CN114805215B - Fluorescent sensing material, preparation method thereof and application of fluorescent sensing material in aspect of detecting nerve agent with high sensitivity - Google Patents

Fluorescent sensing material, preparation method thereof and application of fluorescent sensing material in aspect of detecting nerve agent with high sensitivity Download PDF

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CN114805215B
CN114805215B CN202110112273.5A CN202110112273A CN114805215B CN 114805215 B CN114805215 B CN 114805215B CN 202110112273 A CN202110112273 A CN 202110112273A CN 114805215 B CN114805215 B CN 114805215B
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nerve agent
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CN114805215A (en
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车延科
邱长坤
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Institute of Chemistry CAS
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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
    • C07D401/14—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 three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D235/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings
    • C07D235/02—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings condensed with carbocyclic rings or ring systems
    • C07D235/04—Benzimidazoles; Hydrogenated benzimidazoles
    • C07D235/06—Benzimidazoles; Hydrogenated benzimidazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached in position 2
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    • 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
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/64—Fluorescence; Phosphorescence
    • G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
    • G01N21/643—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" non-biological material
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • 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
    • 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
    • C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/64—Fluorescence; Phosphorescence
    • G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
    • G01N2021/6432—Quenching

Abstract

The application provides a compound shown in a formula (I) based on two functional units (benzimidazole and end capping groups), fluorescent molecules in fluorescent materials prepared by the compound enhance the formation of charge transfer Complexes (CT) through synergistic effect so as to enhance the sensitivity of detecting nerve agents. The mechanism of the synergistic action is that the benzimidazole group can perform hydrogen bonding with the nerve agent to cause the cleavage of P-X (X=Cl, CN, F), and the cleaved product can more easily react with the end capping group to form a charge transfer complex, so that a ratio fluorescence change signal is generated. The concentration of the detected nerve agent vapor is ppb-ppm, and the nerve agent vapor has no obvious response to common interference gases such as organic solvents and the like. The fluorescent material has the advantages of strong stability, high fluorescence quantum yield and wide application prospect.

Description

Fluorescent sensing material, preparation method thereof and application of fluorescent sensing material in aspect of detecting nerve agent with high sensitivity
Technical Field
The application belongs to the field of organic fluorescent sensing materials, and particularly relates to a preparation method of a fluorescent sensing material and application of the fluorescent sensing material in the aspect of detecting nerve agents with high sensitivity.
Background
Neurotoxic agents are a highly toxic, highly effective, contagious lethal agent, non-irritating, including G-type neurotoxic agents (sarin, isopropyl methylphosphonate), soman and tagon, and V-type neurotoxic agents (such as vex (VX, S- (2-diisopropylaminoethyl) -methyl thiophosphonate ethyl)) which are highly toxic organic phosphates capable of irreversibly inhibiting acetylcholinesterase in the nerve synapse to interfere with nerve impulse delivery, and in severe cases, causing respiratory muscle paralysis to cause death. Once dispersed in the environment, neurotoxic agents, particularly VX and the like, which are not easily volatilized, have extremely high toxicity, which can be kept for several hours to several weeks, and form a great threat to life and environmental safety. There is therefore an urgent need to develop a portable detection technique that is fast, efficient, highly sensitive, highly selective and suitable for use in the field.
Techniques based on various instruments and chemical detection have been developed such as gas chromatography, liquid chromatography (GC-MS, LC-MS), surface acoustic wave methods, chemical ionization mass spectrometry, ion mobility spectrometry, surface enhanced raman spectroscopy, nuclear fourth order resonance spectroscopy, electrochemical methods, chromogenic methods, and the like. The international military field develops and applies the detection technology, and the detection technology comprises chemical detection papers M8 and M9 which display different colors for distinguishing detection after being contacted with different toxic agents, a detection package M256A 1 of the chromogenic chemical agent, a surface acoustic wave micro chemical agent detector SWA MINICAD MK II, a Drager Multi-IMS ion migration spectrum detector and the like. However, these detection techniques have one or more drawbacks during the detection process, including high cost, long operation time, and complex operation. Compared with the method, the fluorescence detection method has the characteristics of simplicity, rapidness, portability, high sensitivity and high selectivity, and has been widely applied to detection of chemical warfare agents. Diethyl Chlorophosphate (DCP) is commonly used as a G-series nerve agent mimetic agent to evaluate their performance. However, the performance of a fluorescent sensor using DCP may be biased due to the large difference between DCP and sarin (e.g., DCP is more electrophilic). In contrast, diethyl Cyanophosphate (DCNP) is more suitable for use in mimics of the G-series nerve agents. In addition, acid impurities that may be generated in the mimetic may lead to similar fluorescent responses, resulting in false positive signals. Thus, developing fluorescence sensors with high sensitivity and selectivity (especially for acids) to sarin and soman remains challenging.
We have designed fluorescent molecules with two molecular recognition functional units (benzimidazole and end capping groups such as pyridine, cyano, alkoxy). The two molecular recognition units may enhance Charge Transfer (CT) formation by synergy to enhance detection sensitivity, as compared to nucleophilic interactions between the neurotoxic agent molecule and the capping group alone. The mechanism of this synergy is presumed to be that the benzimidazole group can undergo hydrogen bonding with the nerve agent to cause cleavage of P-X (x=cl, CN, F), and the cleaved product more readily reacts with pyridine or cyano, alkoxy groups to form a charge transfer complex, thereby generating a ratiofluorescence change signal. Importantly, the ratiometric fluorescence response is different from the parallel response of the various interferences, thus providing selectivity for the interferences. In addition, the benzimidazole unit with stronger alkalinity in the target molecule can capture acid preferentially, so that the sensitivity of the benzimidazole unit to acid is greatly reduced. Thus, the novel fluorescent molecules having two synergistic molecular recognition units allow for a greatly improved sensitivity and selectivity for detection of sarin and soman.
Disclosure of Invention
The application provides a compound shown as the following formula (I):
wherein each R 1 、R 2 The same or different, independently of one another, from hydrogen, C 1-40 Alkyl, C 1-40 Alkyloxy, C 2-40 Alkenyl, C 2-40 Alkenyloxy, C 6-20 Aryl, C 6-20 Aryloxy, 5-20 membered heteroaryl, 5-20 membered heteroaryloxy, C 3-20 Cycloalkyl, C 3-20 Cycloalkyloxy, 3-20 membered heterocyclyl, C 3-40 Heterocyclyloxy; r is R 3 、R 4 Identical or different, independently of one another, from cyano, C which is unsubstituted or substituted by 1,2 or more Ra 1-40 Alkyl, C 6-20 Aryl, 5-20 membered heteroaryl, C 1-40 Alkoxy, C 6-20 Aryl C 1-40 Alkyl, 5-20 membered heteroarylalkyl, C 1-40 Alkoxy C 1-40 An alkyl group; a. b are identical or different and are each independently selected from the group consisting of numbers 1 to 10;
each Ra, which are identical or different, are independently selected from CN, C 1-40 Alkyl, C 1-40 Alkoxy, C 6-20 Aryl, 5-20 membered heteroaryl.
According to an embodiment of the application, each R 1 、R 2 The same or different, independently of one another, from hydrogen, C 1-12 An alkyl group; r is R 3 、R 4 Identical or different, independently of one another, from cyano, C which is unsubstituted or substituted by 1,2 or more Ra 1-12 Alkyl, C 6-14 Aryl, 5-14 membered heteroaryl, C 1-12 Alkoxy, C 6-14 Aryl C 1-12 Alkyl, 5-14 membered heteroarylalkyl, C 1-12 Alkoxy C 1-12 An alkyl group; a. b are identical or different and are each independently selected from the group consisting of 1 to 6;
each Ra, which are identical or different, are independently selected from CN, C 1-12 Alkyl, C 1-12 Alkoxy, C 6-14 Aryl, 5-14 membered heteroaryl.
According to an embodiment of the application, each R 1 、R 2 The same or different, independently of one another, from hydrogen, C 1-12 An alkyl group; r is R 3 、R 4 The same or different, independently of one another, are selected from cyano, cyanophenyl, pyridinyl, cyanophenyl C 1-6 Alkyl, pyridyl C 1-6 Alkyl, methoxy C 1-6 An alkyl group; a. b are identical or different and are each independently selected from the group consisting of 1 to 3.
According to an embodiment of the application, each R 1 、R 2 The same or different, independently of one another, are selected from the following groups:
according to an embodiment of the application, R 3 、R 4 The same or different, independently of one another, are selected from the following groups: CN,
Wherein, the marked end is the group connecting point.
According to an embodiment of the application, R 1 、R 2 Is hexyl, R 3 、R 4 Cyano or pyridinyl, a=b=1.
The application also provides a preparation method of the compound shown in the formula (I), which comprises the following steps:
(I-1): compound 1 was combined with a bisboronic acid pinacol ester (i.e., 4', 5',5' -octamethyl-2, 2-bi-1, 3, 2-dioxapentaborane) to obtain an intermediate 2;
reacting the product intermediate 2 of the step (I-1) with 2, 7-dibromo-9, 9-dialkylfluorene to obtain an intermediate 3;
reacting the product intermediate 3 of the step (I-2) with pinacol biborate to obtain an intermediate 4;
optionally, repeating the conditions a-1 times in the step (I-2) and the step (I-3) by taking the product intermediate 4 of the step (I-3) as a substrate to obtain an intermediate 5a;
(I-5) optionally, R in steps (I-1) - (I-4) 1 、R 3 And a, respectively substituted by R 2 、R 4 And b, sequentially obtaining an intermediate 5b according to the same reaction conditions in the steps (I-1) - (I-4);
(I-6) when a and b are the same, R 1 And R is 3 Identical, R 2 And R is 4 In the same time, the compound 4, 7-dibromobenzimidazole reacts with an intermediate 5a to obtain the compound of the formula (I);
when a and b, R 1 And R is 3 、R 2 And R is 4 At least one group of compounds different from each other, the compound dibromobenzimidazole is reacted with an intermediate 5a and then reacted with an intermediate 5b to obtain the compound of the formula (I).
According to an embodiment of the present application, in the step (I-1), the reaction may be performed in a solvent, which may be an organic solvent, for example, an ether solvent such as 1, 4-dioxane, tetrahydrofuran;
according to an embodiment of the application, in step (I-1), the molar ratio of compound 1 to pinacol ester of diboronic acid is 1 (1-8), for example 1 (2-5);
according to an embodiment of the present application, in the step (I-1), the reaction is carried out in a catalyst system comprising a palladium catalyst and an alkali metal salt; the palladium catalyst may be [1,1' -bis (diphenylphosphino) ferrocene ] palladium dichloride; the alkali metal salt can be potassium acetate, sodium carbonate, potassium carbonate, cesium carbonate;
according to an embodiment of the present application, in the step (I-1), the molar ratio of the compound 1, the palladium catalyst and the alkali metal salt may be 1 (0.01 to 0.5): 1 to 10, for example, 1 (0.03 to 0.4): 2 to 8.
According to an embodiment of the present application, in the step (I-2), the reaction is carried out in a solvent, which may be an organic solvent, for example, an ether solvent such as 1, 4-dioxane, tetrahydrofuran;
according to an embodiment of the application, in said step (I-2), the molar ratio of intermediate 2 to 2, 7-dibromo-9, 9-dialkylfluorene is 1 (0.8-5), for example 1 (1-3).
According to an embodiment of the present application, in the step (I-2), the reaction is carried out in a catalyst system comprising a palladium catalyst and an alkali metal salt; the palladium catalyst may be tetrakis (triphenylphosphine) palladium; the alkali metal salt can be potassium acetate, sodium carbonate, potassium carbonate, cesium carbonate;
according to an embodiment of the present application, in the step (I-2), the molar ratio of the intermediate 2, the palladium catalyst and the alkali metal salt may be 1 (0.01 to 0.5): 1 to 10, for example, 1 (0.05 to 0.2): 2 to 5;
according to an embodiment of the present application, in the step (I-2), the reaction is performed under the protection of an inert gas, the reaction temperature is 70 to 90 ℃, and the reaction time is 6 to 12 hours.
According to an embodiment of the present application, in the step (I-3), the reaction is performed in a solvent, which may be an organic solvent, for example, an ether solvent such as 1, 4-dioxane, tetrahydrofuran;
according to an embodiment of the application, in step (I-3), the molar ratio of intermediate 3 to pinacol ester of biboronic acid is 1 (1-8), for example 1 (2-5);
according to an embodiment of the present application, in the step (I-3), the reaction is performed in a catalyst system comprising a palladium catalyst and an alkali metal salt; the palladium catalyst may be [1,1' -bis (diphenylphosphino) ferrocene ] palladium dichloride; the alkali metal salt can be potassium acetate, sodium carbonate, potassium carbonate, cesium carbonate;
according to an embodiment of the present application, in the step (I-3), the molar ratio of the intermediate 3, the palladium catalyst and the alkali metal salt may be 1 (0.01 to 0.5): 1 to 10, for example, 1 (0.03 to 0.4): 2 to 8.
According to an embodiment of the present application, in the step (I-6), the reaction is performed in a solvent, which may be a mixed solvent of an organic solvent, which may be an ether-type solvent such as 1, 4-dioxane, tetrahydrofuran, and water;
according to an embodiment of the present application, in the step (I-6), the reaction is performed in a catalyst system comprising a palladium catalyst and an alkali metal salt; the palladium catalyst may be tetrakis (triphenylphosphine) palladium; the alkali metal salt can be potassium acetate, sodium carbonate, potassium carbonate, cesium carbonate;
according to an embodiment of the present application, in the step (I-6), when a and b are the same, R 1 And R is 3 Identical, R 2 And R is 4 At the same time, the molar ratio of intermediate 5a to dibromobenzimidazole is 1 (1.5-5), e.g., 1 (2-3); when a and b, R 1 And R is 3 、R 2 And R is 4 At least one group of non-identical, the molar ratio of intermediate 5a, intermediate 5b to dibromobenzimidazole is 1 (0.5-1.2): 0.5-1.2, for example 1 (0.8-1): 0.8-1;
according to an embodiment of the present application, in the step (I-6), the molar ratio of the intermediate 5a, the palladium catalyst and the alkali metal salt may be 1 (0.01-0.5): 1-10, for example 1 (0.05-0.2): 2-5;
according to an embodiment of the present application, in the step (I-6), the reaction is performed under the protection of an inert gas, the reaction temperature is 70 to 90 ℃, and the reaction time is 6 to 12 hours.
The application also provides an organic fluorescent nano strip aggregate, which comprises a compound shown as a formula (I).
According to an embodiment of the present application, the elongated aggregate is an elongated aggregate assembled from small molecules composed of fluorene and benzimidazole.
According to an embodiment of the application, the length of the elongated aggregates is 30-50 μm, preferably 35-45 μm;
according to an embodiment of the application, the elongated aggregate has a fluorescence quantum yield of 5-40%, for example 10%, 15%, 20% or 25%.
The application also provides a preparation method of the organic fluorescent nano long-strip aggregate, which comprises the step of self-assembling the compound shown in the formula (I) between molecules to obtain the organic fluorescent nano long-strip aggregate.
According to the application, the intermolecular self-assembly is achieved by contacting the compound with a mixture of its good and bad solvents. Preferably, contacting the compound with a mixture of its good solvent and poor solvent comprises dissolving the compound in its good solvent, then adding its poor solvent, and standing.
According to an embodiment of the present application, the volume ratio of the good solvent to the poor solvent is 1:5 to 1:30, preferably 1:5 to 1:20, and more preferably 1:5 to 1:10.
According to an embodiment of the present application, the good solvent is selected from at least one of halogenated hydrocarbon solvents, such as chloroform, dichloromethane.
According to an embodiment of the present application, the poor solvent is selected from at least one of an alcohol solvent, a ketone solvent, or an alkane solvent, such as methanol, acetone, n-hexane.
The application also provides a fluorescent material which comprises the compound shown in the formula (I).
Preferably, the fluorescent material comprises the organic fluorescent nanoribbon-like aggregates.
The application also provides application of the fluorescent material, which is used for detecting the nerve agent.
According to embodiments of the present application, the neurotoxic agent may be selected from one or more of Diethyl Cyanophosphate (DCNP), sarin (GB), soman (GD), tartronic acid (GA).
The application also provides a method of detecting a chemical warfare agent comprising contacting the fluorescent material with a nerve agent.
According to embodiments of the present application, the concentration of the nerve agent to be detected may range from 0.1ppb to 500ppm, for example from 1ppb to 200ppm.
Advantageous effects
1) The application integrates two recognition units (benzimidazole and end-capping groups, such as pyridine, cyano and alkoxy) in one compound, and the aggregate or fluorescent material obtained by self-assembly realizes ultrahigh sensitivity (0.1 ppm) and selective fluorescence response to nerve agents through the synergistic effect of the two recognition units, wherein the fluorescence quantum yield of the material is 5-40%; meanwhile, the specific surface area is larger, the surface area contacted with the detection gas is increased, and the detection sensitivity is further improved.
2) The fluorescent material of the present application exhibits fluorescence quenching at 440nm and fluorescence enhancement at 520nm when contacted with nerve agents such as sarin and soman. The fluorescent material responds to other interferents or volatile organic compound agents in a manner that has the same trend of response (both quenched or both enhanced) at 440nm and 520nm, as opposed to being responsive to nerve agents. Thus, the fluorescent material of the present application has high specificity for detecting nerve agents.
Drawings
FIG. 1 shows a nuclear magnetic resonance spectrum of a compound A in example 1 of the present application.
FIG. 2 is a mass spectrum of Compound A in example 1 of the present application.
FIG. 3 in example 1 of the present application, compound A is prepared in chloroform: scanning electron microscope pictures of aggregates formed by self-assembly under methanol (1:10) conditions.
FIG. 4 is a graph showing the ultraviolet-visible absorption spectrum of Compound A in chloroform solution in example 1 of the present application.
Fig. 5 in example 1 of the present application, compound a was prepared in chloroform: fluorescence spectrum of aggregates formed by self-assembly under methanol (1:10) conditions.
FIG. 6. In example 3 of the present application, compound A is prepared in chloroform: aggregate formed by self-assembly under methanol (1:10) condition, fluorescence change time sequence diagram of different concentrations of sarin vapor (upper graph @440nm, lower graph @520 nm).
Fig. 7. In example 4 of the present application, compound a was prepared in chloroform: aggregate formed by self-assembly under methanol (1:10) condition, fluorescence change time sequence diagram of different concentrations of soman vapor (upper graph @440nm, lower graph @520 nm).
Fig. 8. In example 5 of the present application, compound a was prepared in chloroform: aggregate formed by self-assembly under methanol (1:10) condition, fluorescence change time sequence diagram (upper graph @440nm, lower graph @520 nm) of DCNP vapor with different concentrations.
Fig. 9. In example 6 of the present application, compound a was prepared in chloroform: aggregate formed by self-assembly under the condition of methanol (1:10), and fluorescence change time sequence diagram of different concentrations of methanol vapor (upper graph @440nm, lower graph @520 nm).
Fig. 10. In example 7 of the present application, compound a was prepared in chloroform: aggregate formed by self-assembly under methanol (1:10) condition, fluorescence change time sequence diagram of acetonitrile vapor with different concentrations (upper graph @440nm, lower graph @520 nm).
FIG. 11, in example 8 of the present application, compound A was prepared in chloroform: aggregate formed by self-assembly under methanol (1:10) condition, and fluorescence change time sequence diagram of acetone vapor with different concentrations (upper graph @440nm, lower graph @520 nm).
Fig. 12 in example 9 of the present application, compound a was prepared in chloroform: aggregate formed by self-assembly under methanol (1:10) condition, fluorescence change time sequence diagram of ethyl acetate vapor with different concentrations (upper graph @440nm, lower graph @520 nm).
FIG. 13, in example 10 of the present application, compound A was prepared in chloroform: aggregate formed by self-assembly under the condition of methanol (1:10), and fluorescence change time sequence diagram of tetrahydrofuran vapor with different concentrations (upper graph @440nm, lower graph @520 nm).
Fig. 14. In example 11 of the present application, compound a was prepared in chloroform: aggregate formed by self-assembly under the condition of methanol (1:10) and fluorescence change time sequence diagram of dimethyl sulfoxide vapor with different concentrations (upper graph @440nm, lower graph @520 nm).
FIG. 15 is a nuclear magnetic resonance spectrum of Compound B in example 2 of the present application.
FIG. 16 is a mass spectrum of Compound B in example 2 of the present application.
Fig. 17 in example 2 of the present application, compound B was prepared in chloroform: scanning electron microscope pictures of aggregates formed by self-assembly under methanol (1:10) conditions.
Fig. 18, in example 2 of the present application, compound B was prepared in chloroform: aggregate formed by self-assembly under methanol (1:10) condition, fluorescence change time sequence diagram (upper graph @440nm, lower graph @520 nm) of DCNP vapor with different concentrations.
Definition and description of terms
Unless otherwise indicated, the radical and term definitions recited in the specification and claims of the present application, including as examples, exemplary definitions, preferred definitions, definitions recited in tables, definitions of specific compounds in the examples, and the like, may be arbitrarily combined and coupled with each other. Such combinations and combinations of radical definitions and structures should be understood to be within the scope of the present description and/or claims.
The numerical ranges recited in the specification and claims are equivalent to at least each specific integer number recited therein unless otherwise stated. For example, a numerical range of "1-12" corresponds to the values recited for each integer, i.e., 1,2, 3,4, 5,6, 7, 8, 9, 10, 11, 12. Furthermore, when certain numerical ranges are defined as "numbers," it is to be understood that both endpoints of the range, each integer within the range, and each fraction within the range are delineated. For example, a "number of 0 to 10" should be understood to describe not only each integer of 0, 1,2, 3,4, 5,6, 7, 8, 9 and 10, but also at least the sum of each integer with 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, respectively.
It should be understood that in the description of 1,2 or more herein, "plurality" shall mean an integer greater than 2, such as greater than or equal to 3, such as 3,4, 5,6, 7, 8, 9 or 10.
The term "halogen" means fluorine, chlorine, bromine and iodine.
The term "C 1-40 Alkyl "is understood to mean preferably a straight-chain or branched saturated monovalent hydrocarbon radical having from 1 to 40 carbon atoms, preferably C 1-10 Alkyl and C 1-6 An alkyl group. "C 1-10 Alkyl "is understood to mean preferably a straight-chain or branched saturated monovalent hydrocarbon radical having 1,2, 3,4, 5,6, 7, 8, 9 or 10 carbon atoms. "C 1-6 Alkyl "is understood to mean preferably a straight-chain or branched saturated monovalent hydrocarbon radical having 1,2, 3,4, 5 or 6 carbon atoms. The alkyl is, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, 2-methylbutyl, 1-ethylpropyl, 1, 2-dimethylpropyl,Neopentyl, 1-dimethylpropyl, 4-methylpentyl, 3-methylpentyl, 2-methylpentyl, 1-methylpentyl, 2-ethylbutyl, 1-ethylbutyl, 3-dimethylbutyl, 2-dimethylbutyl, 1-dimethylbutyl, 2, 3-dimethylbutyl, 1, 3-dimethylbutyl, or 1, 2-dimethylbutyl, or the like, or isomers thereof. In particular, the groups have 1,2, 3,4, 5 or 6 carbon atoms (i.e., C 1-6 Alkyl), such as methyl, ethyl, propyl, butyl, isopropyl, isobutyl, sec-butyl, tert-butyl, more particularly said groups having 1,2 or 3 carbon atoms (i.e., C 1-3 Alkyl), such as methyl, ethyl, n-propyl or isopropyl.
The term "C 1-40 Alkoxy "refers to the group-OR, where R is a substituted OR unsubstituted C 1-40 Alkyl group, wherein "C 1-40 Alkyl "has the definition given above. Similarly, the term "C 1-10 Alkoxy "means a group-OC 1-10 Alkyl, "C 1-6 Alkoxy "means a group-OC 1-6 Alkyl, "C 1-3 Alkoxy "means a group-OC 1-3 Alkyl group, wherein "C 1-10 Alkyl "," C 1-6 Alkyl "and" C 1-3 Alkyl "has the definition given above. Specific such alkoxy groups include, but are not limited to: methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, tert-butoxy, sec-butoxy, n-pentoxy, n-hexoxy and 1, 2-dimethylbutoxy.
The term "C 2-40 Alkenyl "is understood to mean preferably a straight-chain or branched monovalent hydrocarbon radical which contains one or more double bonds and has from 2 to 40 carbon atoms, preferably" C 2-10 Alkenyl groups). "C 2-10 Alkenyl "is understood to mean preferably a straight-chain or branched monovalent hydrocarbon radical which contains one or more double bonds and has 2,3, 4,5, 6, 7, 8, 9 or 10 carbon atoms, for example 2,3, 4,5 or 6 carbon atoms (i.e.C 2-6 Alkenyl) having 2 or 3 carbon atoms (i.e., C 2-3 Alkenyl). It will be appreciated that where the alkenyl group comprises more than one double bond, the double bonds may be separated from each other or conjugated. The alkenyl groups are, for example, vinyl, allyl, (-)E) -2-methylvinyl, (Z) -2-methylvinyl, (E) -but-2-enyl, (Z) -but-2-enyl, (E) -but-1-enyl, (Z) -but-1-enyl, pent-4-enyl, (E) -pent-3-enyl, (Z) -pent-3-enyl, (E) -pent-2-enyl, (Z) -pent-2-enyl, (E) -pent-1-enyl, hex-5-enyl, (E) -hex-4-enyl, (Z) -hex-4-enyl, (E) -hex-3-enyl, (Z) -hex-3-enyl, (E) -hex-2-enyl, (Z) -hex-2-enyl, (E) -hex-1-enyl, (Z) -hex-1-enyl, isopropenyl, 2-methylprop-2-enyl, 2-methylprop-1-enyl, (E) -1-methylprop-1-enyl, (Z) -1-methylprop-1-enyl, 3-methylbut-3-enyl, 2-methylbut-3-enyl, 1-methylbut-3-enyl, 3-methylbut-2-enyl, (E) -2-methylbut-2-enyl, (Z) -2-methylbut-2-enyl, (E) -1-methylbut-2-enyl, (Z) -1-methylbut-2-enyl, (E) -3-methylbut-1-enyl, (Z) -3-methylbut-1-enyl, (E) -2-methylbut-1-enyl, (Z) -2-methylbut-1-enyl, (E) -1-methylbut-1-enyl, (Z) -1-methylbut-1-enyl, 1-dimethylprop-2-enyl, 1-ethylprop-1-enyl, 1-propylvinyl, 1-isopropylvinyl.
The term "C 3-20 Cycloalkyl "is understood to mean a saturated monovalent monocyclic or bicyclic hydrocarbon ring, which may be a spiro ring or bridged ring, having 3 to 20 carbon atoms, preferably" C 3-10 Cycloalkyl groups). For example, the term "C 3-10 Cycloalkyl "is understood to mean a saturated monovalent mono-or bicyclic hydrocarbon ring, which may be a spiro ring or bridged ring, having 3,4, 5,6, 7, 8, 9 or 10 carbon atoms. The C is 3-10 Cycloalkyl may be a monocyclic hydrocarbon group such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl or cyclodecyl, or a bicyclic hydrocarbon group such as a decalin ring. For example, the term "C 3-6 Cycloalkyl "is understood to mean a saturated monovalent monocyclic or bicyclic hydrocarbon ring, which may be a spiro ring or bridged ring, having 3,4, 5 or 6 carbon atoms. The C is 3-6 Cycloalkyl radicals can be, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, bicyclo [1.1.0]Butyl, spiropentyl, spiro [2.3]Hexyl, bicyclo [1.1.1]Amyl, bicyclo [2.1.0 ]]Amyl, bicyclo [2.1.1]Hexyl or bicyclo [3.1.0 ]]A hexyl group.
The term "3-20 membered heterocyclyl" means a monovalent group of a 3-20 membered non-aromatic ring system having ring carbon atoms and 1 to 5 ring heteroatoms, which may be saturated or contain one or more double bonds, which may be monocyclic, bicyclic, spiro or bridged, wherein each ring heteroatom is independently selected from N, O, S, B, P and Si. The "3-20 membered heterocyclic group" may be, for example, "3-10 membered heterocyclic group", "3-7 membered heterocyclic group" or "5-6 membered heterocyclic group". The term "3-10 membered heterocyclyl" means a monovalent radical of a 3-10 membered non-aromatic ring system having ring carbon atoms and 1 to 5 ring heteroatoms, which may be monocyclic, bicyclic, spiro or bridged, wherein each ring heteroatom is independently selected from N, O, S, B, P and Si, preferably comprising 1-3 heteroatoms selected from N, O and S. The term "3-7 membered heterocyclyl" means a monovalent group of a 3 to 7 non-aromatic ring system having ring carbon atoms and 1 to 3 ring heteroatoms, which may be monocyclic, bicyclic, spiro or bridged, wherein each ring heteroatom is independently selected from N, O, S, B, P and Si, preferably comprising 1 to 3 heteroatoms selected from N, O and S. The term "5-6 membered heterocyclyl" means a monovalent group of a 5 to 6 non-aromatic ring system having ring carbon atoms and 1 to 3 ring heteroatoms, the non-aromatic ring system typically being a single ring, wherein each ring heteroatom is independently selected from N, O, S, B, P and Si, preferably comprising 1 to 3 heteroatoms selected from N, O and S. The heterocyclic group may be attached to the remainder of the molecule through any of the carbon atoms or a nitrogen atom, if present. Whether or not the heterocyclic group is previously modified with "substituents", each atom of the heterocyclic group is independently optionally substituted, e.g., with 1 to 5 substituents, 1 to 3 substituents, or 1 substituent, suitable substituents include, but are not limited to, hydroxy, amino, oxo, halogen, cyano, nitro, C 1-40 Alkyl, C 2-40 Alkenyl, C 2-40 Alkynyl groups, and the like. In particular, the heterocyclic groups may include, but are not limited to: 3-membered rings such as aziridinyl, oxetanyl and thiiranyl; 4-membered rings such as azetidinyl, oxetanyl and thietanyl; 5-membered rings, e.g. dihydrofuryl, tetrahydrofuranyl, dihydrothienyl, tetrahydrothienyl, dioxyHeterocyclopentyl, pyrrolidinyl, dihydropyrrolyl, imidazolidinyl, pyrazolidinyl, pyrrolinyl, dioxolanyl, oxathiolanyl (oxathiolanyl), dithiolanyl (disulfuranyl), oxazolidin-2-one, triazolinyl, oxadiazolinyl and thiadiazolinyl; or a 6 membered ring such as dihydropyranyl, tetrahydropyranyl, piperidinyl, morpholinyl, dihydropyridinyl, thiacyclohexyl, dithianyl, thiomorpholinyl, piperazinyl, dithianyl, dioxanyl and trithianyl; or 7-membered rings such as diazepanyl, azepanyl, oxepinyl and thiepinyl. Bicyclic heterocycles, e.g. but not limited to 5,5 membered rings, e.g. hexahydrocyclopenta [ c ]]Pyrrol-2 (1H) -yl ring, or 5,6 membered bicyclic ring, e.g. hexahydropyrrolo [1,2-a ]]Pyrazin-2 (1H) -yl ring. The ring containing nitrogen atoms may be partially unsaturated, i.e. it may contain one or more double bonds, such as but not limited to 2, 5-dihydro-1H-pyrrolyl, 4H- [1,3,4]Thiadiazinyl, 4, 5-dihydrooxazolyl or 4H- [1,4]Thiazinyl, or it may be benzo-fused, such as, but not limited to, dihydroisoquinolinyl.
The term "C 6-20 Aryl "is understood to mean preferably a mono-, bi-or tricyclic hydrocarbon ring, preferably" C ", of monovalent aromatic or partly aromatic nature having from 6 to 20 carbon atoms 6-14 Aryl group). The term "C 6-14 Aryl "is understood to mean preferably a mono-, bi-or tricyclic hydrocarbon ring (" C ") having a monovalent aromatic or partially aromatic character of 6, 7, 8, 9, 10, 11, 12, 13 or 14 carbon atoms 6-14 Aryl), in particular a ring having 6 carbon atoms ("C) 6 Aryl "), such as phenyl; or biphenyl, or a ring having 9 carbon atoms ("C 9 Aryl "), e.g. indanyl or indenyl, or a ring having 10 carbon atoms (" C 10 Aryl "), such as tetralin, dihydronaphthyl or naphthyl, or a ring having 13 carbon atoms (" C " 13 Aryl "), e.g. fluorenyl, or a ring having 14 carbon atoms (" C) 14 Aryl "), such as anthracenyl.
The term "5-20 membered heteroaryl" is understood to include such monovalent monocyclic, bicyclic or tricyclic aromatic ring systems: having 5 to 20 ring atoms and containing 1 to 5 heteroatoms independently selected from N, O and S, such as "5-14 membered heteroaryl". The term "5-14 membered heteroaryl" is understood to include such monovalent monocyclic, bicyclic or tricyclic aromatic ring systems: it has 5,6, 7, 8, 9, 10, 11, 12, 13 or 14 ring atoms, in particular 5 or 6 or 9 or 10 carbon atoms, and it contains 1 to 5, preferably 1 to 3 heteroatoms each independently selected from N, O and S and, in addition, can be benzo-fused in each case. The term "5-6 membered heteroaryl" is understood as a monovalent monocyclic aromatic ring system having 5 or 6 ring atoms which contains 1 to 3 heteroatoms each independently selected from N, O and S, and which may be benzo-fused in each case. In particular, the heteroaryl group is selected from thienyl, furyl, pyrrolyl, oxazolyl, thiazolyl, imidazolyl, pyrazolyl, isoxazolyl, isothiazolyl, oxadiazolyl, triazolyl, thiadiazolyl, thia-4H-pyrazolyl and the like and their benzo derivatives, such as benzofuryl, benzothienyl, benzoxazolyl, benzisoxazolyl, benzimidazolyl, benzotriazole, indazolyl, indolyl, isoindolyl and the like; or pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, and the like, and their benzo derivatives, such as quinolinyl, quinazolinyl, isoquinolinyl, and the like; or an axcinyl group, an indolizinyl group, a purinyl group, etc., and their benzo derivatives; or cinnolinyl, phthalazinyl, quinazolinyl, quinoxalinyl, naphthyridinyl, pteridinyl, carbazolyl, acridinyl, phenazinyl, phenothiazinyl, phenoxazinyl, and the like.
The term "inert gas" as used herein includes gases inert to the reaction, such as nitrogen and noble gases or mixtures thereof, unless otherwise indicated.
Detailed Description
The technical scheme of the application will be further described in detail below with reference to specific embodiments. It is to be understood that the following examples are illustrative only and are not to be construed as limiting the scope of the application. All techniques implemented based on the above description of the application are intended to be included within the scope of the application.
Unless otherwise indicated, the starting materials and reagents used in the following examples were either commercially available or may be prepared by known methods.
Example 1
Preparation of Compound A
(1) 4 g of 4- (pyridin-4-yl) phenylboronic acid is added into a round bottom flask, 10 g of 9, 9-dihexyl-2, 7-dibromofluorene, 1.16 g of tetra (triphenylphosphine) palladium and 4.8 g of potassium carbonate are added into the flask, 50 ml of 1, 4-dioxane and 8 ml of water are then added into the flask, argon is introduced into the flask under stirring to deoxidize for 10 minutes, the reaction is carried out for 8 hours at 80 ℃, and the obtained product is separated by column chromatography;
(2) Taking 4.5 g of the product obtained in the step (1), adding 2.4 g of bisboronic acid pinacol ester, 2.5 g of potassium acetate and 0.3 g of 1,1' -bis (diphenylphosphino) ferrocene palladium (II) dichloride into a round-bottom flask, adding 40 ml of 1, 4-dioxane, introducing argon under stirring to deoxidize for 10 minutes, and reacting for 10 hours at 80 ℃, and separating the obtained product by column chromatography;
(3) Taking 4.6 g of the product obtained in the step (2), adding 1 g of 4, 7-dibromo-1H-benzimidazole, 0.3 g of tetra (triphenylphosphine) palladium and 2.5 g of potassium carbonate into a round bottom flask, adding 30 ml of 1, 4-dioxane and 5 ml of water, introducing argon under stirring to deoxidize for 10 minutes, and reacting for 8 hours at 80 ℃, and separating the obtained product by column chromatography; the nuclear magnetic characterization result of the product is shown in figure 1, and the mass spectrum detection result is shown in figure 2.
(4) Dissolving 50 mg of the compound A obtained in the step (3) in 10 ml of chloroform solution, taking out 100 microlitres of the solution after the compound A is completely dissolved, adding the solution into 1 ml of methanol, rapidly stirring, standing for 1 day, and self-assembling the compound A through pi-pi interaction to obtain a suspension of the long-strip aggregate. The above-obtained aggregate 10. Mu.l was taken on a silicon wafer and dried in a dryer. The dried aggregate was placed in a lycra ion sputtering apparatus, platinum particles with a particle size of 10 nm were loaded on the surface of the aggregate, and then the aggregate was placed in a field emission scanning electron microscope for morphology observation, and the SEM image was as shown in fig. 3.
As shown in fig. 4, the characteristic peak of the ultraviolet-visible absorption spectrum of the compound a is at 370 nm, and after the compound a is aggregated, the compound a gradually self-assembles into long-strip-shaped structure aggregates through pi-pi interaction in a poor solvent.
The above-prepared aggregate was coated on a glass sheet, dried, excited with 385 nm light source, and measured for fluorescence emission spectrum, as shown in fig. 5, the aggregate had the strongest fluorescence emission at 440 nm.
The method for measuring the fluorescence quantum yield comprises the following steps:
and (3) dripping the aggregate on a polytetrafluoroethylene film, and selecting the optimal excitation wavelength by measuring the fluorescence excitation spectrum of the sample.
The instrument used for measurement was a Hamamatsu C11247 fluorescence quantum yield spectrometer.
And (3) testing, namely selecting a single-wavelength scanning mode, measuring the fluorescence quantum yield of the sample under the optimal excitation wavelength, performing parallel testing on 3 diaphragms of each sample drop, and taking an average value.
Based on the above method, a small amount of aggregate is placed in an instrument for measuring fluorescence quantum yield, the excitation wavelength is selected to be 385 nanometers, and the fluorescence quantum yield is detected to be 5%.
Example 2
Preparation of Compound B
(1) 3.7 g of 4-cyanophenyl boric acid is added into a round bottom flask, 9.5 g of 9, 9-dihexyl-2, 7-dibromofluorene, 1 g of tetra (triphenylphosphine) palladium and 3.9 g of potassium carbonate are added into the round bottom flask, 40 ml of 1, 4-dioxane and 7 ml of water are then added, argon is introduced into the round bottom flask under stirring condition to deoxidize for 10 minutes, the reaction is carried out for 8 hours at 80 ℃, and the obtained product is obtained after separation by column chromatography;
(2) Taking 4.3 g of the product obtained in the step (1), adding 2.6 g of bisboronic acid pinacol ester, 2.8 g of potassium acetate and 0.32 g of 1,1' -bis (diphenylphosphino) ferrocene palladium (II) dichloride into a round-bottom flask, adding 30 ml of 1, 4-dioxane, introducing argon under stirring to deoxidize for 10 minutes, and reacting for 10 hours at 80 ℃, and separating the obtained product by column chromatography;
(3) Taking 2.3 g of the product obtained in the step (2), adding 0.43 g of 4, 7-dibromo-1H-benzimidazole, 0.17 g of tetra (triphenylphosphine) palladium and 1.45 g of potassium carbonate into a round bottom flask, adding 40 ml of 1, 4-dioxane and 7 ml of water, introducing argon under stirring to deoxidize for 10 minutes, and reacting for 8 hours at 80 ℃, wherein the obtained product is obtained after separation by column chromatography; the nuclear magnetic characterization result of the product is shown in fig. 15, and the mass spectrum detection result is shown in fig. 16.
(4) Dissolving 25 mg of the compound B obtained in the step (3) in 5 ml of chloroform solution, taking out 100 microlitres of the solution after the compound B is completely dissolved, adding the solution into 1 ml of methanol, rapidly stirring, standing for 1 day, and obtaining a suspension of needle-shaped aggregates by self-assembly. 20. Mu.l of the above-obtained aggregate was taken on a silicon wafer and dried in a desiccator. The dried aggregate was placed in a lycra ion sputtering apparatus, platinum particles with a particle size of 10 nm were loaded on the surface of the aggregate, and then the aggregate was placed in a field emission scanning electron microscope for morphology observation, and the SEM image was as shown in fig. 17.
Based on the above method, a small amount of aggregate is placed in an instrument for measuring fluorescence quantum yield, the excitation wavelength is selected to be 385 nanometers, and the fluorescence quantum yield is detected to be 30%.
Example 3
The aggregate prepared by self-assembly in a mixed solution of chloroform and methanol was used for detecting sarin vapor using the compound a obtained in example 1.
The aggregate prepared by self-assembling the compound A is coated in a quartz tube, and then the aggregate is excited by using a 385 nm excitation light source. Different concentrations of sarin vapor were aspirated with a 10 ml syringe and blown into the quartz tube at a rate of 2 ml/sec, and the detection result showed that fluorescence was quenched at 440nm, fluorescence was enhanced at 520nm, and the detection sensitivity was high, with a minimum detectable concentration of sarin vapor of 0.2ppm, as shown in fig. 6.
Example 4
The procedure of example 3 was used to test the response of the aggregates prepared by self-assembly of compound a to soman, except that different concentrations of soman vapors were blown in. As shown in fig. 7, the soman was fluorescence quenched at 440nm and fluorescence enhanced at 520nm with a minimum detectable concentration of 0.5ppm of soman vapor.
Example 5
Using the procedure in example 3, the response of aggregates prepared by self-assembly of Compound A to nerve agent mimetic DCNP was tested with the exception that different concentrations of DCNP vapors were blown. As shown in fig. 8, DCNP fluorescence quenched at 440nm and increased at 520 nm.
Example 6
To demonstrate the selective response of the aggregates prepared by self-assembly of compound a to nerve agents in example 1, methanol vapor was blown using the procedure of example 3. The fluorescence intensity of methanol at 440nm and 520nm was elevated (fig. 9), in a completely different manner from that of nerve agent. Thus, methanol does not interfere with the detection.
Example 7
To demonstrate the selective response of the aggregates prepared by self-assembly of compound a to nerve agents in example 1, acetonitrile vapor was blown using the procedure of example 3. The fluorescence intensity of acetonitrile at 440nm and 520nm was decreased (fig. 10), in a completely different manner from the response of nerve agents. Thus, acetonitrile does not interfere with the detection.
Example 8
To demonstrate the selective response of the aggregates prepared by self-assembly of compound a to nerve agents in example 1, acetone vapor was blown using the procedure of example 3. The fluorescence intensity of acetone at 440nm and 520nm was decreased (fig. 11), which is quite different from the response mode of nerve agent. Thus, acetone does not interfere with the detection.
Example 9
To demonstrate the selective response of the aggregates prepared by self-assembly of compound a to nerve agents in example 1, ethyl acetate vapor was blown using the procedure of example 3. The fluorescence intensity of ethyl acetate at both 440nm and 520nm was rising (fig. 12), in a completely different manner from the response of nerve agents. Thus, ethyl acetate does not interfere with the detection.
Example 10
To demonstrate the selective response of aggregates prepared by self-assembly of compound a to nerve agents in example 1, tetrahydrofuran vapor was blown using the procedure of example 3. The fluorescence intensity of tetrahydrofuran at 440nm and 520nm was decreased (fig. 13), which is quite different from the response mode of nerve agents. Therefore, tetrahydrofuran does not interfere with the detection.
Example 11
To demonstrate the selective response of the aggregates prepared by self-assembly of compound a to nerve agents in example 1, dimethyl sulfoxide vapor was blown using the procedure of example 3. The fluorescence intensity of dimethyl sulfoxide was elevated at both 440nm and 520nm (fig. 14), in a completely different manner from that of nerve agents. Thus, dimethyl sulfoxide does not interfere with detection.
Example 12
The aggregate prepared by self-assembly in a mixed solution of chloroform and methanol was used for detecting the nerve agent mimetic DCNP vapor using the compound B obtained in example 2.
The aggregate prepared by self-assembling the compound B is coated in a quartz tube, and then the aggregate is excited by using a 385 nm excitation light source. Different concentrations of sarin vapor were aspirated with a 10 ml syringe and blown into the quartz tube at a rate of 2 ml/sec, and the detection result showed that fluorescence enhanced at 440nm and 520nm occurred, as shown in fig. 18.
The embodiments of the present application have been described above. However, the present application is not limited to the above embodiment. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application should be included in the protection scope of the present application.

Claims (20)

1. A compound of formula (i):
wherein each R 1 、R 2 The same or different, independently of one another, from hydrogen, C 1-12 An alkyl group; r is R 3 、R 4 The same or different, independently of one another, are selected from cyano, the following radicals, unsubstituted or substituted by 1,2 or more Ra: c (C) 6-14 Aryl, 5-14 membered heteroaryl; a. b are identical or different and are each independently selected from the group consisting of 1 to 3;
each Ra, which are identical or different, are independently selected from CN, C 1-12 Alkyl group,C 1-12 An alkoxy group.
2. The compound of claim 1, wherein each R 1 、R 2 The same or different, independently of one another, from hydrogen, C 1-12 An alkyl group; r is R 3 、R 4 The same or different, independently selected from cyano, pyridinyl; a. b are identical or different and are each independently selected from the group consisting of 1 to 3.
3. The compound of claim 1, wherein each R 1 、R 2 The same or different, independently of one another, are selected from the following groups:
4. a compound according to claim 1, wherein R 3 、R 4 The same or different, independently of one another, are selected from the following groups: CN,
Wherein, the marked end is the group connecting point.
5. A compound according to claim 1, wherein R 1 、R 2 Is hexyl, R 3 、R 4 Cyano or pyridinyl, a=b=1.
6. A process for the preparation of a compound as claimed in any one of claims 1 to 5 comprising the steps of:
reacting compound 1 with pinacol diboronate to give intermediate 2;
reacting the product intermediate 2 of the step (I-1) with 2, 7-dibromo-9, 9-dialkylfluorene to obtain an intermediate 3;
reacting the product intermediate 3 of the step (I-2) with pinacol biborate to obtain an intermediate 4;
optionally, repeating the conditions a-1 times in the step (I-2) and the step (I-3) by taking the product intermediate 4 of the step (I-3) as a substrate to obtain an intermediate 5a;
(I-5) optionally, R in steps (I-1) - (I-4) 1 、R 3 And a, respectively substituted by R 2 、R 4 And b, sequentially obtaining an intermediate 5b according to the same reaction conditions in the steps (I-1) - (I-4);
(I-6) when a and b are the same, R 1 And R is 3 Identical, R 2 And R is 4 In the same time, the compound 4, 7-dibromobenzimidazole reacts with an intermediate 5a to obtain the compound of the formula (I);
when a and b, R 1 And R is 3 、R 2 And R is 4 At least one group of non-identical compounds dibromobenzimidazole is reacted with intermediate 5aAnd then reacting with an intermediate 5b to obtain the compound shown in the formula (I).
7. An organic fluorescent nanoribbon aggregate comprising a compound of any of claims 1-5.
8. The method for preparing the organic fluorescent nano strip aggregate according to claim 7, which is characterized by comprising the step of self-assembling the compound shown in the formula (I) between molecules to obtain the organic fluorescent nano strip aggregate.
9. The method according to claim 8, wherein the intermolecular self-assembly is achieved by contacting the compound represented by formula (I) with a mixture of a good solvent and a poor solvent thereof;
the poor solvent is selected from halogenated hydrocarbon solvents, and the poor solvent is selected from alcohol solvents, ketone solvents or alkane solvents.
10. The method according to claim 9, wherein the contacting comprises dissolving the compound represented by the formula (I) in a good solvent thereof, then adding a poor solvent thereof, and standing.
11. The method of claim 9, wherein the volume ratio of the good solvent to the poor solvent is 1:5 to 1:30.
12. The method of claim 9, wherein the volume ratio of the good solvent to the poor solvent is 1:5 to 1:20.
13. The method of claim 9, wherein the volume ratio of the good solvent to the poor solvent is 1:5 to 1:10.
14. The method according to claim 9, wherein the good solvent is at least one selected from chloroform and methylene chloride;
the poor solvent is selected from at least one of methanol, acetone and n-hexane.
15. A fluorescent material comprising the compound of any one of claims 1-5.
16. The fluorescent material of claim 15, wherein the fluorescent material comprises the organic fluorescent nanobar aggregate of claim 7.
17. Use of the fluorescent material of claim 15 for detecting a nerve agent;
the nerve agent is selected from one or more of diethyl cyanophosphate, sarin, soman and Tacron.
18. A method of detecting a chemical warfare agent comprising contacting the fluorescent material of claim 15 with a nerve agent.
19. The method of claim 18, wherein the concentration of the nerve agent detected ranges from 0.1ppb to 500ppm.
20. The method of claim 18, wherein the concentration of the nerve agent detected ranges from 1ppb to 200ppm.
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