CN115181252A - Five-membered aromatic heterocycle fused BODIPY-based high polymer material and preparation method thereof - Google Patents
Five-membered aromatic heterocycle fused BODIPY-based high polymer material and preparation method thereof Download PDFInfo
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- CN115181252A CN115181252A CN202210985030.7A CN202210985030A CN115181252A CN 115181252 A CN115181252 A CN 115181252A CN 202210985030 A CN202210985030 A CN 202210985030A CN 115181252 A CN115181252 A CN 115181252A
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Abstract
The invention relates to a high polymer material based on five-membered aromatic heterocycle fused BODIPY and a preparation method thereof, belonging to the technical field of organic functional materials, wherein the structural general formula of the high polymer material is shown as formula I, wherein n is an integer of 3-200, m is an integer of 0-200, a monomer A is shown as formula II, and a monomer B is a repeating unit shown as formula III-V. The polymer material is prepared from corresponding monomers through Stille polymerization reaction. The polymer material based on the five-membered aromatic heterocycle fused BODIPY has short wave infrared absorption property, the absorption spectrum can be expanded to 1500nm, and meanwhile, the synthesis is simple, the mass preparation is easy, and the polymer material has a very high molar absorption coefficient and good photo-thermal stability. The polymer material hasThe infrared camouflage film has the potential of being applied to the fields of infrared camouflage, photo-thermal treatment, photoelectric detection and the like.
Description
Technical Field
The invention relates to the technical field of organic functional materials, in particular to a high polymer material based on five-membered aromatic heterocycle fused BODIPY and a preparation method thereof.
Background
Boron-dipyrromethene (boron-dipyrromethene), referred to as BODIPY for short, is a common organic fluorescent dye, has many unique photochemical and photophysical properties, and is widely concerned by the scientific community. The BODIPY compound generally has good light stability, higher fluorescence quantum yield and molar extinction coefficient, and has a plurality of modification sites, and fluorescent materials with specific absorption/emission wavelengths can be obtained through modification of a plurality of sites and different modification groups, so that different application requirements are met. Based on the characteristics, the BODIPY compounds have great application potential in the fields of fluorescent sensors, biological imaging, organic photodiodes, photocatalytic reactions, organic solar cells and the like.
The wavelength range of the short wave infrared is 1100nm-3000nm. Organic materials with strong absorption/emission properties in the short-wave infrared band have many application requirements in the fields of photoelectric detection, biological imaging, night vision equipment and the like. However, the absorption/emission wavelength of the BODIPY element is around 500nm, and the absorption/emission wavelength of the small molecule/high molecular material designed based on the BODIPY element is partially red-shifted to the near infrared region. The reported macromolecular/small molecular material designed based on BODIPY element is difficult to satisfy the related application facing short wave infrared band. In the strategy of red-shifting BODIPY absorption/emission wavelength, based on the BODIPY basic unit fused aromatic unit, the expansion of pi conjugated system is a very effective means. For example, chinese patent application publication No. CN114249758a discloses a dimer based on five-membered aromatic heterocyclic BODIPY, the BODIPY fused unit employs five-membered aromatic heterocyclic rings, which has a smaller dihedral angle when forming the dimer, and is beneficial to extension conjugation; the introduction of phenyl derivatives at both ends of the dimer facilitates further red-shift spectrum, and the absorption spectrum can be extended to 1100nm. The conjugated unit obtains high molecules through a reasonable polymerization method, and the extension of a pi conjugated system is also a common method in the synthesis of organic compounds. Therefore, the invention provides a polymer based on five-membered aromatic heterocycle fused BODIPY, and research on design, synthesis and application of the polymer has few related literature reports, so that the polymer is worthy of being deeply explored and developed, and can further red-shift an absorption/emission spectrum of the BODIPY while maintaining a high molar absorption coefficient.
Disclosure of Invention
In view of this, the technical problem to be solved by the present invention is to provide a polymer material based on five-membered aromatic heterocyclic fused BODIPY and a preparation method thereof. Compared with a dimer of five-membered aromatic heterocycle fused BODIPY, the high polymer material disclosed by the invention can further red shift the absorption/emission spectrum of the BODIPY to a short-wave infrared region, has a certain transparent property in a visible light region, and is simple in synthesis method and mild in reaction conditions. The compound has optical properties of strong absorption/emission and high molar absorption coefficient epsilon in a short-wave infrared region.
In order to solve the technical problems, the technical scheme of the invention is as follows:
the invention provides a high polymer material based on five-membered aromatic heterocycle fused BODIPY, which is composed of at least 1 monomer A or at least 1 monomer A and at least 1 monomer B independently, and has the following structural general formula:
in the formula I, n is an integer of 3-200, and m is an integer of 0-200;
when m is not 0, the proportional relationship of n, m is 10;
when m is 0, the proportional relation of n and m is n: m =1:0;
when a plurality of monomers A exist in the high polymer material, the monomers A can be the same or different, and when a plurality of monomers B exist in the high polymer material, the monomers B can be the same or different;
monomer A is a repeating unit represented by formula II below:
in formula II, X is a nitrogen atom (N) or a carbon atom (C-R) to which an R group is attached, R being one of the following structures:
y is an oxygen atom (O), a sulfur atom (S) or a selenium atom (Se);
R a1 ，R a2 each independently is one of the following structures:
R b1 ，R b2 each independently is one of the following structures:
R c1 ，R c2 each independently is one of the following structures:
R、R a1 、R a2 、R b1 、R b2 、R c1 、R c2 in, R d Each independently is hydrogen, alkyl, arylalkyl, heteroalkyl, or aryl with or without a substituent attached; when there are more than one R d When they are the same, they may be different;
the monomer B is one of the repeating units represented by the following formulas III-V:
Ar 1 、Ar 2 each independently is C 2-23 Unsaturated aromatic ring of (A) or (C) 2-23 Of unsaturated aromatic heterocycles of (a), wherein C 2-23 The unsaturated aromatic heterocycle at least comprises a heteroatom, and the heteroatom at least comprises one of nitrogen, oxygen, sulfur and selenium; the following structures may be mentioned:
X 1 、X 2 、X 3 each independently is one of the following structures:
wherein k is an integer of 1 to 12;
Ar 1 、Ar 2 、X 1 、X 2 、X 3 in, R e Each independently is hydrogen, alkyl, arylalkyl, heteroalkyl, or aryl with or without a substituent attached; when there are more than one R e When they are used, they may be the same or different.
It is preferable that:
the proportion relation of n and m is 4;
more preferably:
the proportional relation of n and m is n: m =1:0 or 1:1 or 2:1, and the proportional structure is selected, so that the stable properties of the material can be ensured, the synthetic method is relatively simple, the reaction yield is high, and the synthetic repeatability is good.
It is preferable that:
when a plurality of monomers A exist in the high polymer material, the number of different monomer A structures is less than 4, and when a plurality of monomers B exist in the high polymer material, the number of different monomer B structures is less than 6.
More preferably:
when a plurality of monomers A exist in the high polymer material, different monomer A structures are 1 or 2, and when a plurality of monomers B exist in the high polymer material, different monomer B structures are less than 4, so that the selection can reduce the synthesis cost of the high polymer material and is favorable for rapid and efficient synthesis.
It is preferable that: x is one of the following structures:
the preferable X structure is selected, so that the synthesis is simple and easy to implement.
More preferably: x is one of the following structures:
the more preferable X structure is selected, so that the band gap is reduced, and the absorption in a visible light region is weakened.
In the above technical solution, it is preferable that: y is an oxygen atom (O) or a sulfur atom (S).
The preferable Y structure is selected, so that the stability of the high polymer material is improved.
It is preferable that: r is a1 ，R a2 Each independently is one of the following structures:
wherein b is an integer of 1 to 12, preferably 1 to 5; e and f are each independently an integer of 0 to 16, preferably 6 to 14.
The above-mentioned preferred R is selected a1 ，R a2 The structure is favorable for improving the solubility of the high polymer material and the molecular weight of the high polymer material.
It is preferable that: r b1 ，R b2 Each independently is one of the following structures:
the above-mentioned preferred R is selected b1 ，R b2 The structure and the substituent group have electron-rich property, which is beneficial to red shift of the spectrum.
More preferably: r b1 ，R b2 Each independently is one of the following structures:
the more preferable R mentioned above is selected b1 ，R b2 The structure is favorable for the high-efficiency synthesis of high polymer materials.
Wherein b is an integer of 1 to 17, preferably 13 to 17; x is an integer of 1 to 12, preferably 1 to 5; y and z are each independently an integer of 0 to 16, preferably 0 to 8.
The above-mentioned preferred R is selected b1 ，R b2 The structure is favorable for the high-efficiency synthesis of high polymer materials.
It is preferable that: r c1 ，R c2 Each independently one of the following structures:
wherein a is an integer of 1 to 17, preferably 1 to 8; q and d are each independently an integer of 0 to 16, preferably 0 to 8.
The above-mentioned preferred R is selected c1 ，R c2 The structure is favorable for ensuring the planarity of the conjugated skeleton of the high polymer material and is favorable for the high polymer material to absorb the wavelength red shift.
It is preferable that: ar (Ar) 1 、Ar 2 Each independently is one of the following structures:
the above-mentioned preferred Ar is selected 1 、Ar 2 The structure is beneficial to ensuring the planarity of the conjugated skeleton of the high polymer material and ensuring the effective conjugation among the polymerized monomers of the high polymer material.
More preferably: ar (Ar) 1 、Ar 2 Each independently is one of the following structures:
the more preferable Ar mentioned above is selected 1 、Ar 2 The structure is favorable for ensuring the solubility of the high polymer material, and the high polymer material has good solution processability.
Wherein h is an integer of 1 to 17, preferably 1 to 8; i and g are each independently an integer of 0 to 16, preferably 0 to 8.
It is preferable that: x 1 、X 2 、X 3 Each independently is one of the following structures:
the above-mentioned preferred X is selected 1 、X 2 、X 3 The structure is beneficial to ensuring the planarity of the conjugated skeleton of the high polymer material and ensuring the effective conjugation among the polymerized monomers of the high polymer material.
It is preferable that: the polymer material based on the five-membered aromatic heterocyclic fused BODIPY shown in the formula I is selected from any one of structures shown in formulas A1-1 to J-5, but is not limited thereto, substituent groups on the structures may be replaced by other substituent groups, alkyl side chains may also be replaced by different lengths or different branching sites, and n is an integer of 3 to 200:
the invention also provides a preparation method of the five-membered aromatic heterocycle fused BODIPY-based high polymer material, which comprises the following steps:
when m =1:0, the unit A substituted by alpha-bromine and the distannum salt are used as polymerization monomers;
when m =1:1, the unit A substituted by alpha-bromine and the unit B of the distannum salt are used as polymerization monomers;
n, m is 10 >;
the monomer is subjected to Stille polymerization reaction to obtain a high polymer material which has an absorption wavelength reaching a short wave infrared region and is based on five-membered aromatic heterocyclic fused BODIPY;
the structural formula of the alpha-bromine substituted unit A is shown as a formula VI, the structural formula of the bisstannate is shown as a formula VII, the structural formula of the unit B of the bisstannate is shown as a formula VIII, and the structural formula of the bromine substituted unit B is shown as a formula IX;
in the formula VII, R 4 Is methyl, ethyl or n-butyl;
in the formula VIII, R 5 Is methyl, ethyl or n-butyl.
It is preferable that: r 4 Is n-butyl;
it is preferable that: r 5 Is methyl or n-butyl;
it is preferable that: the preparation method comprises the following specific steps: under the protection of argon or nitrogen, dissolving a polymerization monomer in an organic solvent, adding a catalyst, and carrying out Stille polymerization reaction under the conditions of light shielding and heating to obtain the polymer material based on the five-membered aromatic heterocycle fused BODIPY with the absorption wavelength reaching a short-wave infrared region.
Further preferred are: the organic solvent is toluene, chlorobenzene or o-dichlorobenzene, the palladium catalyst is tris (dibenzylideneacetone) dipalladium, and the ligand is tris (o-methylphenyl) phosphine;
it is further preferred that: the concentration of each of the polymerization monomers in the organic solvent is 0.005 to 0.2mM.
Further preferred are: m =1:0, the ratio of the amounts of material of α -bromo substituted unit a, the bistin salt, tris (dibenzylideneacetone) dipalladium, tris (o-methylphenyl) phosphine is 1:1: (0.01-0.05): (0.04-0.2).
Further preferred are: m =1:1, the ratio of the amounts of material of α -bromo substituted unit a, unit B of the bistin salt, tris (dibenzylideneacetone) dipalladium, tris (o-methylphenyl) phosphine is 1:1: (0.01-0.05): (0.04-0.2).
Further preferred are: n, m is 10 > < n > m > < 1> and n: m ≠ 1:1, the ratio of the amounts of α -bromo-substituted unit A, bromo-substituted unit B, the bisttannate, tris (dibenzylideneacetone) dipalladium, tris (o-methylphenyl) phosphine species is n: m: n + m: (0.01-0.05) × (n + m) < 0.04-0.2) × (n + m).
Further preferred are: the reaction temperature of the Stille polymerization reaction is 90-150 ℃, and the polymerization reaction time is 1-72 h.
The beneficial effects of the invention are:
the polymer material based on the fused BODIPY of the five-membered aromatic heterocycle provided by the invention expands a conjugated system of BODIPY elements in a [ b ] -fused mode, and the structure of the five-membered aromatic heterocycle ensures the plane configuration among polymerization units, so that the two points are beneficial to expanding the conjugated system of the polymer material based on the fused BODIPY of the five-membered aromatic heterocycle, and the band gap and the red shift spectrum are reduced. Compared with a dimer, the polymer structure has a larger conjugated system, the product molecules are more stable, and the infrared optical performance is more excellent.
The copolymerized unit B can regulate and control the properties of the polymer such as energy level, mobility, crystallinity and the like on the basis of ensuring the short wave infrared absorption of the polymer material of the five-membered aromatic heterocycle fused BODIPY. Meanwhile, the B unit is used as a bridging structure, so that the connection and the transmission of a conjugated system are ensured, better optical performance is ensured, the molecular rigidity is reduced relative to a conjugated chain segment with higher degree of freedom, the possibility is provided for molecular modification and molecular modification, the material processing and application are facilitated, the performance of the material is improved, and a solid foundation is laid for expanding the application field.
The preparation method of the five-membered aromatic heterocycle fused BODIPY-based high polymer material provided by the invention has the advantages of simple reaction, high reaction yield, mild reaction conditions and many modifiable sites.
Experimental results show that the five-membered aromatic heterocyclic fused BODIPY-based polymer material provided by the invention has an extremely narrow optical band gap, the main absorption wavelength is distributed from 900nm to 1600nm, a short wave infrared region is achieved, and the molar absorption coefficient is higher. Through modifying substituent groups on the five-membered aromatic heterocycle fused BODIPY unit and regulating and controlling the copolymerization unit, the structure can be effectively enriched, the absorption/emission wavelength of the material can be regulated and controlled, and different practical application requirements can be met. The compounds are expected to have great application potential in the fields of organic solar cells, photoelectric detection, biological imaging, laser protection and the like.
Drawings
The present invention will be described in further detail with reference to the accompanying drawings and specific embodiments.
FIG. 1 is a scheme of intermediates A1 to M1 1 H NMR spectrum.
FIG. 2 is a drawing of intermediates B1-M 1 H NMR spectrum.
Fig. 3 shows an ultraviolet-visible-near infrared absorption spectrum of the polymer material A1-1.
Fig. 4 shows an ultraviolet-visible-near-infrared absorption spectrum of the polymer material A1 to 4.
FIG. 5 shows an ultraviolet-visible-near infrared absorption spectrum of the polymer material E1-1.
FIG. 6 shows the UV-visible-NIR absorption spectrum of the polymer F1-1
FIG. 7 shows an ultraviolet-visible-near infrared absorption spectrum of the polymer material G1-1.
FIG. 8 is an electrochemical cyclic voltammogram of the polymer material A1-1.
FIG. 9 is an electrochemical cyclic voltammogram of the polymer material A1-4.
FIG. 10 is an electrochemical cyclic voltammogram of the polymer material E1-1.
FIG. 11 is an electrochemical cyclic voltammogram of the polymer material F1-1.
FIG. 12 shows the UV-VIS-NIR transmission spectra of the binary blend film of polymer materials A1-4 and PMMA.
FIG. 13 is a photograph of a binary blend film of the polymeric materials A1-4 and PMMA.
Detailed Description
In order to further illustrate the present invention, the following synthesis examples and examples are provided to describe the five-membered aromatic heterocycle fused BODIPY-based polymer material, the preparation method thereof, and the photo-physical property test in detail, but they should not be construed as limiting the scope of the present invention.
In the following examples, various procedures and methods not described in detail are conventional methods well known in the art. Materials, reagents, devices, instruments, apparatuses and the like used in the following examples are commercially available unless otherwise specified. The terms used in the present invention generally have meanings commonly understood by those of ordinary skill in the art, unless otherwise specified.
Intermediates A1-M1 Synthesis of S7 in Synthesis example 2 with reference to patent application CN114249758A, except that the substituent on the pyrrole ring is replaced by-C 7 H 15 Substitution to-C 17 H 35 Of intermediates A1-M1 1 The H NMR spectrum is shown in FIG. 1. Intermediates B1-M were synthesized according to S11 of Synthesis example 3 of patent application CN114249758A, preparation of intermediates B1-M 1 The H NMR spectrum is shown in FIG. 2.
Synthesis example 1: synthesis of intermediates A1-M2
A1-M1 (280mg, 0.3mmol), tin tetrachloride (78mg, 0.3mmol), trimethylsilyl cyanide (592mg, 6.0 mmol), dried dichloromethane (50 mL) were charged into a 250mL round-bottomed flask and reacted at room temperature for 1 hour under an argon atmosphere. Extraction with dichloromethane was carried out three times, the organic phases were combined, dried over anhydrous sodium sulfate, the organic phases were concentrated under reduced pressure, and the obtained crude product was separated by silica gel column chromatography (eluent was a mixed solution of petroleum ether: dichloromethane in a volume ratio of = 1:2) to obtain the product A1-M2 (202 mg, yield 71%). The results of elemental analysis and matrix-assisted laser desorption time-of-flight mass spectrometry (MALDI-TOF) analysis of the products A1-M2 were as follows: elemental analysis: calculated C,61.76; h,7.72; b,1.13; br,16.77; n,5.88; s,6.73. Experimental value C,61.77; h,7.72; and N,5.88. Matrix-assisted laser desorption time-of-flight mass spectrometry (MALDI-TOF) analysis: theoretical value 950.4; experimental value 950.4.
Synthesis example 2: synthesis of intermediate A2-M2
The synthesis method of the intermediate A2-M2 is the same as that of the intermediate A1-M2, except that the reaction intermediate A2-M2 is A2-M1, and the reaction intermediate A1-M2 is A1-M1. Product A2-M2 (203 mg, 69% yield) was obtained. Elemental analysis: calcd for C,63.92; h,7.99; b,1.17; br,17.36; n,6.08; and O,3.48. The experimental value is C,63.95; h,7.99; and N,6.08. Matrix-assisted laser desorption time-of-flight mass spectrometry (MALDI-TOF) analysis: theoretical value 918.4; experimental value 918.4.
Synthesis example 3: synthesis of intermediates A1-M3
A1-M1 (50mg, 0.053 mmol) and dry THF (2 mL) were charged in a 50mL round-bottomed flask, and 1-propynylmagnesium bromide (0.5M in THF,0.6mL, 0.300mmol) was slowly added and reacted at room temperature under an argon atmosphere for 1 hour. Extraction with dichloromethane was carried out three times, the organic phases were combined, dried over anhydrous sodium sulfate, the organic phases were concentrated under reduced pressure, and the obtained crude product was separated by silica gel column chromatography (eluent was a mixed solution of petroleum ether: dichloromethane in a volume ratio of = 5:1) to obtain the product A1-M3 (32 mg, yield 61%). The results of elemental analysis and matrix-assisted laser desorption time-of-flight mass spectrometry (MALDI-TOF) analysis of the products A1-M3 were as follows: elemental analysis: calculated as C,65.03; h,8.13; b,1.10; br,16.32; n,2.86; s,6.55. The experimental value is C,65.00; h,8.13; and N,2.90. Matrix-assisted laser desorption time-of-flight mass spectrometry (MALDI-TOF) analysis: theoretical value 976.4; experimental value 976.4.
Synthesis example 4: synthesis of intermediates A2-M3
The synthesis method of the intermediates A2-M3 is the same as that of the intermediates A1-M3, except that the reaction intermediates of the intermediates A2-M3 are A2-M1, and the reaction intermediates of the intermediates A1-M3 are A1-M1. Product A2-M3 (203 mg, 69% yield) was obtained. Elemental analysis: calcd for C,67.23; h,8.41; b,1.14; br,16.88; n,2.96; and O,3.38. The experimental value is C,67.26; h,8.43; and N,2.93. Matrix-assisted laser desorption time-of-flight mass spectrometry (MALDI-TOF) analysis: theoretical value 944.5; experimental value 944.5.
Synthesis example 5: synthesis of intermediates A1-M4
A50 mL round bottom flask was charged with A1-M1 (50mg, 0.053 mmol), dried dichloromethane (2 mL), cooled well in an ice-water bath at 0 ℃ under argon, and phenylmagnesium bromide (1M in THF,0.13mL, 0.13mmol) was added slowly and reacted for 10min at 0 ℃. Dichloromethane was extracted three times, organic phases were combined, dried using anhydrous sodium sulfate, and the organic phases were concentrated under reduced pressure to obtain a crude product, which was separated using silica gel column chromatography (eluent was a mixed solution of petroleum ether: dichloromethane in a volume ratio of = 4:1) to obtain products A1-M4 (13 mg, yield 23%). The results of elemental analysis and matrix-assisted laser desorption time-of-flight mass spectrometry (MALDI-TOF) analysis of the products A1-M4 were as follows: elemental analysis: calculated C,67.17; h,7.93; b,1.02; br,15.15; n,2.66; and S,6.08. Experimental value C,67.18; h,7.95; n,2.67. Matrix assisted laser desorption time of flight mass spectrometry (MALDI-TOF) analysis: theoretical value 1052.5; experimental value 1052.5.
Synthesis example 6: synthesis of intermediates A2-M4, B1-M1, B2-M1, C1-M2, C2-M2
The intermediates A2-M4, B1-M1, B2-M1, C1-M2 and C2-M2 were prepared in the same manner as in A1-M4 of Synthesis example 5 except that the substrates A1-M1 were replaced with A2-M1, B1-M, B-M, C-M1 and C2-M1, respectively. The synthetic results and material characterization data are shown in the following table:
synthesis example 7: synthesis of intermediates A1-M5
A50 mL round-bottom flask was charged with A1-M1 (50mg, 0.053 mmol), aluminum trichloride (11mg, 0.08mmol), dry dichloromethane (2 mL), and reacted at 50 ℃ for 15min under an argon atmosphere. Methanol (1 mL) was added to the reaction mixture, and the mixture was reacted at room temperature for 15min. Extraction with dichloromethane was carried out three times, the organic phases were combined, dried over anhydrous sodium sulfate, the organic phases were concentrated under reduced pressure, and the resulting crude product was separated by silica gel column chromatography (eluent was a mixed solution of petroleum ether: dichloromethane in a volume ratio of = 4:1) to give the products A1-M5 (23 mg, yield 45%). The results of elemental analysis and matrix-assisted laser desorption time-of-flight mass spectrometry (MALDI-TOF) analysis of the products A1-M5 were as follows: elemental analysis: calculated C,61.12; h,8.27; b,1.12; br,16.60; n,2.91; o,3.32; and S,6.66. The experimental value is C,61.15; h,8.30; and N,2.98. Matrix-assisted laser desorption time-of-flight mass spectrometry (MALDI-TOF) analysis: theoretical value 960.4; experimental value 960.4.
Synthesis example 8: synthesis of intermediates A2-M5, B1-M2, B2-M2, C1-M4, C2-M4
The intermediates A2-M5, B1-M2, B2-M2, C1-M4 and C2-M4 were prepared in the same manner as in A1-M5 of Synthesis example 7 except that the substrates A1-M1 were replaced with A2-M1, B1-M, B-M, C-M1 and C2-M1, respectively. The synthetic results and material characterization data are shown in the following table:
synthesis example 9: synthesis of intermediates C1-M5
A50 mL round-bottomed flask was charged with C1-M1 (50mg, 0.074mmol), aluminum trichloride (20mg, 0.15mmol), and dried methylene chloride (5 mL) and reacted at 50 ℃ for 15min under an argon atmosphere. Trimethylsilylacetate (196mg1.481mmol) was added to the reaction mixture, and the mixture was reacted at room temperature for 1 hour. Extraction with dichloromethane was carried out three times, the organic phases were combined, dried over anhydrous sodium sulfate, the organic phases were concentrated under reduced pressure, and the obtained crude product was separated by silica gel column chromatography (eluent was a mixed solution of petroleum ether: dichloromethane in a volume ratio of = 2:1) to obtain the product C1-M5 (34 mg, yield 61%). The results of elemental analysis and matrix-assisted laser desorption time-of-flight mass spectrometry (MALDI-TOF) analysis of the products C1-M5 were as follows: elemental analysis: calcd for C,47.71; h,2.94; b,1.43; br,21.16; n,5.56; o,12.71; and S,8.49. The experimental value is C,47.72; h,2.95; and N,5.55. Matrix assisted laser desorption time of flight mass spectrometry (MALDI-TOF) analysis: theoretical value 752.9; experimental value 752.9.
Synthesis example 10: synthesis of intermediates B1-M3, B2-M3, C2-M5
The intermediates B1-M3, B2-M3 and C1-M5 were prepared in the same manner as in C1-M5 of Synthesis example 9 except that the substrates C1-M1 were replaced with B1-M, B-M, C-M1, respectively. The synthetic results and material characterization data are shown in the following table:
synthesis example 11: synthesis of intermediates B1 to M5
Synthesis of intermediate S2:
to a 250mL round bottom flask was added 3-methoxythiophene (3.0 g, 26.28mmol), 1-hexadecanol (12.7 g, 52.56mmol), p-toluenesulfonic acid monohydrate (0.5 g, 2.63mmol), dried toluene (45 mL), and stirred at 115 ℃ for 3h under an argon atmosphere. Extraction with dichloromethane was carried out three times, the organic phases were combined, dried over anhydrous sodium sulfate, the organic phases were concentrated under reduced pressure, and the crude product obtained was isolated by column chromatography on silica gel (eluent petroleum ether) to give the product S2 (7.6 g, 89% yield). Elemental analysis and matrix-assisted laser desorption time-of-flight mass spectrometry (MALDI-TOF) analysis of product S2 resulted in the following: elemental analysis: calculated value C,74.01; h,11.18; o,4.93; and S,9.88. The experimental value is C,74.03; h,11.19. Matrix-assisted laser desorption time-of-flight mass spectrometry (MALDI-TOF) analysis: theoretical value 324.3; experimental value 324.3.
Synthesis of intermediate S3:
a250 mL round bottom flask was charged with S2 (1.9g, 5.8mmol), dry THF (100 mL), cooled well in a-78 deg.C dry ice acetone bath under argon, added n-butyllithium (2.5M in hexane,7 mL), reacted at 78 deg.C for 2.5h, charged dry DMF (1.8mL, 23.2mmol) to the reaction flask, allowed to slowly warm to room temperature and stirred overnight. Extraction with dichloromethane was carried out three times, the organic phases were combined, dried over anhydrous sodium sulfate, the organic phases were concentrated under reduced pressure, and the crude product obtained was separated by column chromatography on silica gel (eluent was a mixed solution of petroleum ether: dichloromethane in a volume ratio of = 1:1) to obtain product S3 (0.62g, 30%). Elemental analysis and matrix-assisted laser desorption time-of-flight mass spectrometry (MALDI-TOF) analysis of product S3 resulted in the following: elemental analysis: calcd for C,71.54; h,10.29; o,9.08; and S,9.09. Experimental value C,71.55; h,10.29. Matrix-assisted laser desorption time-of-flight mass spectrometry (MALDI-TOF) analysis: theoretical value 352.2; experimental value 352.2.
Synthesis of intermediate S4:
a100 mL round bottom flask was charged with S3 (917mg, 2.6mmol), ethyl azidoacetate (1350mg, 10.4mmol), dried THF (13 mL), dried EtOH (13 mL), the reaction flask was placed in a-10 ℃ ice salt bath and sufficiently cooled, etONa (708mg, 10.4mmol) was slowly added to the reaction solution, and the reaction was carried out at-10 ℃ for 2.5 hours under an argon atmosphere. To the reaction mixture was added a saturated ammonium chloride solution (10 mL), and the mixture was stirred at room temperature for 5min. Extraction with ether was carried out three times, the organic phases were combined, dried over anhydrous sodium sulfate, and the organic phases were concentrated under reduced pressure to give a crude product, which was separated by column chromatography on silica gel (eluent was a mixed solution of petroleum ether: dichloromethane in a volume ratio of = 6:1) to give the product S4 (423 mg, yield 38%). Elemental analysis and matrix-assisted laser desorption time-of-flight mass spectrometry (MALDI-TOF) analysis of product S4 resulted in the following: elemental analysis: calcd for C,68.92; h,9.49; n,3.22; o,11.02; and S,7.36. Experimental value C,68.90; h,9.49; n,3.22. Matrix-assisted laser desorption time-of-flight mass spectrometry (MALDI-TOF) analysis: theoretical value 435.3; experimental value 435.3.
Synthesis of intermediate S5:
a100 mL round-bottom flask was charged with S4 (423mg, 0.97mmol), naOH (580mg, 14.50mmol), etOH (10 mL), H 2 O (5 mL), 100 ℃ under an argon atmosphere for 1h. Slowly adding 6M hydrochloric acid into the reaction solution to adjust the pH of the reaction solution<7, filtered using a Buchner funnel and the solid on the filter paper was placed in a vacuum oven to dry at 70 ℃ to give product S5 (356 mg, 90% yield). Elemental analysis and matrix-assisted laser desorption time-of-flight mass spectrometry (MALDI-TOF) analysis of product S5 resulted in the following: elemental analysis: calculated C,67.77; h,9.15; n,3.44; o,11.78; and S,7.87. Experimental value C,67.75; h,9.16; and N,3.45. Matrix-assisted laser desorption time-of-flight mass spectrometry (MALDI-TOF) analysis: theoretical value 407.3; experimental value 407.3.
Synthesis of intermediate S6:
s5 (330mg, 0.81mmol) and trifluoroacetic acid (5 mL) were added to a 100mL round-bottomed flask, and stirred at 40 ℃ for 0.5h under an argon atmosphere, and trifluoroacetic anhydride (1.5 mL) was added to the reaction mixture and stirred at 80 ℃ for 5h. The reaction solution was slowly added to a saturated sodium bicarbonate solution to a solution pH >7, filtered through a buchner funnel, and the blue-brown solid on the filter paper was placed in a vacuum oven to dry at 70 ℃. To a 100mL round bottom flask was added the above dry blue-brown solid, dry dichloromethane (50 mL), boron trifluoride etherate (0.7 mL), triethylamine (0.5 mL), and stirred at room temperature for 2h under argon atmosphere. Dichloromethane was extracted three times, organic phases were combined, dried using anhydrous sodium sulfate, and the organic phases were concentrated under reduced pressure to obtain a crude product, which was separated using silica gel column chromatography (eluent was a mixed solution of petroleum ether: dichloromethane in a volume ratio of = 2:1) to obtain a product S6 (159 mg, yield 23%). Elemental analysis and matrix-assisted laser desorption time-of-flight mass spectrometry (MALDI-TOF) analysis of product S6 resulted in the following: elemental analysis: calcd for C,64.77; h,8.27; b,1.27; f,11.14; n,3.28; o,3.75; s,7.52. Experimental value C,64.77; h,8.25; and N,3.7. Matrix-assisted laser desorption time-of-flight mass spectrometry (MALDI-TOF) analysis: theoretical value 852.5; experimental value 852.5.
Synthesis of intermediates B1-M5:
s6 (85mg, 0.1mmol) in dry THF (2 mL) was added to a 100mL round-bottom flask, the mixture was cooled well in an ice-water bath at 0 ℃ and NBS (38mg, 0.21mmol) was added slowly to the flask, and the mixture was reacted at room temperature under argon atmosphere for 1 hour. Extraction with dichloromethane was carried out three times, the organic phases were combined, dried over anhydrous sodium sulfate, the organic phases were concentrated under reduced pressure, and the resulting crude product was separated by silica gel column chromatography (eluent was a mixed solution of petroleum ether: dichloromethane in a volume ratio of = 6:1) to give the products B1-M5 (86 mg, yield 85%). The results of elemental analysis and matrix-assisted laser desorption time-of-flight mass spectrometry (MALDI-TOF) analysis of the products B1-M5 were as follows: elemental analysis: calcd for C,54.66; h,6.78; b,1.07; br,15.81; f,9.40; n,2.77; o,3.17; s,6.34. Experimental value C,54.67; h,6.77; n,2.77. Matrix-assisted laser desorption time-of-flight mass spectrometry (MALDI-TOF) analysis: theoretical value 1008.3; experimental value 1008.3.
Synthesis example 12: synthesis of intermediates B2-M5
Intermediates B2 to M5 were prepared in the same manner as in B1 to M5 of Synthesis example 11 except that the reaction substrate S1 was replaced with 3-methoxyfuran. The synthetic results and material characterization data are shown in the following table:
synthesis example 13: synthesis of intermediates C1-M3
A50 mL round bottom flask was charged with C1-M1 (50mg, 0.074mmol), TEA (15mg, 0.150mmol), dry dichloromethane (5 mL), and dibutyl trifluoromethanesulfonate (1M in CH) was added slowly under an argon atmosphere 2 Cl 2 41mg, 0.150mmol), at room temperature for 1.5h. Dichloromethane extraction three times, organic phases were combined, dried using anhydrous sodium sulfate, the organic phases were concentrated under reduced pressure, and the resulting crude product was separated using silica gel column chromatography (eluent was a mixed solution of petroleum ether: dichloromethane in a volume ratio = 5:1) to give product C1-M3 (17 mg, 30% yield). The results of elemental analysis and matrix-assisted laser desorption time-of-flight mass spectrometry (MALDI-TOF) analysis of the products C1-M3 were as follows: elemental analysis: calcd for C,54.35; h,4.56; b,1.44; br,21.27; n,5.59; o,4.26; s,8.53. Experimental value C,54.38; h,4.57; and N,5.61. Matrix-assisted laser desorption time-of-flight mass spectrometry (MALDI-TOF) analysis: theoretical value 749.1; experimental value 749.1.
Synthesis example 14: synthesis of intermediates B1-M4, B2-M4, C2-M3
The intermediates B1 to M4, B2 to M4 and C2 to M3 were prepared in the same manner as in Synthesis example 12, except that the substrates C1 to M1 were replaced with B1-M, B-M, C-M1, respectively. The synthetic results and material characterization data are shown in the following table:
example 1: synthesis of Polymer Material A1-1
The preparation method of the high polymer material comprises the following steps: a50 mL round-bottomed flask was charged with A1-M1 (93.9mg, 0.1mmol), hexa-n-butylditin (58.0mg, 0.1mmol), tris (dibenzylideneacetone) dipalladium (1.4mg, 0.0015mmol), tris (o-methylphenyl) phosphorus (3.7mg, 0.012mmol), dried toluene (4 mL), and reacted at 110 ℃ for 24 hours under an argon atmosphere. Cooling the reaction solution to room temperature, dropwise adding the reaction solution into a methanol solution, filtering the solution by using a Buchner funnel, placing the solid on the filter paper in a vacuum drying oven to be dried at 70 ℃, using a Soxhlet extractor to sequentially wash off small molecules and the catalyst by using acetone and n-hexane to obtain a polymer material crude product, and finally extracting the polymer material by using chloroform to obtain the polymer material A1-1 (74 mg, yield 95%). The gel permeation chromatography analysis and the element analysis were performed on the polymer material A1-1, and the results were as follows: gel permeation chromatography (GPC, trichlorobenzene, polystyrene standard, 150 ℃ C.): m n =8kDa, PDI =1.81. Elemental analysis: calculated C,72.46; h,9.45; b,1.39; f,4.88; n,3.60; and S,8.23. Experimental value C,72.48; h,9.49; and N,3.57.
And (3) performance testing:
the ultraviolet-visible-near infrared absorption spectrometer is used for testing the photophysical properties of the high polymer material A1-1 prepared in example 1 of the invention, an ultraviolet-visible-near infrared absorption spectrum is shown in figure 3, strong absorption peaks at 1219nm and 1407nm are shown in the A1-1 film state, an absorption side band reaches 1630nm, and strong absorption in a short wave infrared region from 1100nm to 1600nm can be realized. Electrochemical property tests are carried out by using the electrochemical workstation high molecular material A1-1, and a cyclic voltammetry curve is shown in FIG. 8, wherein the LUMO energy level of A1-1 is-4.30eV, the HOMO energy level is-5.28 eV, the electrochemical band gap is 0.98eV, and the material is a narrow-band gap molecular material.
Examples 2 to 30: synthesis of high molecular material A1-2-C2-5
The production methods of the polymer materials A1-2 to C2-5 were the same as those of the polymer material A1-1 in example 1, except that the reaction substrates A1 to M1 were replaced with A1 to M2 to C2 to M5, respectively. The synthetic results and material characterization data are listed in the table below.
The ultraviolet-visible-near infrared absorption spectrometer is used for testing the photophysical properties of the high polymer material A1-4 prepared in the embodiment 4 of the invention, the ultraviolet-visible-near infrared absorption spectrum is shown in figure 4, the A1-4 shows strong absorption peaks at 1130nm and 1330nm in a film state, the absorption sideband reaches 1520nm, and the strong absorption in the short wave infrared region from 1100nm to 1520nm can be realized. An electrochemical workstation is used for carrying out electrochemical property tests on the high molecular material A1-4, the cyclic voltammetry curve is shown in FIG. 9, the LUMO energy level of A1-4 is-4.00eV, the HOMO energy level is-5.23 eV, the electrochemical bandgap is 1.23eV, and the material is a narrow-bandgap molecular material.
Example 31: synthesis of Polymer Material D1-1
The preparation method of the high polymer material comprises the following steps: a50 mL round-bottomed flask was charged with A1-M1 (46.9mg, 0.05mmol), A1-M2 (47.6mg, 0.05mmol), hexa-n-butylditin (58.0mg, 0.1mmol), tris (dibenzylideneacetone) dipalladium (1.4mg, 0.0015mmol), tris (o-methylphenyl) phosphorus (3.7mg, 0.012mmol), dry toluene (4 mL), and reacted at 110 ℃ for 24 hours under an argon atmosphere. Cooling the reaction solution to room temperature, dropwise adding the reaction solution into a methanol solution, filtering the solution by using a Buchner funnel, placing the solid on the filter paper in a vacuum drying oven to be dried at 70 ℃, using a Soxhlet extractor to sequentially wash off small molecules and the catalyst by using acetone and n-hexane, and finally extracting the high polymer material by using chloroform to obtain the high polymer material D1-1 (68 mg, yield 87%). The gel permeation chromatography analysis and the element analysis were performed on the polymer material D1-1, and the results were as follows: gel permeation chromatography (GPC, trichlorobenzene, polystyrene standard, 150 ℃ C.): m n =7kda,pdi =1.95. Elemental analysis: calculated C,73.34; h,9.36; b,1.38; f,2.42; n,5.35; and S,8.16. The experimental value is C,73.36; h,9.39; n,5.33.
Examples 32 to 35: synthesis of Polymer materials D1-2 to D1-5
Polymer materials D1-2, D1-3, D1-4 and D1-5 were prepared in the same manner as in Polymer material D1-1 of example 31 except that the reaction substrates A1-M1 and A1-M2 were replaced with A1-M1 and A2-M3, A1-M2 and B1-M1, B1-M5 and B2-M1, and C2-M5 and B2-M1, respectively. The synthetic results and material characterization data are listed in the table below.
Example 36: synthesis of Polymer Material E1-1
The preparation method of the high polymer material comprises the following steps: a50 mL round bottom flask was charged with A1-M4 (105.5mg, 0.1mmol), trans-1,2-bis (tributyltin) ethylene (60.6 mg, 0.1mmol), tris (dibenzylideneacetone) dipalladium (1.4 mg, 0.0015mmol), tris (o-methylphenyl) phosphonium (3.7 mg, 0.012mmol), dried toluene (4 mL), and reacted at 110 ℃ for 24h under argon. Cooling the reaction solution to room temperature, dropwise adding the reaction solution into a methanol solution, filtering the solution by using a Buchner funnel, placing the solid on the filter paper in a vacuum drying oven to be dried at 70 ℃, using a Soxhlet extractor to sequentially wash off small molecules and the catalyst by using acetone and n-hexane to obtain a polymer material crude product, and finally extracting the polymer material by using chloroform to obtain the polymer material E1-1 (83 mg, yield 90%). The gel permeation chromatography analysis and the element analysis were performed on the polymer material E1-1, and the results were as follows: gel permeation chromatography (GPC, trichlorobenzene, polystyrene standard, 150 ℃ C.): m n =21kda, pdi =1.85. Elemental analysis: calcd for C,79.53; h,9.30; b,1.17; n,3.04; and S,6.96. Experimental value C,79.53; h,9.31; and N,3.03.
And (3) performance testing:
the ultraviolet-visible-near infrared absorption spectrometer is used for testing the photophysical properties of the high polymer material E1-1 prepared in example 36 of the invention, the ultraviolet-visible-near infrared absorption spectrum is shown in FIG. 5, the E1-1 film shows a strong absorption peak at 1241nm, the absorption side band reaches 1320nm, and strong absorption in the short wave infrared region of 1100nm to 1320nm can be realized. An electrochemical workstation high molecular material E1-1 is used for carrying out an electrochemical property test, and a cyclic voltammetry curve is shown in figure 10, wherein the LUMO energy level of the E1-1 is-3.75eV, the HOMO energy level is-5.32 eV, and the electrochemical band gap is 1.57eV, so that the cyclic voltammetry curve is a narrow-band gap molecular material.
Examples 37 to 40: synthesis of Polymer materials E1-2 to E1-5
Polymer materials E1-2, E1-3, E1-4 and E1-5 were prepared in the same manner as in Polymer material E1-1 of example 36 except that the reaction substrates A1-M4 were replaced with A2-M4, B1-M2, B2-M2 and C1-M5, respectively. The synthetic results and material characterization data are listed in the table below.
Example 41: synthesis of Polymer Material F1-1
The preparation method of the high polymer material comprises the following steps: a50 mL round bottom flask was charged with A1-M4 (105.5mg, 0.1mmol), 2,5-bis (trimethylstannyl) thiophene (41.0mg, 0.1mmol), tris (dibenzylideneacetone) dipalladium (1.4mg, 0.0015mmol), tris (o-methylphenyl) phosphorus (3.7mg, 0.012mmol), dried toluene (4 mL), and reacted at 110 ℃ for 24h under argon atmosphere. Cooling the reaction solution to room temperature, dropwise adding the reaction solution into a methanol solution, filtering the solution by using a Buchner funnel, placing the solid on the filter paper in a vacuum drying oven to be dried at 70 ℃, using a Soxhlet extractor to sequentially wash off small molecules and the catalyst by using acetone and n-hexane to obtain a polymer material crude product, and finally using chloroform to extract the polymer material to obtain the polymer material F1-1 (86 mg, yield 88%). The gel permeation chromatography analysis and the element analysis were performed on the polymer material F1-1, and the results were as follows: gel permeation chromatography (GPC, trichlorobenzene, polystyrene standard, 150 ℃ C.): m n =18kda,pdi =1.72. Elemental analysis: calcd for C,77.42; h,8.77; b,1.11; n,2.87; and S,9.84. The experimental value is C,77.43; h,8.79; and N,2.86.
And (3) performance testing:
the polymer material F1-1 prepared in example 41 of the present invention was subjected to photophysical property testing using an ultraviolet-visible-near infrared absorption spectrometer, and an ultraviolet-visible-near infrared absorption spectrum is shown in fig. 6, wherein the F1-1 exhibits strong absorption peaks at 1105nm and 1288nm in a film state, and absorption sidebands reach 1490nm, and strong absorption in the short wave infrared region from 1100nm to 1490nm can be achieved. An electrochemical workstation high-molecular material F1-1 is used for carrying out an electrochemical property test, and a cyclic voltammetry curve is shown in figure 11, wherein the LUMO energy level of the F1-1 is-3.98eV, the HOMO energy level is-5.30 eV, and the electrochemical band gap is 1.32eV, so that the material is a narrow-band-gap molecular material.
Examples 42 to 45: synthesis of Polymer materials F1-2 to F1-5
Polymer materials F1-2, F1-3, F1-4 and F1-5 were prepared in the same manner as in the polymer material F1-1 of example 41 except that the reaction substrates A1-M4 were replaced with A2-M4, B1-M2, B2-M2 and C1-M5, respectively. The synthetic results and material characterization data are listed in the table below.
Example 46: synthesis of Polymer material G1-1
The preparation method of the high polymer material comprises the following steps: A1-M1 (93.9 mg, 0.1mmol), 4-dodecyl-2,6-bis (trimethylstannyl) -4H-dithieno [3,2-b:2',3' -d ] was added to a 50mL round bottom flask]Pyrrole (67.3mg, 0.1mmol), tris (dibenzylideneacetone) dipalladium (1.4 mg, 0.0015mmol), tris (o-methylphenyl) phosphorus (3.7 mg, 0.012mmol), dried toluene (4 mL), and reaction at 110 ℃ for 24h under an argon atmosphere. Cooling the reaction solution to room temperature, dropwise adding the reaction solution into a methanol solution, filtering the solution by using a Buchner funnel, placing the solid on the filter paper in a vacuum drying oven to be dried at 70 ℃, using a Soxhlet extractor to sequentially wash off small molecules and the catalyst by using acetone and n-hexane to obtain a polymer material crude product, and finally extracting the polymer material by using chloroform to obtain the polymer material G1-1 (100 mg, yield 89%). The gel permeation chromatography analysis and the element analysis were performed on the polymer material G1-1, and the results were as follows: gel permeation chromatography (GPC, trichlorobenzene, polystyrene standard, 150 ℃ C.): m n =9kda, pdi =1.84. Elemental analysis: calcd for C,71.56; h,8.96; b,0.96; f,3.38; n,3.74; and S,11.40. Experimental value C,71.57; h,8.99; and N,3.71.
And (3) performance testing:
the polymer material G1-1 prepared in example 46 of the present invention was subjected to photophysical property testing using an ultraviolet-visible-near infrared absorption spectrometer, and an ultraviolet-visible-near infrared absorption spectrum is shown in fig. 7, wherein G1-1 exhibits a strong absorption peak at 1083nm in the film state, and an absorption sideband reaches 1470nm, and strong absorption in the short-wave infrared region from 1100nm to 1470nm was achieved.
Examples 47 to 50: synthesis of Polymer materials G1-2 to G1-5
Polymer materials G1-2, G1-3, G1-4 and G1-5 were prepared in the same manner as in Polymer material G1-1 of example 46 except that the reaction substrates A1-M1 were replaced with A2-M4, B1-M2, B2-M2 and C1-M5, respectively. The synthetic results and material characterization data are listed in the table below.
Example 51: synthesis of Polymer Material H1-1
The preparation method of the high polymer material comprises the following steps: A1-M4 (105.5 mg, 0.1mmol), 2,5-bis (2-butyloctyl) -3,6-bis (5- (trimethylstannyl) thiophen-2-yl) pyrrolo [3,4-c ] was charged to a 50mL round bottom flask]Pyrrole-1,4 (2H, 5H) -dione (96.3mg, 0.1mmol), tris (dibenzylideneacetone) dipalladium (1.4mg, 0.0015mmol), tris (o-methylphenyl) phosphonium (3.7mg, 0.012mmol), dried toluene (4 mL), and argon atmosphere at 110 ℃ for 24h. Cooling the reaction solution to room temperature, dropwise adding the reaction solution into a methanol solution, filtering the solution by using a Buchner funnel, placing the solid on the filter paper in a vacuum drying oven to be dried at 70 ℃, using a Soxhlet extractor to sequentially wash off small molecules and the catalyst by using acetone and n-hexane to obtain a polymer material crude product, and finally extracting the polymer material by using chloroform to obtain the polymer material H1-1 (135 mg, yield 88%). The gel permeation chromatography analysis and the element analysis are carried out on the high molecular material H1-1, and the results are as follows: gel permeation chromatography (GPC, trichlorobenzene, polystyrene standard, 150 ℃ C.): m n ＝8kDa，PDI＝1.77. Elemental analysis: calcd for C,76.14; h,9.02; b,0.71; n,3.66; o,2.09; and S,8.38. Experimental value C,76.17; h,9.07; and N,3.63.
Examples 52 to 55: synthesis of high molecular materials H1-2-H1-5
Polymer materials H1-2, H1-3, H1-4 and H1-5 were prepared in the same manner as in the polymer material H1-1 of example 51 except that the reaction substrates A1-M4 were replaced with A2-M4, B1-M2, B2-M2 and C1-M5, respectively. The synthetic results and material characterization data are listed in the table below.
Example 56: synthesis of Polymer Material J1-1
The preparation method of the high polymer material comprises the following steps: a50 mL round-bottom flask was charged with A1-M4 (70.7mg, 0.67mmol), 2,5-dibromothiophene (8.0mg, 0.33mmol), hexa-n-butylditin (58.0mg, 0.1mmol), tris (dibenzylideneacetone) dipalladium (1.4mg, 0.0015mmol), tris (o-methylphenyl) phosphorus (3.7mg, 0.012mmol), dried toluene (4 mL), and reacted at 110 ℃ for 24h under an argon atmosphere. Cooling the reaction solution to room temperature, dropwise adding the reaction solution into a methanol solution, filtering the solution by using a Buchner funnel, placing the solid on the filter paper in a vacuum drying oven to be dried at 70 ℃, using a Soxhlet extractor to sequentially wash off small molecules and the catalyst by using acetone and n-hexane, and finally extracting the high polymer material by using chloroform to obtain the high polymer material J1-1 (52 mg, yield 84%). The gel permeation chromatography analysis and the element analysis were performed on the polymer material J1-1, and the results were as follows: gel permeation chromatography (GPC, trichlorobenzene, polystyrene standard, 150 ℃ C.): m n =15kda, pdi =2.20. Elemental analysis: meterThe value is C,78.25; h,9.04; b,1.15; n,2.99; and S,8.56. The experimental value is C,78.26; h,9.07; and 2.97.
Examples 57 to 60: synthesis of Polymer materials J1-2 to J1-5
Polymer materials J1-2, J1-3, J1-4 and J1-5 were prepared in the same manner as in Polymer material J1-1 of example 56 except that the reaction substrates A1-M4 were replaced with A2-M4, B1-M2, B2-M2 and C1-M5, respectively. The synthetic results and material characterization data are listed in the table below.
Example 61: preparation of binary blend film of A1-4 and PMMA
0.89mg of A1-4 was blended with 0.59g of optical grade PMMA (Mitsubishi VH001, japan) and stirred in 10mL of chloroform at room temperature for 5h to ensure complete dissolution. Adding a 2.9cm × 4.9cm clean soda-lime glass sheet into a 3cm × 5cm polytetrafluoroethylene mold, adding the prepared chloroform solution into the mold, volatilizing at room temperature to form a film, shaping, and drying in a 70 ℃ oven to obtain a film with a thickness of 240 μm.
And (3) performance testing:
the ultraviolet-visible-near infrared absorption spectrometer is used for testing the photophysical properties of the A1-4/PMMA binary blend film prepared in the embodiment 61 of the invention, the ultraviolet-visible-near infrared transmission spectrum is shown in FIG. 12, the average transmittance of the A1-4/PMMA binary blend film in the 1100nm-1400nm region is only 10%, and the average transmittance in the visible light region is 32%, so that the selective absorption of short-wave infrared light can be realized to a certain extent. A photograph of the flexible high polymer film is shown in FIG. 13, and the A1-4/PMMA binary blend film still has certain transparency under the low short-wave infrared light transmittance.
In conclusion, the five-membered aromatic heterocycle fused BODIPY-based polymer material provided by the invention has short-wave infrared absorption property, and the absorption spectrum can be expanded to 1600nm; the synthesis is simple, and the mass preparation is easy; and has high molar absorption coefficient and good photo-thermal stability. The binary blend film prepared by blending the PMMA and the film-spreading method has strong short-wave infrared absorption of 900-1600nm and certain transparency in a visible light region. The properties show that the polymer material has great potential in the fields of infrared camouflage, photo-thermal treatment, photoelectric detection and the like.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications derived therefrom are intended to be within the scope of the invention.
Claims (10)
1. A high polymer material based on five-membered aromatic heterocycle fused BODIPY is characterized by being composed of at least 1 monomer A or at least 1 monomer A and at least 1 monomer B independently, and the structural general formula is as follows:
in the formula I, n is an integer of 3-200, and m is an integer of 0-200;
when m is not 0, the proportional relationship of n, m is 10;
when m is 0, the proportional relation of n and m is n: m =1:0;
monomer A is a repeating unit represented by formula II below:
in formula II, X is a nitrogen atom or a carbon atom attached to an R group, R is one of the following structures:
y is oxygen atom, sulfur atom or selenium atom;
R a1 ，R a2 each independently one of the following structures:
R b1 ，R b2 each independently is one of the following structures:
R c1 ，R c2 each independently one of the following structures:
R、R a1 、R a2 、R b1 、R b2 、R c1 、R c2 in, R d Each independently is hydrogen, alkyl, arylalkyl, heteroalkyl, or aryl with or without a substituent attached;
the monomer B is one of the repeating units represented by the following formulas III-V:
wherein Ar is 1 、Ar 2 Each independently is C 2-23 Unsaturated aromatic ring of (A) or (C) 2-23 Of unsaturated aromatic heterocycles of (a), wherein C 2-23 The unsaturated aromatic heterocycle at least comprises a heteroatom, and the heteroatom at least comprises one of nitrogen, oxygen, sulfur and selenium;
X 1 、X 2 、X 3 each independently one of the following structures:
wherein k is an integer of 1 to 12; r is e Hydrogen, alkyl, arylalkyl, heteroalkyl, or aryl with or without substituents attached.
2. The polymeric material according to claim 1, wherein the ratio of n, m is 4.
3. A polymeric material according to claim 1, wherein when a plurality of monomers a are present in the polymeric material, there are less than 4 different monomer a structures; when a plurality of monomers B exist in the high polymer material, the number of different monomer B structures is less than 6;
x is one of the following structures:
R a1 ，R a2 each independently is one of the following structures:
wherein b is an integer of 1 to 12, and e and f are integers of 0 to 16, respectively;
R b1 ，R b2 each independently is one of the following structures:
wherein b is an integer of 1 to 17, x is an integer of 1 to 12, and y and z are integers of 0 to 16, respectively;
R c1 ，R c2 each independently is one of the following structures:
wherein a is an integer of 1 to 17, and q and d are each an integer of 0 to 16.
4. A polymeric material according to claim 1, wherein Ar is Ar 1 、Ar 2 Each independently is one of the following structures:
wherein h is an integer of 1 to 17, and i and g are each an integer of 0 to 16.
5. A polymeric material according to claim 1, wherein X is 1 、X 2 、X 3 Each independently is one of the following structures:
6. the polymer material according to claim 1, wherein the polymer material is selected from any one of structures represented by formula A1-1 to formula J-5:
7. a method for preparing the five-membered aromatic heterocycle fused BODIPY-based polymer material according to claim 1, comprising the steps of:
when m =1:0, the unit A substituted by alpha-bromine and the distannum salt are used as polymerization monomers;
when m =1:1, the unit A substituted by alpha-bromine and the unit B of the distannum salt are used as polymerization monomers;
n, m is 10 >; the monomer is subjected to Stille polymerization reaction to obtain a polymer material which has an absorption wavelength reaching a short wave infrared region and is based on five-membered aromatic heterocyclic fused BODIPY;
the structural formula of the alpha-bromine substituted unit A is shown as a formula VI, the structural formula of the bisstannate is shown as a formula VII, the structural formula of the unit B of the bisstannate is shown as a formula VIII, and the structural formula of the bromine substituted unit B is shown as a formula IX;
in the formula VII, R 4 Is methyl, ethyl or n-butyl;
in the formula VIII, R 5 Is methyl, ethyl or n-butyl.
8. The method of claim 7, comprising the steps of:
under the protection of argon or nitrogen, dissolving a polymerization monomer in an organic solvent, adding a catalyst, and carrying out Stille polymerization reaction under the conditions of light shielding and heating to obtain the polymer material based on the five-membered aromatic heterocycle fused BODIPY with the absorption wavelength reaching a short-wave infrared region.
9. The method according to claim 8, wherein the organic solvent is toluene, chlorobenzene or o-dichlorobenzene, the catalyst is tris (dibenzylideneacetone) dipalladium, and the ligand is tris (o-methylphenyl) phosphine;
m =1:0, the ratio of the amounts of material of α -bromo substituted unit a, the bistin salt, tris (dibenzylideneacetone) dipalladium, tris (o-methylphenyl) phosphine is 1:1: (0.01-0.05): (0.04-0.2);
m =1:1, the ratio of the amounts of substances of α -bromo-substituted unit a, unit B of the bistin salt, tris (dibenzylideneacetone) dipalladium, tris (o-methylphenyl) phosphine is 1:1: (0.01-0.05): (0.04-0.2);
n, m is 10 > < n > m > < 1> and n: m ≠ 1:1, the ratio of the amounts of α -bromo-substituted unit A, bromo-substituted unit B, the bisttannate, tris (dibenzylideneacetone) dipalladium, tris (o-methylphenyl) phosphine species is n: m: n + m: (0.01-0.05) × (n + m) < 0.04-0.2) × (n + m).
10. The method according to claim 8, wherein the Stille polymerization reaction temperature is 90-150 ℃ and the polymerization reaction time is 1-72 h.
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