580nm and the relationship between the optical density change and the amount of embedded charge per unit area are shown in the figure. Figure 6 As shown in a, the film is at 20 mV s -1 The cyclic voltammetry curves in the potential window of 0-1.6 V (vs. silver wire) show a pair of obvious reversible redox peaks, which are attributed to Fe 2+ / Fe 3+ The film showed a reversible redox reaction of 7.2 and 1.7 s in the fading and coloring processes, respectively. Figure 6 b The calculated coloring efficiency of the film is as high as 1133.2 cm 2 C -1 The above results indicate that the two-dimensional network iron-based non-fully conjugated metal-supramolecular polymer has excellent electrochromic properties.

[0058] The optical memory performance of the two-dimensional network non-fully conjugated metal-supramolecular polymer film prepared in Example 1 was tested.

[0059] Figure 7 This is a test curve of the film memory performance: specifically, the film is disconnected after applying a 1.5V potential for 100s, and the optical transmittance of the film at 580nm changes.

[0060] Depend on Figure 7 It can be seen that the transmittance of the film gradually decreases with time, but after 2500 seconds of disconnection of the potential, the transmittance completely recovers to its initial state. Compared with the two-dimensional fully conjugated metal-supramolecular polymer, the synthesized two-dimensional non-fully conjugated metal-supramolecular polymer has significantly improved optical memory properties.

[0061] The cyclic stability test of the two-dimensional network iron-based non-fully conjugated metal-supramolecular polymer film prepared in Example 2 was performed.

[0062] Figure 8 The curves of the optical transmittance of the film changing with time when square wave voltages of 0.5 V and 1.5 V (relative to the silver wire) are applied to the film.

[0063] Depend on Figure 8 As can be seen from the figure, after more than 1000 cycles, the spectrum of the film has a slight attenuation and after 2000 cycles, the spectrum shows an overall upward shift. This is because the film has undergone structural damage after multiple cycles and cannot be completely colored. Despite this, after 5000 cycles, the optical modulation range of the film has only decayed by 9.7%, indicating that the synthesized two-dimensional network iron-based non-fully conjugated metal-supramolecular polymer has excellent cyclic stability.

[0064] Example 2

[0065] This embodiment provides a method for synthesizing a two-dimensional network iron-based non-fully conjugated metal-supramolecular polymer electrochromic nanomaterial, comprising the following steps:

[0066] S1. Prepare a tridentate intermediate with a non-conjugated unit by combining 4'-(4-(pyridyl-4-phenyl)-2,2':6',2"-terpyridine with 1,3,5-tris(bromomethyl)benzene: Specifically, first, take 4'-(4-(pyridyl-4-phenyl)-2,2':6',2"-terpyridine (0.24 g, 0.60 mmol) and 1,3,5-tris(bromomethyl)benzene (0.11 g, 0.30 mmol) and add them to a 25 mL Schlenk flask, repeatedly evacuate and release the gas three times, and add 10 mL of DMF under a nitrogen flow. The above solution is refluxed at 130°C for 72 h; after the reaction solution is cooled to room temperature, the reaction solution is added dropwise to 50 mL of acetone and fully stirred. The solution is filtered to obtain an off-white solid, and the precipitate is washed with ether and dried to obtain a white powder.

[0067] S2. The 1,1',1"-(benzene-1,3,5-tris(methylene))tris(4-([2,2':6'-2"-terpyridine]-4'-yl)phenyl)pyridin-1-ium) obtained in step S1 is reacted with ferrous acetate to obtain a two-dimensional network iron-based non-fully conjugated metal-supramolecular polymer electrochromic nanomaterial. Specifically, 1,1',1"-(benzene-1,3,5-tris(methylene))tris(4-([2,2':6'-2"-bipyridine]-4'-yl)phenyl)pyridin-1-ium) (45.5 mg, 0.03 mmol) and Fe(OAc)2 (10.4 mg, 0.06 mmol) were added to a 50 mL round-bottom flask. After evacuation and degassing three times, 30 mL of CH3OH solution was slowly added under N2 protection. The above solution was refluxed at 90°C for 12 h. After cooling to room temperature, the solution was evaporated to dryness using a rotary evaporator, and then 30 mL of ACN solution was added for ultrasonic washing, and the solution was filtered and dried to obtain a dark purple solid.

[0068] Example 3

[0069] This embodiment provides a method for synthesizing a two-dimensional mesh-type iron-based non-fully conjugated metal-supramolecular polymer electrochromic nanomaterial, comprising the following steps:

[0070] S1. Prepare a tridentate intermediate with a non-conjugated unit by reacting 4'-(4-(pyridyl-4-phenyl)-2,2':6',2"-terpyridine with 1,3,5-tris(bromomethyl)benzene: Specifically, first, take 4'-(4-(pyridyl-4-phenyl)-2,2':6',2"-terpyridine (0.27 g, 0.75 mmol) and 1,3,5-tris(bromomethyl)benzene (0.11 g, 0.30 mmol) and add them to a 25 mL Schlenk flask, repeat the gas extraction and degassing three times, and add 10 mL of DMF under a nitrogen flow. The above solution is refluxed at 130°C for 56 hours; after the reaction solution is cooled to room temperature, the reaction solution is added dropwise to 50 mL of vigorously stirred acetone, and then the solution is filtered after sufficient stirring to obtain an off-white solid, and the precipitate is washed with ether and dried to obtain a white powder.

[0071] S2. The 1,1',1"-(phenyl-1,3,5-tris(methylene))tris(4-([2,2':6'-2"-bipyridyl]-4'-yl)phenyl)pyridin-1-ium) obtained in step S1 was reacted with ferrous acetate to obtain a two-dimensional network iron-based non-fully conjugated metal-supramolecular polymer electrochromic nanomaterial. Specifically, 1,1',1"-(phenyl-1,3,5-tris(methylene))tris(4-([2,2':6'-2"-bipyridyl]-4'-yl)phenyl)pyridin-1-ium) (45.5 mg, 0.03 mmol) and Fe(OAc)2 (13.9 mg, 0.08 mmol) were added to a 50 mL round-bottom flask. After repeated evacuation and degassing three times, 30 mL of CH3OH was slowly added under N2 protection. The above solution was refluxed at 90°C for 36 hours. After cooling to room temperature, the solution was evaporated to dryness using a rotary evaporator, and then 30 mL of ACN solution was added for ultrasonic washing, and the solution was filtered and dried to obtain a dark purple solid.

[0072] Example 4

[0073] This embodiment provides a method for synthesizing a two-dimensional network iron-based non-fully conjugated metal-supramolecular polymer electrochromic nanomaterial, comprising the following steps:

[0074] S1. Prepare a tridentate intermediate with a non-conjugated unit by reacting 4'-(4-(pyridyl-4-phenyl)-2,2':6',2"-terpyridine with 1,3,5-tris(bromomethyl)benzene: Specifically, first, take 4'-(4-(pyridyl-4-phenyl)-2,2':6',2"-terpyridine (0.48 g, 1.20 mmol) and 1,3,5-tris(bromomethyl)benzene (0.11 g, 0.30 mmol) and add them to a 25 mL Schlenk flask, repeat the gas extraction and degassing three times, and add 10 mL of DMF under a nitrogen flow. The above solution is refluxed at 120°C for 48 h; after the reaction solution is cooled to room temperature, the reaction solution is added dropwise to 50 mL of vigorously stirred acetone, and then after sufficient stirring, the solution is filtered to obtain an off-white solid, and the precipitate is washed with ether and dried to obtain a white powder.

[0075] S2. The 1,1',1"-(phenyl-1,3,5-tris(methylene))tris(4-([2,2':6'-2"-bipyridyl]-4'-yl)phenyl)pyridin-1-ium obtained in step S1 is reacted with ferrous acetate to obtain a two-dimensional network-type iron-based non-fully conjugated metal-supramolecular polymer electrochromic nanomaterial. Specifically, 1,1',1"-(phenyl-1,3,5-tris(methylene))tris(4-([2,2':6'-2"-bipyridyl]-4'-yl)phenyl)pyridin-1-ium) (45.5 mg, 0.03 mmol) and Fe(OAc)2 (20.1 mg, 0.12 mmol) were added to a 50 mL round-bottom flask. After repeated evacuation and degassing three times, 30 mL of CH3OH was slowly added under N2 protection. The above solution was refluxed at 80°C for 48 hours. After cooling to room temperature, the solution was evaporated to dryness using a rotary evaporator, and then 30 mL of ACN solution was added for ultrasonic washing, and the solution was filtered and dried to obtain a dark purple solid.

[0076] Example 5

[0077] This embodiment provides a method for synthesizing a two-dimensional network iron-based non-fully conjugated metal-supramolecular polymer electrochromic nanomaterial, comprising the following steps:

[0078] S1. Prepare a tridentate intermediate with a non-conjugated unit by reacting 4'-(4-(pyridyl-4-phenyl)-2,2':6',2"-terpyridine with 1,3,5-tris(bromomethyl)benzene: Specifically, first, take 4'-(4-(pyridyl-4-phenyl)-2,2':6',2"-terpyridine (0.48 g, 1.20 mmol) and 1,3,5-tris(bromomethyl)benzene (0.11 g, 0.30 mmol) and add them to a 25 mL Schlenk flask, repeat the gas extraction and degassing three times, and add 10 mL of DMF under a nitrogen flow. The above solution is refluxed at 120°C for 72 h; after the reaction solution is cooled to room temperature, the reaction solution is added dropwise to 50 mL of vigorously stirred acetone, and then after sufficient stirring, the solution is filtered to obtain an off-white solid, and the precipitate is washed with ether and dried to obtain a white powder.

[0079] S2. The 1,1',1"-(phenyl-1,3,5-tris(methylene))tris(4-([2,2':6'-2"-bipyridyl]-4'-yl)phenyl)pyridin-1-ium) obtained in step S1 was reacted with ferrous acetate to obtain a two-dimensional network-type iron-based non-fully conjugated metal-supramolecular polymer electrochromic nanomaterial. Specifically, 1,1',1"-(phenyl-1,3,5-tris(methylene))tris(4-([2,2':6'-2"-bipyridyl]-4'-yl)phenyl)pyridin-1-ium) (45.5 mg, 0.03 mmol) and Fe(OAc)2 (20.1 mg, 0.12 mmol) were added to a 50 mL round-bottom flask. After evacuation and degassing three times, 30 mL of CH3OH was slowly added under N2 protection. The above solution was refluxed at 80°C for 36 hours. After cooling to room temperature, the solution was evaporated to dryness using a rotary evaporator, and then 30 mL of ACN solution was added for ultrasonic washing, and the solution was filtered and dried to obtain a dark purple solid.

[0080] Example 6

[0081] This embodiment provides a method for synthesizing a two-dimensional network iron-based non-fully conjugated metal-supramolecular polymer electrochromic nanomaterial, comprising the following steps:

[0082] S1. Prepare a tridentate intermediate with a non-conjugated unit by reacting 4'-(4-(pyridyl-4-phenyl)-2,2':6',2"-terpyridine with 1,3,5-tris(bromomethyl)benzene: Specifically, first, take 4'-(4-(pyridyl-4-phenyl)-2,2':6',2"-terpyridine (0.60 g, 1.5 mmol) and 1,3,5-tris(bromomethyl)benzene (0.11 g, 0.30 mmol) and add them to a 25 mL Schlenk flask, repeat the gas extraction and degassing three times, and add 10 mL of DMF under a nitrogen flow. The above solution is refluxed at 110°C for 56 h; after the reaction solution is cooled to room temperature, the reaction solution is added dropwise to 50 mL of vigorously stirred acetone, and then after sufficient stirring, the solution is filtered to obtain an off-white solid, and the precipitate is washed with ether and dried to obtain a white powder.

[0083] S2. The 1,1',1"-(benzene-1,3,5-tris(methylene))tris(4-([2,2':6'-2"-terpyridine]-4'-yl)phenyl)pyridin-1-ium) obtained in step S1 was reacted with ferrous acetate to obtain a two-dimensional network-type iron-based non-fully conjugated metal-supramolecular polymer electrochromic nanomaterial. Specifically, 1,1',1"-(benzene-1,3,5-tris(methylene))tris(4-([2,2':6'-2"-bipyridine]-4'-yl)phenyl)pyridin-1-ium) (45.5 mg, 0.03 mmol) and Fe(OAc)2 (17.4 mg, 0.1 mmol) were added to a 50 mL round-bottom flask. After repeated evacuation and degassing three times, 30 mL of CH3OH was slowly added under N2 protection. The above solution was refluxed at 70°C for 48 hours. After cooling to room temperature, the solution was evaporated to dryness using a rotary evaporator, and then 30 mL of ACN solution was added for ultrasonic washing, and the solution was filtered and dried to obtain a dark purple solid.

[0084] Example 7

[0085] This embodiment provides a method for synthesizing a two-dimensional network iron-based non-fully conjugated metal-supramolecular polymer electrochromic nanomaterial, comprising the following steps:

[0086] S1. Prepare a tridentate intermediate with a non-conjugated unit by reacting 4'-(4-(pyridyl-4-phenyl)-2,2':6',2"-terpyridine with 1,3,5-tris(bromomethyl)benzene: Specifically, first, take 4'-(4-(pyridyl-4-phenyl)-2,2':6',2"-terpyridine (0.6 g, 1.50 mmol) and 1,3,5-tris(bromomethyl)benzene (0.11 g, 0.30 mmol) and add them to a 25 mL Schlenk flask, repeat the gas extraction and degassing three times, and add 10 mL of DMF under a nitrogen flow. The above solution is refluxed at 115°C for 48 h; after the reaction solution is cooled to room temperature, the reaction solution is added dropwise to 50 mL of vigorously stirred acetone, and then after sufficient stirring, the solution is filtered to obtain an off-white solid, and the precipitate is washed with ether and dried to obtain a white powder.

[0087] S2. The 1,1',1"-(benzene-1,3,5-tris(methylene))tris(4-([2,2':6'-2"-terpyridine]-4'-yl)phenyl)pyridin-1-ium) obtained in step S1 was reacted with ferrous acetate to obtain a two-dimensional network iron-based non-fully conjugated metal-supramolecular polymer electrochromic nanomaterial. Specifically, 1,1',1"-(benzene-1,3,5-tris(methylene))tris(4-([2,2':6'-2"-bipyridine]-4'-yl)phenyl)pyridin-1-ium) (45.5 mg, 0.03 mmol) and Fe(OAc)2 (17.4 mg, 0.1 mmol) were added to a 50 mL round-bottom flask. After repeated evacuation and degassing three times, 30 mL of CH3OH was slowly added under N2 protection. The above solution was refluxed at 70°C for 12 h. After cooling to room temperature, the solution was evaporated to dryness using a rotary evaporator, and then 30 mL of ACN solution was added for ultrasonic washing, and the solution was filtered and dried to obtain a dark purple solid.

[0088] Example 8

[0089] This embodiment provides a method for synthesizing a two-dimensional network cobalt-based non-fully conjugated metal-supramolecular polymer electrochromic nanomaterial, comprising the following steps:

[0090] S1. Prepare a tridentate intermediate with a non-conjugated unit by reacting 4'-(4-(pyridyl-4-phenyl)-2,2':6',2"-terpyridine with 1,3,5-tris(bromomethyl)benzene: Specifically, first, take 4'-(4-(pyridyl-4-phenyl)-2,2':6',2"-terpyridine (0.6 g, 1.50 mmol) and 1,3,5-tris(bromomethyl)benzene (0.11 g, 0.30 mmol) and add them to a 25 mL Schlenk flask, repeat the gas extraction and degassing three times, and add 10 mL of DMF under a nitrogen flow. The above solution is refluxed at 115°C for 48 h; after the reaction solution is cooled to room temperature, the reaction solution is added dropwise to 50 mL of vigorously stirred acetone, and then after sufficient stirring, the solution is filtered to obtain an off-white solid, and the precipitate is washed with ether and dried to obtain a white powder.

[0091] S2. The 1,1',1"-(benzene-1,3,5-tris(methylene))tris(4-([2,2':6'-2"-terpyridine]-4'-yl)phenyl)pyridin-1-ium) obtained in step S1 is reacted with cobalt chloride to obtain a two-dimensional network cobalt-based non-fully conjugated metal-supramolecular polymer electrochromic nanomaterial. Specifically, 1,1',1"-(benzene-1,3,5-tris(methylene))tris(4-([2,2':6'-2"-bipyridine]-4'-yl)phenyl)pyridin-1-ium) (45.5 mg, 0.03 mmol) and CoCl2 (12.98 mg, 0.1 mmol) were added to a 50 mL round-bottom flask, and the gas was repeatedly evacuated three times, and then 20 mL of CH3OH was slowly added under nitrogen protection. The above solution was refluxed at 70°C for 12 hours. After cooling to room temperature, the solution was evaporated to dryness using a rotary evaporator, followed by addition of 30 mL of ACN for ultrasonic washing, and filtered and dried to obtain an orange solid.

[0092] Example 9

[0093] This embodiment provides a method for synthesizing a two-dimensional network ruthenium-based non-fully conjugated metal-supramolecular polymer electrochromic nanomaterial, comprising the following steps:

[0094] S1. Prepare a tridentate intermediate with a non-conjugated unit by reacting 4'-(5-(pyridin-4-yl)furan-2-yl)-2,2':6',2"-bipyridine with 1,3,5-tri(chloromethyl)benzene: Specifically, first, take 4'-(5-(pyridin-4-yl)furan-2-yl)-2,2':6',2"-bipyridine (1.50 mmol) and 1,3,5-tri(chloromethyl)benzene (0.30 mmol) and add them to a 10 mL Schlenk flask, repeatedly evacuate and release the gas three times, and add 5 mL of acetonitrile under a nitrogen flow. The above solution is refluxed at 110°C for 64 hours; after the reaction solution is cooled to room temperature, the reaction solution is added dropwise to 30 mL of vigorously stirred acetone, and then after sufficient stirring, the solution is filtered to obtain an off-white solid, and the precipitate is washed with ether and dried to obtain a white powder.

[0095] S2. The tridentate intermediate obtained in step S1 is reacted with ruthenium chloride to obtain a two-dimensional network iron-based non-fully conjugated metal-supramolecular polymer electrochromic nanomaterial. Specifically, the tridentate intermediate (0.03mmol) and ruthenium chloride (0.045mmol) are added to a 25mL round-bottom flask, and the gas is repeatedly evacuated three times and then slowly added to 10mL of CH3OH under N2 protection. The above solution is refluxed at 70°C for 12h. Subsequently, 10mL of saturated methanol solution of ammonium hexafluorophosphate (NH4PF6) is added and stirring is continued for 12h to fully replace the counter anion with PF 6- , then filtered, washed and dried to obtain a solid product.

[0096] Example 10

[0097] This embodiment provides a method for synthesizing a two-dimensional network zinc-based non-fully conjugated metal-supramolecular polymer electrochromic nanomaterial, comprising the following steps:

[0098] S1. Prepare a tridentate intermediate with a non-conjugated unit by reacting 4'-(5-(pyridin-4-yl)thiophen-2-yl)-2,2':6',2"-bipyridine with 1,3,5-tris(bromomethyl)benzene: Specifically, first, take 4'-(5-(pyridin-4-yl)thiophen-2-yl)-2,2':6',2"-bipyridine (0.5mmol) and 1,3,5-tris(bromomethyl)benzene (0.25mmol) and add them to a 25mL Schlenk flask, repeatedly evacuate and release the gas three times, and add 10mL of DMF under a nitrogen flow. The above solution is refluxed at 115°C for 48h; after the reaction solution is cooled to room temperature, the reaction solution is added dropwise to 50mL of vigorously stirred acetone, and then after sufficient stirring, the solution is filtered to obtain an off-white solid, and the precipitate is washed with ether and dried to obtain a white powder.

[0099] S2. The tridentate intermediate obtained in step S1 is reacted with zinc chloride to obtain a two-dimensional network iron-based non-fully conjugated metal-supramolecular polymer electrochromic nanomaterial. Specifically, the tridentate intermediate (0.05 mmol) and zinc chloride (0.1 mmol) are added to a 50 mL round-bottom flask, and the gas is repeatedly pumped and released three times, and then slowly added to 10 mL of methanol under N2 protection. The above solution is refluxed at 70 ° C for 48 hours. After cooling to room temperature, the solution is evaporated to dryness using a rotary evaporator, followed by ultrasonic washing with 30 mL of ACN solution, and filtered and dried to obtain a solid product.

[0100] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the scope of protection of the present invention.

Claims

1. A two-dimensional network non-fully conjugated metal-supramolecular polymer, characterized in that: The structural formula is shown below: The anion balanced with the metal ion is any one or two or more of acetate, acetylacetonate, cyclohexanebutyrate, halide, hexafluorophosphate, hexafluoroacetylacetonate, nitrate, perchlorate, phosphate, sulfate, tetrafluoroborate or fluoromethanesulfonate.

2. The method for preparing the two-dimensional network non-fully conjugated metal-supramolecular polymer according to claim 1, characterized in that: The following steps are involved: S1, terpyridine derivatives and 1,3,5-tris(halogenated methyl)benzene react to synthesize a tridentate intermediate with a non-conjugated unit; S2. The tridentate intermediate and metal ions are subjected to coordination reaction to prepare a two-dimensional network non-fully conjugated metal-supramolecular polymer.

3. The method for preparing the two-dimensional network non-fully conjugated metal-supramolecular polymer according to claim 2, characterized in that: The terpyridine derivatives are 4'-(4-(pyridinyl-4-phenyl)-2,2':6',2"-terpyridine, 4'-(4-(pyridin-4-yl)cyclopentadien-1-yl)-2,2':6',2"-terpyridine, 4'-(5-(pyridin-4-yl)furan-2-yl)-2,2':6',2"-terpyridine or 4'-(5-(pyridin-4-yl)thiophene-2-yl)-2,2':6',2"-terpyridine.

4. The method for preparing the two-dimensional network non-fully conjugated metal-supramolecular polymer according to claim 2, characterized in that: The 1,3,5-tris(halogenated methyl)benzene is 1,3,5-tris(bromomethyl)benzene, 1,3,5-tris(chloromethyl)benzene or 1,3,5-tris(iodomethyl)benzene.

5. The method for preparing the two-dimensional network non-fully conjugated metal-supramolecular polymer according to claim 3 or 4, characterized in that: The molar ratio of the 1,3,5-tris(halogenated methyl)benzene to the terpyridine derivative is 1:(2-5); the reaction temperature in step S1 is 110-130° C., and the reaction time is 48-72 hours.

6. The method for preparing the two-dimensional network non-fully conjugated metal-supramolecular polymer according to claim 2, characterized in that: In step S2, the metal ion is Fe 2+ , Ru 2+ , Os 2+ , Cu 2+ , Zn 2+ Any one of .

7. The method for preparing the two-dimensional network non-fully conjugated metal-supramolecular polymer according to claim 6, characterized in that: The molar ratio of the tridentate intermediate to the metal ion is 1:(1.5-4).

8. The method for preparing the two-dimensional network non-fully conjugated metal-supramolecular polymer according to claim 7, characterized in that: The reaction temperature of the coordination reaction in step S2 is 70-90° C., and the reaction time is 12-48 hours.

9. Use of the two-dimensional network non-fully conjugated metal-supramolecular polymer according to claim 1 as an electrochromic material, characterized in that: Electrochromic nanofilms were prepared using two-dimensional network non-fully conjugated metal-supramolecular polymers.

10. The use of the two-dimensional network non-fully conjugated metal-supramolecular polymer as an electrochromic material according to claim 9, characterized in that: The preparation of the electrochromic nanofilm comprises the following steps: Y1. dissolving a two-dimensional network non-fully conjugated metal-supramolecular polymer electrochromic nanomaterial in a solvent to obtain a nanomaterial ink; Y2. The nanomaterial ink obtained in step Y1 is constructed into a two-dimensional network non-fully conjugated metal-supramolecular polymer electrochromic nanofilm on a transparent conductive substrate through a wet film forming method.

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