CN117551077A - Preparation of carbazolyl 3, 5-dicyanopyridine derivative, room temperature phosphorescence and anti-counterfeiting performance - Google Patents

Preparation of carbazolyl 3, 5-dicyanopyridine derivative, room temperature phosphorescence and anti-counterfeiting performance Download PDF

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CN117551077A
CN117551077A CN202311400944.3A CN202311400944A CN117551077A CN 117551077 A CN117551077 A CN 117551077A CN 202311400944 A CN202311400944 A CN 202311400944A CN 117551077 A CN117551077 A CN 117551077A
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carbazolyl
dicyanopyridine
synthesizing
room temperature
solvent
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王永涛
郭健美
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Guilin University of Technology
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Guilin University of Technology
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/10—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a carbon chain containing aromatic rings
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    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom

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  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Plural Heterocyclic Compounds (AREA)

Abstract

The invention discloses preparation of carbazolyl 3, 5-dicyanopyridine derivatives, room temperature phosphorescence and anti-counterfeiting performance thereof. The preparation method comprises the following steps: adding o/m/p-carbazolyl benzaldehyde and malononitrile into a reaction bottle, taking sodium hydroxide as a catalyst and absolute methanol as a solvent, stirring the mixture at room temperature for reaction, and separating and purifying a reaction crude product to obtain the o/m/p-carbazolyl 3, 5-dicyanopyridine. And (3) obtaining three compound crystals by using methylene dichloride-petroleum ether as a solvent through a solvent diffusion method to obtain the crystalline room temperature phosphorescent material. The above crystals were mixed with urea/triphenylphosphine in an amount of 1:100, and heating to melt after grinding and mixing uniformly to obtain host-guest doped phosphorescent material, and applying the novel material to the field of anti-counterfeiting patterns.

Description

Preparation of carbazolyl 3, 5-dicyanopyridine derivative, room temperature phosphorescence and anti-counterfeiting performance
Technical Field
The invention belongs to the field of organic functional materials, and particularly relates to a preparation method of a carbazolyl 3, 5-dicyanopyridine derivative and a room-temperature phosphorescence performance optimization method.
Background
The ultra-long organic room temperature phosphorescence (UORTP) material has low price, good biocompatibility and low toxicity, and has wide application prospect in the high-tech fields such as data storage, biological imaging, sensors, anti-counterfeiting and the like. In general, the construction of phosphors mainly involves two aspects: promote intersystem transitions and inhibit non-radiative decay of triplet excitons. The former relies on the reduction of singlet states (S) by the introduction of carbonyl groups, heteroatoms and heavy atoms 1 ) And triplet (T) 1 ) Band gap (DeltaE) ST ) The latter generally depends on crystal engineering and host-guest doping. Thus, many twistsDonor-acceptor (D-A or D-A-D/A-D-A) luminophores of (E) have a small delta E ST But exhibits excellent Room Temperature Phosphorescence (RTP) properties. Among them, carbazole, triphenylamine, phenothiazine, and the like are often used as electron donors, which are conjugated with electron acceptors such as benzoic acid, benzaldehyde, and cyanobenzene through nitrogen atoms to form a distorted D-a molecular configuration. However, 3, 5-Dicyanopyridine (DCP) units rarely act as electron acceptors for D-A phosphorescent materials. In addition, the DCP unit not only contains a plurality of electron withdrawing and electron donating groups such as cyano, pyridine units, methoxy and amino, but also is expected to generate cluster phosphorescence through space conjugation of functional groups besides generating intrinsic phosphorescence, and the DCP has the characteristics of simple preparation, high yield and mild reaction conditions.
In addition to inhibiting the non-radiative decay of triplet excitons, crystal engineering plays a critical role in exploring the intrinsic mechanism of RTP. The crystals have an ordered molecular arrangement and stacking form, and the exact molecular conformation and stacking mode can be easily obtained by single crystal X-ray diffraction. The combination of crystal analysis and theoretical calculations can reveal key parameters of photophysical properties, thus obtaining key factors affecting RTP performance. Isomers have the same molecular formula but different molecular configurations, as well as intermolecular arrangements and stacking modes, generally result in high-contrast optical properties. Thus, a series of isomers with excellent crystallinity contributes to the building of structure-function relationships, revealing the intrinsic mechanism behind RTP deeply. In addition, the disadvantages of poor repeatability of the crystal and severe growth conditions greatly limit the application thereof. The exploration of amorphous RTP systems has therefore become a hotspot in the current research of pure organic room temperature phosphorescent materials. Particularly, low-melting-point small molecules are selected as main materials, organic phosphorescent small molecules are doped into the main materials, and the RTP performance of the organic phosphorescent small molecules can be improved by providing a rigid environment, so that the organic phosphorescent small molecules have the advantages of flexibility, easiness in processing and the like, and are convenient for application of various technologies.
Disclosure of Invention
The invention aims to deeply discuss and excavate the structure-performance relation of the pure organic room temperature phosphorescent material, obtain the room temperature phosphorescent material with long service life and time dependence, and strengthen the imitation difficulty of the anti-counterfeiting material.
The invention adopts the following ideas: sodium hydroxide is added into a reaction bottle as a catalyst, absolute methanol is used as a solvent, carbazolyl benzaldehyde and malononitrile are stirred to react completely under the condition of room temperature under the catalysis of sodium hydroxide, and the crude reaction product is separated and purified to obtain the carbazolyl 3, 5-dicyanopyridine derivative. The method comprises the steps of obtaining three compound crystals by using methylene dichloride-n-hexane as a solvent through a solvent diffusion method, doping a host and a guest, designing and drawing patterns, and constructing an advanced anti-counterfeiting pattern by means of different fluorescence and phosphorescence emission.
The aim of the invention is achieved by the following technical scheme.
A synthesis method of carbazolyl 3, 5-dicyanopyridine derivatives comprises the following preparation processes:
adding carbazolyl benzaldehyde, malononitrile, sodium hydroxide and a solvent into a reaction vessel in an atmospheric environment, stirring at room temperature for reacting for 2 hours, and separating and purifying a crude product by column chromatography to obtain the carbazolyl 3, 5-dicyanopyridine derivative.
Further, the formula of the preparation equation of the carbazolyl 3, 5-dicyanopyridine derivative is shown as follows:
in the preparation method, the molar ratio of carbazolyl benzaldehyde to malononitrile to sodium hydroxide is 1:2:1.2.
In the preparation method, the organic solvent is anhydrous methanol, and the volume ratio is 10:1.
the principle of the invention is as follows: 3, 5-dicyanopyridine is selected as electron withdrawing group, carbazole is selected as electron donating group, a distorted donor (D) -pi-acceptor (A) molecular configuration is constructed through benzene connection, and the energy gap and spin orbit coupling constant between the lowest singlet state and triplet state are regulated through different substitution positions. The distorted molecular conformation helps to reduce the energy gap between the lowest singlet and triplet states, thereby helping to accelerate triplet exciton formation. Meanwhile, urea and triphenylphosphine have low melting points and good crystallization performance, and non-radiative transition of triplet excitons of a luminophor can be reduced by host-guest doping, so that the room-temperature phosphorescence performance is enhanced. The fusion dispersion of the luminophor, urea and triphenylphosphine can simultaneously form the single-molecule dispersion and aggregate dispersion of the luminophor, and hetero atoms on the 3, 5-dicyanopyridine units in the luminophor can form spatial interaction with amino groups and carbonyl groups of urea molecules, so that a cluster triplet state luminescence center is further generated. The single molecule, aggregate and cluster luminescence center have different phosphorescence lifetimes, thereby generating time-dependent room temperature phosphorescence and enhancing the application value in the fields of anti-counterfeiting and encryption.
Compared with the prior art, the invention has the following advantages:
(1) In different doped matrixes of urea and triphenylphosphine, the invention realizes that the same compound emits different fluorescence and phosphorescence, simultaneously forms binary phosphorescence emission of single molecules and aggregates, forms ternary phosphorescence emission of single molecules, aggregates and clusters in the urea matrix, has different room temperature phosphorescence lifetimes, and therefore presents time dependent phosphorescence emission. At present, the generation of ternary phosphorescence emission by host-guest doping is rarely reported, which is helpful to enhance the imitation difficulty of anti-counterfeiting materials;
(2) The invention synthesizes three isomers, only ortho isomer doped in urea matrix can generate visible afterglow under the excitation of 380 nm and 400 nm, and the afterglow under the excitation of 400 nm is as long as 0.5 s. Thus, in addition to time-dependent room temperature phosphorescence, a higher level of encryption can be achieved with different excitation wavelengths.
Drawings
FIGS. 1, 2 and 3 show the hydrogen spectrum, carbon spectrum and mass spectrum of the target product o-CzAD obtained in example 1;
FIGS. 4, 5 and 6 show the hydrogen spectrum, carbon spectrum and mass spectrum of the target product m-CzAD obtained in example 1;
FIGS. 7, 8 and 9 show the hydrogen spectrum, carbon spectrum and mass spectrum of the target product p-CzAD obtained in example 1;
FIG. 10 is fluorescence and room temperature phosphorescence spectra of three crystals of the target product obtained in example 1;
FIG. 11 phosphorescence spectra of Urea/o-CzAD at different delay times;
FIG. 12 phosphorescence spectra of Urea/p-CzAD at different delay times;
FIG. 13 PPh 3 Phosphorescence spectra of/o-CzAD at different delay times;
FIG. 14 PPh 3 Phosphorescence spectra of/p-CzAD at different delay times;
FIG. 15 afterglow pictures of four doping systems
FIG. 16 is a drawing of an abstract showing an anti-counterfeit encryption pattern
Detailed Description
The invention is further described by way of specific examples, but the scope and embodiments of the invention are not limited thereto.
Example 1
In a two-necked flask, o/m/p carbazolyl benzaldehyde (1 g,3.7 mmol), malononitrile (0.49 g,7.4 mmol), sodium hydroxide (0.18 g,4.4 mmol) and anhydrous methanol (20 mL) were charged, and the reaction was stirred at room temperature for 2 hours, and the mixture was transferred to water and extracted with ethyl acetate (30×3 mL). The organic phases are then combined and combined with anhydrous Na 2 SO 4 And (5) drying. The solvent was removed by rotary evaporator under reduced pressure using petroleum ether/ethyl acetate (3:1, v/v) as eluent and the product was purified by column chromatography to give 0.92 g as a yellow solid. Yield: 60%.
By a solvent diffusion method, a saturated Dichloromethane (DCM) solution of the carbazolyl 3, 5-dicyanopyridine derivative is slowly diffused into n-hexane, and crystals of three compounds are successfully cultured.
Adding 0.1 g o/p-carbazolyl 3, 5-dicyanopyridine (o-CzAD/p-CzAD) into 10 g triphenylphosphine/urea, grinding and dispersing by a glass rod, and heating to the melting temperature of the triphenylphosphine/urea to obtain urea/o-CzAD, urea/p-CzAD, PPh 3 /o-CzAD, PPh 3 a/p-CzAD host-guest doping system.
Soaking two pieces of filter paper in molten urea and PPh respectively 3 In (C)The o-CzAD and p-CzAD were then dissolved in ethyl acetate, respectively, and used as inks. By using the same template and treated filter paper, a series of maple leaves were drawn, which were cut and arranged in the proper order. In sunlight, only white maple leaves can be seen due to the main absorption bands of the host and the object below 400 nm, but they show deep blue or light blue fluorescence under the irradiation of ultraviolet rays of 365 nm. When the ultraviolet lamp is turned off, three different afterglow colors can be observed, including orange, deep blue, and yellow, which are used to represent "horizontal", "dot", and "blank", respectively. Thus, correct information is not available under both sunlight and ultraviolet light. Taking the first line as an example, when the ultraviolet lamp is turned off, we can obtain "horizontal", "spot", "horizontal" and "spot" information as correct reading information. Comparing the correct information with the international code table, the first row may be interpreted as the letter "C". The remaining four rows are decrypted sequentially as "H", "I", "N" and "a" using the same strategy. Finally, the complete encrypted information is decrypted to "CHINA".
The structural characterization data of the obtained target product o-CzAD are shown as follows:
1 H NMR (500 MHz, d 6 -DMSO) δ/ppm = 8.15 (d, J = 5 Hz, 2H), 7.84~7.77 (m, 4H), 7.63 (d, J = 5 Hz, 1H), 7.34~7.23 (m, 7H), 3.77 (s, 3H); 13 C NMR (500 MHz, d 6 -DMSO) δ/ppm =165.63, 161.02, 158.79, 141.09, 141.08, 135.71, 133.82, 132.72, 131.70, 130.17, 129.67, 126.01, 123.35, 120.77, 115.73, 115.33, 111.27, 111.18, 84.45, 84.34, 55.11; HRMS (MALDI-TOF): m/z 416.1506 [[M +H] + , calculated 416.1504].
the structural characterization data of the obtained target product m-CzAD are shown as follows:
1 H NMR (500 MHz, d 6 -DMSO) δ/ppm = 8.23 (d, J = 5 Hz, 2H), 7.81 (d, J = 15 Hz, 4H), 7.64 (d, J = 5 Hz, 1H), 7.56 (d, J = 5 Hz, 2H), 7.40 (t, J = 15 Hz, 2H), 7.29 (t, J = 5 Hz, 2H), 3.96 (s, 3H); 13 C NMR (500 MHz, d 6 -DMSO) δ/ppm = 166.20, 161.63, 159.90, 140.39, 137.64, 131.16, 127.02, 126.80, 13.39, 121.05, 120.86, 110.25, 83.89, 55.28; HRMS (MALDI-TOF): m/z 416.1506 [[M +H] + , calculated 416.1512].
the structural characterization data of the obtained target product p-CzAD are shown as follows:
1 H NMR (500 MHz, d 6 -DMSO) δ/ppm = 8.27 (d, J = 5 Hz, 2H), 7.87~7.83 (m, 5H), 7.49~7.44 (m, 5H), 7.32 (t, J = 10 Hz, 2H), 4.00 (s, 3H); 13 C NMR (500 MHz, d 6 -DMSO) δ/ppm =166.33, 161.75, 160.39, 140.23, 139.08, 133.34, 130.96, 127.03, 126.93, 123.50, 121.14, 120.95, 116.01, 110.08, 83.95, 83.75, 55.29; HRMS (MALDI-TOF): m/z 416.1506 [[M +H] + , calculated 416.1507].
the structure of the target compound was deduced from the above characterization data as follows:

Claims (9)

1. a synthesis method of carbazolyl 3, 5-dicyanopyridine derivatives is characterized by comprising the following steps:
adding o/m/p-carbazolyl benzaldehyde and malononitrile into a reaction bottle, taking sodium hydroxide as a catalyst and absolute methanol as a solvent, stirring the mixture at room temperature for reaction, and separating and purifying a reaction crude product to obtain o/m/p-carbazolyl 3, 5-dicyanopyridine; the method comprises the steps of obtaining three compound crystals by using methylene dichloride-n-hexane as a solvent through a solvent diffusion method; according to the following steps of 1:100 weight ratio, mixing the crystal with urea/triphenylphosphine, grinding and mixing uniformly, and heating to melt to obtain a host-guest doped long-life phosphorescent material; soaking two pieces of filter paper in molten urea and PPh respectively 3 Then o-CzAD and p-CzAD were dissolved in ethyl acetate, respectively, to be used as inks; by using the same template and treated filter paper, a series of maple leaves are depicted, which are cut and arranged in the proper order to obtain an encrypted pattern;
the carbazolyl 3, 5-dicyano groupThe pyridine derivative has the structural general formula of。
2. The method for synthesizing the carbazolyl 3, 5-dicyanopyridine derivative according to claim 1, wherein the feeding molar ratio of carbazolyl benzaldehyde to sodium hydroxide catalyst is 1:1.2.
3. The method for synthesizing a carbazolyl 3, 5-dicyanopyridine derivative according to claim 1, wherein the feeding molar ratio of carbazolyl benzaldehyde to malononitrile is 1:2.
4. The method for synthesizing a carbazolyl 3, 5-dicyanopyridine derivative according to claim 1, wherein the solvent is anhydrous methanol in a volume ratio of 10:1.
5. The method for synthesizing a carbazolyl 3, 5-dicyanopyridine derivative according to claim 1, wherein the reaction time of the preparation method is 2 hours.
6. The method for synthesizing a carbazolyl 3, 5-dicyanopyridine derivative according to claim 1, wherein the reaction temperature of the preparation method is room temperature.
7. The method for synthesizing carbazolyl 3, 5-dicyanopyridine derivatives according to claim 1, wherein the crude product is separated by column chromatography using ethyl acetate and petroleum ether as eluent.
8. The method for synthesizing a carbazolyl 3, 5-dicyanopyridine derivative according to claim 1, wherein the mixed solvent of the cultured crystals is methylene chloride-n-hexane.
9. The method for synthesizing carbazolyl 3, 5-dicyanopyridine derivatives according to claim 1, wherein the method for constructing host-guest doping system of carbazolyl 3, 5-dicyanopyridine derivatives, urea and triphenylphosphine is characterized in that the doping weight ratio of carbazolyl 3, 5-dicyanopyridine derivatives to urea/triphenylphosphine is 1:100, the melting temperature is 90-140 ℃.
CN202311400944.3A 2023-10-26 2023-10-26 Preparation of carbazolyl 3, 5-dicyanopyridine derivative, room temperature phosphorescence and anti-counterfeiting performance Pending CN117551077A (en)

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