CN114478357A - Halogen bond-containing piezochromic aggregation-induced emission molecule - Google Patents

Halogen bond-containing piezochromic aggregation-induced emission molecule Download PDF

Info

Publication number
CN114478357A
CN114478357A CN202210393876.1A CN202210393876A CN114478357A CN 114478357 A CN114478357 A CN 114478357A CN 202210393876 A CN202210393876 A CN 202210393876A CN 114478357 A CN114478357 A CN 114478357A
Authority
CN
China
Prior art keywords
piezochromic
aggregation
halogen bond
molecule containing
induced emission
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202210393876.1A
Other languages
Chinese (zh)
Other versions
CN114478357B (en
Inventor
赵润
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Jiangsu New Vision Advanced Functional Fiber Innovation Center Co ltd
Original Assignee
Jiangsu New Vision Advanced Functional Fiber Innovation Center Co ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Jiangsu New Vision Advanced Functional Fiber Innovation Center Co ltd filed Critical Jiangsu New Vision Advanced Functional Fiber Innovation Center Co ltd
Priority to CN202210393876.1A priority Critical patent/CN114478357B/en
Publication of CN114478357A publication Critical patent/CN114478357A/en
Application granted granted Critical
Publication of CN114478357B publication Critical patent/CN114478357B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/56—Ring systems containing three or more rings
    • C07D209/80—[b, c]- or [b, d]-condensed
    • C07D209/82—Carbazoles; Hydrogenated carbazoles
    • C07D209/86—Carbazoles; Hydrogenated carbazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the ring system
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/56—Ring systems containing three or more rings
    • C07D209/80—[b, c]- or [b, d]-condensed
    • C07D209/82—Carbazoles; Hydrogenated carbazoles
    • C07D209/88—Carbazoles; Hydrogenated carbazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to carbon atoms of the ring system
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing three or more hetero rings
    • 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
    • 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
    • C09K9/00—Tenebrescent materials, i.e. materials for which the range of wavelengths for energy absorption is changed as a result of excitation by some form of energy
    • C09K9/02—Organic tenebrescent 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
    • C09K2211/1003—Carbocyclic compounds
    • C09K2211/1007—Non-condensed systems
    • 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
    • C09K2211/1003—Carbocyclic compounds
    • C09K2211/1011—Condensed systems
    • 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
    • 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
    • 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
    • C09K2211/1059—Heterocyclic compounds characterised by ligands containing three nitrogen atoms as heteroatoms
    • 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
    • C09K2211/1092—Heterocyclic compounds characterised by ligands containing sulfur as the only heteroatom

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention relates to a piezochromic aggregation-induced emission molecule containing a halogen bond, which has a structural formula consisting of a core structure and at least two branch structures connected with the core structure; the core structure is
Figure 461492DEST_PATH_IMAGE001
、
Figure 325543DEST_PATH_IMAGE002
、
Figure 733390DEST_PATH_IMAGE003
、
Figure 24694DEST_PATH_IMAGE004
、
Figure 885203DEST_PATH_IMAGE005
、
Figure 146420DEST_PATH_IMAGE006
、
Figure 877616DEST_PATH_IMAGE007
、
Figure 933296DEST_PATH_IMAGE008
、
Figure 749943DEST_PATH_IMAGE009
、
Figure 955796DEST_PATH_IMAGE010
、
Figure 72657DEST_PATH_IMAGE011
Or
Figure 705763DEST_PATH_IMAGE012
(ii) a The branch structure is
Figure 540864DEST_PATH_IMAGE013
Or
Figure 284829DEST_PATH_IMAGE014
Wherein R is1=
Figure 990617DEST_PATH_IMAGE016
X is F, Cl or Br; r2Is composed of
Figure DEST_PATH_IMAGE017
、
Figure 309472DEST_PATH_IMAGE018
、
Figure DEST_PATH_IMAGE019
Or
Figure 303973DEST_PATH_IMAGE020
；R3Is composed of
Figure 976262DEST_PATH_IMAGE017
、
Figure 943081DEST_PATH_IMAGE018
、
Figure 308204DEST_PATH_IMAGE019
Or
Figure 727684DEST_PATH_IMAGE020
(ii) a In each formula, the position of the connection of the core structure and the branch structure is represented; the piezochromic aggregation-induced emission molecule containing the halogen bond has the characteristic of generating near infrared light under the pressure effect of 8-15 GPa. The invention has the advantages of rigid molecular structure, high luminous efficiency, high stability, excellent uniformity, reversibility and no loss.

Description

Halogen bond-containing piezochromic aggregation-induced emission molecule
Technical Field
The invention belongs to the technical field of piezochromic materials, and relates to a piezochromic aggregation-induced emission molecule containing a halogen bond.
Background
With the development of wearable technology, people have higher and higher requirements on material functionalization and intelligent degree, consumers have higher requirements on textiles, the functions of textile and clothes are gradually expanded to the demanded market, and the controllable color-changing intelligent fabric has wide research prospects in the fields of military stealth, fashion, intelligent home and civil clothes, so that the color-changing fiber and the intelligent fabric thereof become popular fields for exploration and research of various national scholars. The color-changing fibers are mainly divided into two categories, namely the passive color-changing fibers which need no power supply and the active color-changing fibers which need no power supply, and the passive color-changing fibers which need no power supply are widely concerned because of the characteristics of resource saving, convenience, strong autonomy and the like.
In the passive color-changing fiber technology, the piezoluminescence color-changing fiber prepared by using the piezoluminescence color-changing material has very important potential application in the fields of artificial muscle, stress sensors, trademark anti-counterfeiting, memory chips, data storage, information materials, anti-counterfeiting, optical recording and the like. The piezoluminescence color-changing material is an intelligent material which presents different luminescence colors or different light and shade intensities under the stimulation of different external forces (such as pressure, shearing force, stretching force and the like), and comprises a piezofluorescence color-changing material and a piezophosphorescence color-changing material, and the color-changing mechanism mainly comprises two types: (1) the color change is realized through the change of a chemical structure; (2) the color change is realized by the change of a physical aggregation state, wherein the former is that material molecules generate chemical reaction under the action of external force, namely the breakage of old bonds and the formation of new bonds occur, and the former is essentially light with different colors emitted by different molecules formed before and after the stress; in the latter, under the action of external force, the stacking mode, molecular conformation or intermolecular interaction among material molecules are changed, so that the energy level of the molecules is influenced, and the difference of the luminescent color before and after stress is caused. The piezoluminescence color-changing material for realizing color change based on the former color-changing mechanism has higher difficulty in synthesis and very limited application range, so that the piezoluminescence color-changing material for realizing color change based on the latter color-changing mechanism, namely, the piezoluminescence aggregation-induced luminescent material becomes the key point of research.
Document 1 (influx of Carbazolyl Groups on Properties of Piezofluorogenic Aggregation-Enhanced Emission Compounds connecting Distyrylanthracene) an Aggregation-inducing luminescent molecule was prepared, of the formula:
Figure 619987DEST_PATH_IMAGE001
(ii) a Document 2 (Deformation-Induced Color Changes in polymeric polymers Blends) prepared a Color-changing molecule of the formula:
Figure 934424DEST_PATH_IMAGE002
preparing a film in a doping mode, and generating blue light by stretching fluorescence wavelength blue shift; however, the two molecules are easy to arrange in crystal lattices due to small molecular structures, so that the crystals are compact, the crystal lattice energy is large, the crystal structures are not easy to damage by external force, and the color is difficult to change.
Reference 3 (influx of Carbazolyl Groups on Properties of Piezofluorogenic Aggregation-Enhanced Emission Compounds connecting Distyrylanthracene) A luminescence molecule was preparedThe formula is as follows:
Figure 476264DEST_PATH_IMAGE003
although the crystal structure of the molecule is easily damaged by external force, after the crystal structure of the molecule is damaged, the molecular structure does not have a group with large steric hindrance, the damaged crystal structure is easy to automatically recover, the recovery time is short, and the piezochromic phenomenon is difficult to observe.
In addition, most of the existing piezochromic aggregation-induced luminescent materials can only release visible light under the action of external force, and can not release near infrared light with antibacterial and building-protective effects, so that the application of the piezochromic aggregation-induced luminescent materials is limited to a certain extent.
Therefore, the research on the piezochromic aggregation-induced luminescent material which is easy to generate piezochromic color and has obvious piezochromic color phenomenon and can release near infrared light under the action of external force has great significance.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provides a piezochromic aggregation-induced emission molecule containing a halogen bond.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the structural formula of the piezochromic aggregation-induced emission molecule containing the halogen bond is composed of a core structure and at least two branch structures connected with the core structure; the core structure is
Figure 850745DEST_PATH_IMAGE004
、
Figure 618981DEST_PATH_IMAGE005
、
Figure 596164DEST_PATH_IMAGE006
、
Figure 992510DEST_PATH_IMAGE007
、
Figure 537892DEST_PATH_IMAGE008
、
Figure 793424DEST_PATH_IMAGE009
、
Figure 839878DEST_PATH_IMAGE010
、
Figure 966097DEST_PATH_IMAGE011
、
Figure 541434DEST_PATH_IMAGE012
、
Figure 143317DEST_PATH_IMAGE013
、
Figure 603248DEST_PATH_IMAGE014
Or
Figure 974187DEST_PATH_IMAGE015
(ii) a The branch structure is
Figure 124021DEST_PATH_IMAGE016
Or
Figure 947620DEST_PATH_IMAGE017
Wherein R is1=
Figure 945663DEST_PATH_IMAGE018
X is F, Cl or Br; r2Is composed of
Figure 171108DEST_PATH_IMAGE019
、
Figure 760353DEST_PATH_IMAGE020
、
Figure 946615DEST_PATH_IMAGE021
Or
Figure 872982DEST_PATH_IMAGE022
；R3Is composed of
Figure 952934DEST_PATH_IMAGE019
、
Figure 181921DEST_PATH_IMAGE020
、
Figure 980113DEST_PATH_IMAGE021
Or
Figure 585537DEST_PATH_IMAGE022
；
In each formula, the position of the connection of the core structure and the branch structure is represented;
the piezochromic aggregation-induced emission molecule containing the halogen bond has the characteristic of generating near infrared light under the pressure effect of 8-15 GPa.
The piezochromic aggregation-induced emission molecule containing the halogen bond has a special propeller-shaped twisted conformation structure, so that the molecule is difficult to be tightly stacked in a crystalline state, the crystalline structure of the molecule is easy to change under the action of external force, the molecular energy level and the emission spectrum of the molecule are changed, and the piezochromic phenomenon is generated; meanwhile, nitrogen atoms and halogen atoms of the cyano groups can form hydrogen bonds and halogen bonds with hydrogen atoms on a benzene ring, and the hydrogen bonds and the halogen bonds are deformed when the hydrogen bonds and the halogen bonds are subjected to external pressure, so that the color of molecules is changed. The fluorescent change of the two factors, namely the change of the molecular aggregation mode in the crystal and the pressure induced discoloration caused by the deformation of weak interaction (halogen bond and hydrogen bond), can generate near infrared light which has the functions of medical care and antibiosis.
As a preferred technical scheme:
the piezochromic aggregation-induced emission molecule containing the halogen bond has the same structure with each branch structure connected with the same core structure.
The piezochromic aggregation-induced emission molecule containing the halogen bond has a core structure
Figure 785575DEST_PATH_IMAGE004
The branch structure is
Figure 185463DEST_PATH_IMAGE016
，R1is-Cl, R2is-CH3(ii) a Alternatively, the core structure is
Figure 470951DEST_PATH_IMAGE005
The branch structure is
Figure 614487DEST_PATH_IMAGE016
，R1is-Br, R2is-OCH3；
Alternatively, the core structure is
Figure 669031DEST_PATH_IMAGE006
The branch structure is
Figure 502470DEST_PATH_IMAGE016
，R1is-Cl, R2Is composed of
Figure 275254DEST_PATH_IMAGE022
(ii) a Alternatively, the core structure is
Figure 956903DEST_PATH_IMAGE007
The branch structure is
Figure 131532DEST_PATH_IMAGE016
，R1is-Cl, R2is-CH3(ii) a Alternatively, the core structure is
Figure 873223DEST_PATH_IMAGE008
The branch structure is
Figure 133303DEST_PATH_IMAGE017
，R1is-F, R3Is composed of
Figure 618642DEST_PATH_IMAGE022
(ii) a Alternatively, the core structure is
Figure 647778DEST_PATH_IMAGE009
(iii) branch knotIs constructed as
Figure 825950DEST_PATH_IMAGE017
，R1is-Cl, R3is-CH3(ii) a Alternatively, the core structure is
Figure 307746DEST_PATH_IMAGE010
The branch structure is
Figure 596776DEST_PATH_IMAGE017
，R1is-Br, R3is-OCH3(ii) a Alternatively, the core structure is
Figure 480419DEST_PATH_IMAGE011
The branch structure is
Figure 829492DEST_PATH_IMAGE017
，R1is-Cl, R3is-H;
alternatively, the core structure is
Figure 798585DEST_PATH_IMAGE012
The branch structure is
Figure 625726DEST_PATH_IMAGE016
，R1is-Cl, R2is-CH3；
Alternatively, the core structure is
Figure 629455DEST_PATH_IMAGE013
The branch structure is
Figure 146499DEST_PATH_IMAGE017
，R1is-Cl, R3is-CH3；
Alternatively, the core structure is
Figure 602888DEST_PATH_IMAGE014
The branch structure is
Figure 233721DEST_PATH_IMAGE016
，R1is-Br, R2is-OCH3；
Alternatively, the core structure is
Figure 826376DEST_PATH_IMAGE015
The branch structure is
Figure 517252DEST_PATH_IMAGE017
，R1is-Cl, R3is-H.
According to the piezochromic aggregation-induced emission molecule containing the halogen bond, the piezochromic aggregation-induced emission molecule containing the halogen bond does not emit fluorescence in tetrahydrofuran, and emits fluorescence in a mixed solution of tetrahydrofuran and water in a volume ratio of 9-99: 1, so that the piezochromic aggregation-induced emission molecule containing the halogen bond has aggregation-induced emission properties.
When the applied pressure is 8-15 GPa, the maximum emission peak position of the piezochromic aggregation-induced luminescent molecule containing the halogen bond is 700-755 nm, the emission intensity decreases with the action time of the pressure, and the change of the pressure and the maximum emission peak position is in a linear relation, which indicates that the piezochromic aggregation-induced luminescent molecule containing the halogen bond not only has piezochromic property, but also has the potential of being applied to pressure sensing; after the external pressure is removed, the maximum emission peak position and the emission intensity of the piezochromic aggregation-induced emission molecule containing the halogen bond are restored to the initial state.
When the applied pressure is 10-20 MPa, the crystal structure of the piezochromic aggregation-induced emission molecule containing the halogen bond is changed, which shows that the molecular crystal structure of the invention is easily damaged by the action of external pressure; after the external pressure is removed, the crystal structure of the piezochromic aggregation-induced emission molecule containing the halogen bond is recovered to the initial state after 10-60 min, which shows that the recovery time of the damaged crystal structure of the molecule is long.
The light-emitting efficiency of the piezochromic aggregation-induced emission molecule containing the halogen bond is 50-80%, and the light-emitting efficiency is still 40-70% after more than 20 times of cycle tests Poor uniformity and reversibility, etc.
Advantageous effects
The piezochromic aggregation-induced emission molecule containing the halogen bond has the advantages of rigid structure, high luminous efficiency, high stability, excellent uniformity and no reversible loss.
Drawings
FIG. 1 is a hydrogen spectrum of a piezochromic aggregation-induced emission molecule containing a halogen bond prepared in example 1;
FIG. 2 is a hydrogen spectrum of a piezochromic aggregation-inducing luminescent molecule having a halogen bond prepared in example 2;
FIG. 3 is a hydrogen spectrum of a piezochromic aggregation-induced emission molecule comprising a halogen bond prepared in example 3;
FIG. 4 is a hydrogen spectrum of a piezochromic aggregation-induced emission molecule comprising a halogen bond prepared in example 4;
FIG. 5 is a hydrogen spectrum of a piezochromic aggregation-inducing luminescent molecule comprising a halogen bond prepared in example 5;
FIG. 6 is a hydrogen spectrum of a piezochromic aggregation-inducing luminescent molecule comprising a halogen bond prepared in example 6;
FIG. 7 is a hydrogen spectrum of a piezochromic aggregation-inducing luminescent molecule comprising a halogen bond prepared in example 7;
FIG. 8 is a hydrogen spectrum of a piezochromic aggregation-inducing luminescent molecule comprising a halogen bond prepared in example 8;
FIG. 9 is a hydrogen spectrum of a piezochromic aggregation-inducing luminescent molecule having halogen bonds prepared in example 9;
FIG. 10 is a hydrogen spectrum of a piezochromic aggregation-inducing luminescent molecule having halogen bonds prepared in example 10;
FIG. 11 is a hydrogen spectrum of a piezochromic aggregation-inducing luminescent molecule having halogen bonds prepared in example 11;
FIG. 12 is a hydrogen spectrum of a piezochromic aggregation-inducing luminescent molecule comprising a halogen bond prepared in example 12;
FIG. 13 is a piezochromic fluorescence spectrum of a piezochromic aggregation-induced emission molecule comprising a halogen bond prepared in example 1;
FIG. 14 is a piezochromic fluorescence spectrum of a piezochromic aggregation-induced emission molecule having a halogen bond prepared in example 2;
FIG. 15 is a piezochromic fluorescence spectrum of a piezochromic aggregation-induced emission molecule comprising a halogen bond prepared in example 3;
FIG. 16 is a piezochromic fluorescence spectrum of a piezochromic aggregation-induced emission molecule containing a halogen bond prepared in example 4;
FIG. 17 is a piezochromic fluorescence spectrum of a piezochromic aggregation-induced emission molecule comprising a halogen bond prepared in example 5;
FIG. 18 is a piezochromic fluorescence spectrum of a piezochromic aggregation-induced emission molecule comprising a halogen bond prepared in example 6;
FIG. 19 is a piezochromic fluorescence spectrum of a piezochromic aggregation-induced emission molecule comprising a halogen bond prepared in example 7;
FIG. 20 is a piezochromic fluorescence spectrum of a piezochromic aggregation-induced emission molecule comprising a halogen bond prepared in example 8;
FIG. 21 is a piezochromic fluorescence spectrum of a piezochromic aggregation-induced emission molecule having a halogen bond prepared in example 9;
FIG. 22 is a piezochromic fluorescence spectrum of a piezochromic aggregation-induced emission molecule having a halogen bond prepared in example 10;
FIG. 23 is a piezochromic fluorescence spectrum of a piezochromic aggregation-induced emission molecule having a halogen bond prepared in example 11;
FIG. 24 is a piezochromic fluorescence spectrum of a piezochromic aggregation-induced emission molecule containing a halogen bond prepared in example 12.
Detailed Description
The invention will be further illustrated with reference to specific embodiments. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention can be made by those skilled in the art after reading the teaching of the present invention, and these equivalents also fall within the scope of the claims appended to the present application.
Example 1
The preparation method of the piezochromic aggregation-induced emission molecule containing the halogen bond comprises the following specific steps:
(1) adding 3, 6-dimethylcarbazole, p-iodobenzoyl chloride, potassium carbonate, 18-crown-6, cuprous iodide and o-dichlorobenzene into a round-bottom flask, vacuumizing at-25 ℃ under a freezing condition, introducing nitrogen for 4 times, and stirring and refluxing at 180 ℃ for 60 hours; after the reaction is finished, repeatedly washing the reaction system by using acid liquor with the mass concentration of 5%, extracting for 3 times by using dichloromethane, drying by using a drying agent, then carrying out rotary evaporation to remove the solvent, and carrying out column chromatography separation to obtain an intermediate product;
wherein the mass ratio of the 3, 6-dimethylcarbazole, the p-iodobenzoyl chloride, the potassium carbonate, the 18-crown-6, the cuprous iodide and the drying agent is 1:1.2:20:0.2:0.2: 30; the volume ratio of the o-dichlorobenzene to the acid solution to the dichloromethane is 1:12: 12; the acid solution is hydrochloric acid; the drying agent is anhydrous magnesium sulfate;
(2) adding the intermediate product prepared in the step (1) and terephthalonitrile into a round-bottom flask, vacuumizing and introducing nitrogen for 4 times, adding 2-propanol and a tetrahydrofuran solution with the water content of 0.004%, stirring and heating to 46 ℃, injecting the tetrahydrofuran solution of potassium 2-propoxide with the concentration of 1mmol/L, and reacting with tetrabutylammonium hydroxide for 2 hours; pouring the system into acetic acid acidified methanol after the reaction is finished, and performing suction filtration and column chromatography separation to obtain the final piezochromic aggregation-induced emission molecule containing the halogen bond;
wherein the mass ratio of the intermediate product, the terephthalonitrile and the potassium 2-propoxide is 2.1:1: 6; the volume ratio of 2-propanol, dried tetrahydrofuran, tetrabutylammonium hydroxide and acetic acid acidified methanol is 1:0.6:0.04: 5.
The hydrogen spectrogram of the prepared piezochromic aggregation-induced emission molecule containing the halogen bond is shown in figure 1, and the structural formula of the prepared piezochromic aggregation-induced emission molecule consists of a core structure and two branch structures connected with the core structure; the structures of all branch structures connected with the same core structure are the same; the core structure is
Figure 601882DEST_PATH_IMAGE004
The branch structure is
Figure 895460DEST_PATH_IMAGE016
，R1is-Cl, R2is-CH3(ii) a Wherein represents the position where the core structure and the branch structure are connected; the piezochromic aggregation-induced emission molecule containing the halogen bond has the characteristic of generating near infrared light under the pressure effect of 8-15 GPa; the piezochromic aggregation-induced emission molecule containing the halogen bond has no fluorescence emission in tetrahydrofuran, and has fluorescence emission in a mixed solution of tetrahydrofuran and water with the volume ratio of 9-99: 1; as shown in fig. 13, when the applied pressure was 15GPa, the maximum emission peak position of the piezochromic aggregation-inducing luminescent molecule containing a halogen bond was 705nm, and the emission intensity decreased with the pressure action time, the pressure and the change of the maximum emission peak position were in a linear relationship; after the external pressure is removed, the maximum emission peak position and the emission intensity of the piezochromic aggregation-induced emission molecule containing the halogen bond are restored to the initial state; when the applied pressure is 20MPa, the crystal structure of the piezochromic aggregation-induced emission molecule containing the halogen bond is changed; after the external pressure is removed, the crystal structure of the piezochromic aggregation-induced emission molecule containing the halogen bond is recovered to the initial state after 60 min; the light-emitting efficiency of the piezochromic aggregation-induced emission molecule containing the halogen bond is 50%, and the light-emitting efficiency is still 40% after more than 20 times of cyclic tests.
Example 2
The preparation method of the piezochromic aggregation-induced emission molecule containing the halogen bond comprises the following specific steps:
(1) adding 3, 6-dimethoxycarbazole, p-iodobenzoyl bromide, potassium carbonate, 18-crown-6, cuprous iodide and o-dichlorobenzene into a round-bottom flask, vacuumizing at-35 deg.C under refrigeration, introducing nitrogen for 4 times, and stirring at 185 deg.C under reflux for 90 hr; after the reaction is finished, repeatedly washing the reaction system by acid liquor with the mass concentration of 6%, extracting for 3 times by dichloromethane, drying by a drying agent, then rotationally evaporating to remove the solvent, and separating by column chromatography to obtain an intermediate product;
wherein the mass ratio of the 3, 6-dimethoxycarbazole, the p-iodobenzoyl bromide, the potassium carbonate, the 18-crown-6, the cuprous iodide and the desiccant is 1:1.3:30:0.3:0.3: 50; the volume ratio of the o-dichlorobenzene to the acid solution to the dichloromethane is 1:15: 15; the acid solution is sulfuric acid; the drying agent is anhydrous calcium sulfate;
(2) adding the intermediate product prepared in the step (1), namely (benzene-1, 3, 5-triyl) triacetonitrile into a round-bottom flask, vacuumizing and introducing nitrogen for 4 times, adding 2-propanol and a tetrahydrofuran solution with the water content of 0.004%, heating to 48 ℃ under stirring, injecting a tetrahydrofuran solution of 2-potassium propoxide with the concentration of 2mmol/L, and reacting with tetrabutylammonium hydroxide for 2 hours; pouring the system into acetic acid acidified methanol after the reaction is finished, and performing suction filtration and column chromatography separation to obtain the final piezochromic aggregation-induced emission molecule containing the halogen bond;
wherein the mass ratio of the intermediate product, (benzene-1, 3, 5-triyl) acetonitrile to potassium 2-propoxide is 3.1:1: 9; the volume ratio of 2-propanol, dried tetrahydrofuran, tetrabutylammonium hydroxide and acetic acid acidified methanol is 1:0.7:0.06: 7.
The hydrogen spectrogram of the prepared piezochromic aggregation-induced emission molecule containing the halogen bond is shown in figure 2, and the structural formula of the prepared piezochromic aggregation-induced emission molecule consists of a core structure and 3 branch structures connected with the core structure; the structures of all branch structures connected with the same core structure are the same; the core structure is
Figure 608201DEST_PATH_IMAGE005
The branch structure is
Figure 204399DEST_PATH_IMAGE016
，R1is-Br, R2is-OCH3(ii) a Wherein represents the position where the core structure and the branch structure are connected; the piezochromic aggregation-induced emission molecule containing the halogen bond has the characteristic of generating near infrared light under the pressure effect of 8-15 GPa; piezochromic aggregates containing halogen bondsThe induced luminescent molecules do not emit fluorescence in tetrahydrofuran, and emit fluorescence in a mixed solution of tetrahydrofuran and water in a volume ratio of 9-99: 1; as shown in fig. 14, when the applied pressure was 14.5GPa, the maximum emission peak position of the piezochromic aggregation-inducing luminescent molecule containing a halogen bond was 711nm, and the emission intensity decreased with the pressure action time, the pressure varied linearly with the maximum emission peak position; after the external pressure is removed, the maximum emission peak position and the emission intensity of the piezochromic aggregation-induced emission molecule containing the halogen bond are restored to the initial state; when the applied pressure is 18.5MPa, the crystal structure of the piezochromic aggregation-induced emission molecule containing the halogen bond is changed; after the external pressure is removed, the crystal structure of the piezochromic aggregation-induced emission molecule containing the halogen bond is recovered to the initial state after 50 min; the light-emitting efficiency of the piezochromic aggregation-induced emission molecule containing the halogen bond is 53%, and the light-emitting efficiency is still 41% after more than 20 times of cyclic tests.
Example 3
The preparation method of the piezochromic aggregation-induced emission molecule containing the halogen bond comprises the following specific steps:
(1) adding carbazole derivative, p-iodobenzoyl chloride, potassium carbonate, 18-crown-6, cuprous iodide and o-dichlorobenzene into a round-bottom flask, vacuumizing and introducing nitrogen for 4 times under a freezing condition of-25 ℃, and stirring and refluxing for 120 hours at 190 ℃; after the reaction is finished, repeatedly washing the reaction system by using acid liquor with the mass concentration of 7%, extracting for 3 times by using dichloromethane, drying by using a drying agent, then carrying out rotary evaporation to remove the solvent, and carrying out column chromatography separation to obtain an intermediate product;
wherein the mass ratio of the carbazole derivative, the p-iodobenzoyl chloride, the potassium carbonate, the 18-crown-6, the cuprous iodide and the drying agent is 1:1.4:40:0.4:0.4: 40; the volume ratio of the o-dichlorobenzene to the acid solution to the dichloromethane is 1:14: 14; the acid solution is hydrobromic acid; the drying agent is anhydrous sodium sulfate; the structural formula of the carbazole derivative is as follows:
Figure 635380DEST_PATH_IMAGE023
(2) adding the intermediate product prepared in the step (1), namely (benzene-1, 2,4, 5-tetra-yl) tetra-acetonitrile into a round-bottom flask, vacuumizing and introducing nitrogen for 3 times, adding 2-propanol and a tetrahydrofuran solution with the water content of 0.004%, stirring and heating to 50 ℃, injecting a tetrahydrofuran solution of potassium 2-propoxide with the concentration of 3mmol/L, and reacting with tetrabutylammonium hydroxide for 2 hours; pouring the system into acetic acid acidified methanol after the reaction is finished, and performing suction filtration and column chromatography separation to obtain the final piezochromic aggregation-induced emission molecule containing the halogen bond;
wherein the mass ratio of the intermediate product, (benzene-1, 2,4, 5-tetra-yl) tetraacetonitrile to the potassium 2-propoxide is 4.1:1: 8; the volume ratio of 2-propanol, dried tetrahydrofuran, tetrabutylammonium hydroxide and acetic acid acidified methanol is 1:0.7:0.08: 9.
The hydrogen spectrogram of the prepared piezochromic aggregation-induced emission molecule containing the halogen bond is shown in figure 3, and the structural formula of the prepared piezochromic aggregation-induced emission molecule consists of a core structure and 4 branch structures connected with the core structure; the structures of all branch structures connected with the same core structure are the same;
the core structure is
Figure 608016DEST_PATH_IMAGE006
The branch structure is
Figure 440842DEST_PATH_IMAGE016
，R1is-Cl, R2Is composed of
Figure 207941DEST_PATH_IMAGE022
(ii) a Wherein represents the position where the core structure and the branch structure are connected; the piezochromic aggregation-induced emission molecule containing the halogen bond has the characteristic of generating near infrared light under the action of pressure intensity of 8-15 GPa; the piezochromic aggregation-induced emission molecule containing the halogen bond does not emit fluorescence in tetrahydrofuran, and emits fluorescence in a mixed solution of tetrahydrofuran and water in a volume ratio of 9-99: 1; as shown in fig. 15, when the applied pressure is 14GPa, the maximum emission peak position of the piezochromic aggregation-inducing luminescent molecule containing a halogen bond is 714nm, and the emission intensity decreases with the pressure action time, and the pressure and the change of the maximum emission peak position are in a linear relationship; the most preferred of the halogen-containing piezochromic aggregation-inducing luminescent molecules isThe large emission peak position and the emission intensity are restored to the initial state; when the applied pressure is 18MPa, the crystal structure of the piezochromic aggregation-induced emission molecule containing the halogen bond is changed; after the external pressure is removed, the crystal structure of the piezochromic aggregation induced emission molecule containing the halogen bond is restored to the initial state after 48 min; the light-emitting efficiency of the piezochromic aggregation-induced emission molecule containing the halogen bond is 55%, and the light-emitting efficiency is still 43% after more than 20 times of cyclic tests.
Example 4
The preparation method of the piezochromic aggregation-induced emission molecule containing the halogen bond comprises the following specific steps:
(1) adding 3, 6-dimethoxycarbazole, p-iodobenzoyl chloride, potassium hydroxide, 18-crown-6, cuprous iodide and o-dichlorobenzene into a round-bottom flask, vacuumizing at-25 deg.C under refrigeration, introducing nitrogen for 4 times, and stirring at 200 deg.C under reflux for 180 hr; after the reaction is finished, repeatedly washing the reaction system by using acid liquor with the mass concentration of 5%, extracting for 3 times by using dichloromethane, drying by using a drying agent, then carrying out rotary evaporation to remove the solvent, and carrying out column chromatography separation to obtain an intermediate product;
wherein the mass ratio of the 3, 6-dimethoxycarbazole, the p-iodobenzoyl chloride, the potassium hydroxide, the 18-crown-6, the cuprous iodide and the desiccant is 1:1.6:60:0.6:0.6: 60; the volume ratio of the o-dichlorobenzene to the acid solution to the dichloromethane is 1:16: 16; the acid solution is hydroiodic acid; the drying agent is anhydrous sodium sulfate;
(2) adding the intermediate product prepared in the step (1), and (benzene-1, 2,3,4,5, 6-hexa-yl) hexa-acetonitrile into a round-bottom flask, vacuumizing and introducing nitrogen for 5 times, adding 2-propanol and a tetrahydrofuran solution with the water content of 0.004%, stirring and heating to 65 ℃, injecting a tetrahydrofuran solution of 10mmol/L potassium-2-propoxide, and reacting with tetrabutylammonium hydroxide for 4 hours; pouring the system into acetic acid acidified methanol after the reaction is finished, and performing suction filtration and column chromatography separation to obtain the final piezochromic aggregation-induced emission molecule containing the halogen bond;
wherein the mass ratio of the intermediate product, (benzene-1, 2,3,4,5, 6-hexa-yl) hexaacetonitrile to the potassium 2-propoxide is 6.1:1: 12; the volume ratio of 2-propanol, dried tetrahydrofuran, tetrabutylammonium hydroxide and acetic acid acidified methanol is 1:0.8:0.10: 12.
The hydrogen spectrogram of the prepared piezochromic aggregation-induced emission molecule containing the halogen bond is shown in figure 4, and the structural formula of the prepared piezochromic aggregation-induced emission molecule consists of a core structure and 6 branch structures connected with the core structure; the structures of all branch structures connected with the same core structure are the same; the core structure is
Figure 126219DEST_PATH_IMAGE007
The branch structure is
Figure 902545DEST_PATH_IMAGE016
，R1is-Cl, R2is-CH3(ii) a Wherein represents the position where the core structure and the branch structure are connected; the piezochromic aggregation-induced emission molecule containing the halogen bond has the characteristic of generating near infrared light under the pressure effect of 8-15 GPa; the piezochromic aggregation-induced emission molecule containing the halogen bond has no fluorescence emission in tetrahydrofuran, and has fluorescence emission in a mixed solution of tetrahydrofuran and water with the volume ratio of 9-99: 1; as shown in fig. 16, when the applied pressure was 13.5GPa, the maximum emission peak position of the piezochromic aggregation-inducing luminescent molecule containing a halogen bond was 719nm, and the emission intensity decreased with the pressure action time, the pressure varied linearly with the maximum emission peak position; after the external pressure is removed, the maximum emission peak position and the emission intensity of the piezochromic aggregation-induced emission molecule containing the halogen bond are restored to the initial state; when the applied pressure is 17MPa, the crystal structure of the piezochromic aggregation-induced emission molecule containing the halogen bond is changed; after the external pressure is removed, the crystal structure of the piezochromic aggregation-induced emission molecule containing the halogen bond is recovered to the initial state after 45 min; the light-emitting efficiency of the piezochromic aggregation-induced emission molecule containing the halogen bond is 58%, and the light-emitting efficiency is still 46% after more than 20 times of cyclic tests.
Example 5
The preparation method of the piezochromic aggregation-induced emission molecule containing the halogen bond comprises the following specific steps:
(1) adding carbazole derivative, p-iodobenzoyl fluoride, potassium carbonate, 18-crown-6, cuprous iodide and o-dichlorobenzene into a round-bottom flask, vacuumizing and introducing nitrogen for 4 times under a freezing condition of-25 ℃, and stirring and refluxing for 60 hours at 180 ℃; after the reaction is finished, repeatedly washing the reaction system by using acid liquor with the mass concentration of 5%, extracting for 3 times by using dichloromethane, drying by using a drying agent, then carrying out rotary evaporation to remove the solvent, and carrying out column chromatography separation to obtain an intermediate product;
wherein the mass ratio of the carbazole derivative, the p-iodobenzoyl fluoride, the potassium carbonate, the 18-crown-6, the cuprous iodide and the drying agent is 1:1.25:25:0.25:0.25: 40; the volume ratio of the o-dichlorobenzene to the acid solution to the dichloromethane is 1:12: 12; the acid solution is hydroiodic acid; the drying agent is anhydrous calcium chloride; the structural formula of the carbazole derivative is as follows:
Figure 324299DEST_PATH_IMAGE023
(2) the intermediate product prepared in the step (1),
Figure 524948DEST_PATH_IMAGE024
Adding into a round-bottom flask, vacuumizing and introducing nitrogen for 4 times, adding 2-propanol and a tetrahydrofuran solution with the water content of 0.004%, heating to 50 ℃ while stirring, injecting the tetrahydrofuran solution of potassium 2-propoxide with the concentration of 4mmol/L, and reacting with tetrabutylammonium hydroxide for 2 hours; pouring the system into acetic acid acidified methanol after the reaction is finished, and performing suction filtration and column chromatography separation to obtain the final piezochromic aggregation-induced emission molecule containing the halogen bond;
wherein, the intermediate product,
Figure 664943DEST_PATH_IMAGE024
The mass ratio of 2-potassium propoxide is 2.4:1: 7; the volume ratio of 2-propanol, dried tetrahydrofuran, tetrabutylammonium hydroxide and acetic acid acidified methanol is 1:0.65:0.05: 6.
The hydrogen spectrogram of the prepared piezochromic aggregation-induced emission molecule containing the halogen bond is shown in figure 5, and the structural formula of the prepared piezochromic aggregation-induced emission molecule consists of a core structure and two branch structures connected with the core structure; the structures of all branch structures connected with the same core structure are the same; the core structure is
Figure 244960DEST_PATH_IMAGE008
The branch structure is
Figure 786800DEST_PATH_IMAGE017
，R1is-F, R3Is composed of
Figure 161280DEST_PATH_IMAGE022
(ii) a Wherein represents the position where the core structure and the branch structure are connected; the piezochromic aggregation-induced emission molecule containing the halogen bond has the characteristic of generating near infrared light under the pressure effect of 8-15 GPa; the piezochromic aggregation-induced emission molecule containing the halogen bond has no fluorescence emission in tetrahydrofuran, and has fluorescence emission in a mixed solution of tetrahydrofuran and water with the volume ratio of 9-99: 1; as shown in fig. 17, when the applied pressure is 13GPa, the maximum emission peak position of the piezochromic aggregation-inducing luminescent molecule containing a halogen bond is 722nm, and the emission intensity decreases with the pressure action time, the pressure and the change of the maximum emission peak position are in a linear relationship; after the external pressure is removed, the maximum emission peak position and the emission intensity of the piezochromic aggregation-induced emission molecule containing the halogen bond are restored to the initial state; when the applied pressure is 16MPa, the crystal structure of the piezochromic aggregation-induced emission molecule containing the halogen bond is changed; after the external pressure is removed, the crystal structure of the piezochromic aggregation-induced emission molecule containing the halogen bond is recovered to the initial state after 40 min; the light-emitting efficiency of the piezochromic aggregation-induced emission molecule containing the halogen bond is 60%, and the light-emitting efficiency is still 50% after more than 20 times of cyclic tests.
Example 6
The preparation method of the piezochromic aggregation-induced emission molecule containing the halogen bond comprises the following specific steps:
(1) adding 2,4,5, 7-tetramethyl carbazole, p-iodobenzoyl chloride, potassium carbonate, 18-crown-6, cuprous iodide and o-dichlorobenzene into a round-bottom flask, vacuumizing at-25 ℃ under a refrigeration condition, introducing nitrogen for 4 times, and stirring and refluxing at 180 ℃ for 60 hours; after the reaction is finished, repeatedly washing the reaction system by using acid liquor with the mass concentration of 5%, extracting for 3 times by using dichloromethane, drying by using a drying agent, then carrying out rotary evaporation to remove the solvent, and carrying out column chromatography separation to obtain an intermediate product;
wherein the mass ratio of the 2,4,5, 7-tetramethyl carbazole to the p-iodobenzoyl chloride to the potassium carbonate to the 18-crown-6 to the cuprous iodide to the drying agent is 1:1.2:20:0.2:0.2: 30; the volume ratio of the o-dichlorobenzene to the acid solution to the dichloromethane is 1:12: 12; the acid solution is hydrochloric acid; the drying agent is anhydrous magnesium sulfate;
(2) the intermediate product prepared in the step (1),
Figure 788571DEST_PATH_IMAGE025
Adding into a round-bottom flask, vacuumizing and introducing nitrogen for 4 times, adding 2-propanol and a tetrahydrofuran solution with the water content of 0.004%, heating to 46 ℃ under stirring, injecting the tetrahydrofuran solution of potassium 2-propoxide with the concentration of 5mmol/L, and reacting with tetrabutylammonium hydroxide for 2 hours; pouring the system into acetic acid acidified methanol after the reaction is finished, and performing suction filtration and column chromatography separation to obtain the final piezochromic aggregation-induced emission molecule containing the halogen bond;
wherein, the intermediate product,
Figure 906699DEST_PATH_IMAGE025
The mass ratio of 2-potassium propoxide is 2.1:1: 6; the volume ratio of 2-propanol, dried tetrahydrofuran, tetrabutylammonium hydroxide and acetic acid acidified methanol is 1:0.6:0.04: 5.
The hydrogen spectrogram of the prepared piezochromic aggregation-induced emission molecule containing the halogen bond is shown in figure 6, and the structural formula of the prepared piezochromic aggregation-induced emission molecule consists of a core structure and two branch structures connected with the core structure; the structures of all branch structures connected with the same core structure are the same; the core structure is
Figure 303046DEST_PATH_IMAGE009
The branch structure is
Figure 848428DEST_PATH_IMAGE017
，R1is-Cl, R3is-CH3(ii) a Wherein represents the position where the core structure and the branch structure are connected; the piezochromic aggregation-induced emission molecule containing the halogen bond has the characteristic of generating near infrared light under the pressure effect of 8-15 GPa; halogen bond-containing piezochromic aggregation-induced emission moleculeNo fluorescence emission exists in the hydrogen furan, and the fluorescence emission exists in a mixed solution of tetrahydrofuran and water with the volume ratio of 9-99: 1; as shown in fig. 18, when the applied pressure was 12.8GPa, the maximum emission peak position of the piezochromic aggregation-inducing luminescent molecule containing a halogen bond was 728nm, and the emission intensity decreased with the pressure action time, the pressure varied linearly with the maximum emission peak position; after the external pressure is removed, the maximum emission peak position and the emission intensity of the piezochromic aggregation-induced emission molecule containing the halogen bond are restored to the initial state; when the applied pressure is 15MPa, the crystal structure of the piezochromic aggregation-induced emission molecule containing the halogen bond is changed; after the external pressure is removed, the crystal structure of the piezochromic aggregation-induced emission molecule containing the halogen bond is recovered to the initial state after 38 min; the light-emitting efficiency of the piezochromic aggregation-induced emission molecule containing the halogen bond is 62%, and the light-emitting efficiency is still 53% after more than 20 times of cyclic tests.
Example 7
The preparation method of the piezochromic aggregation-induced emission molecule containing the halogen bond comprises the following specific steps:
(1) adding 2,4,5, 7-tetramethoxycarbazole, p-iodobenzoyl bromide, potassium carbonate, 18-crown-6, cuprous iodide and o-dichlorobenzene into a round-bottom flask, vacuumizing at-25 deg.C under refrigeration, introducing nitrogen for 4 times, and stirring at 200 deg.C under reflux for 110 h; after the reaction is finished, repeatedly washing the reaction system by using acid liquor with the mass concentration of 7%, extracting for 3 times by using dichloromethane, drying by using a drying agent, then carrying out rotary evaporation to remove the solvent, and carrying out column chromatography separation to obtain an intermediate product;
wherein the mass ratio of the 2,4,5, 7-tetramethoxycarbazole to the p-iodobenzoyl chloride to the potassium carbonate to the 18-crown-6 to the cuprous iodide to the drying agent is 1:1.5:48:0.48:0.48: 120; the volume ratio of the o-dichlorobenzene to the acid solution to the dichloromethane is 1:14: 14; the acid solution is hydrochloric acid; the drying agent is anhydrous magnesium sulfate;
(2) the intermediate product prepared in the step (1),
Figure 963014DEST_PATH_IMAGE026
Adding into round bottom flask, vacuumizing, introducing nitrogen for 4 times, adding 2-propanol and tetrahydrofuran solution with water content of 0.004%, and stirringHeating to 56 ℃, injecting a tetrahydrofuran solution of potassium 2-propoxide with the concentration of 6mmol/L, and reacting with tetrabutylammonium hydroxide for 2 hours; pouring the system into acetic acid acidified methanol after the reaction is finished, and performing suction filtration and column chromatography separation to obtain the final piezochromic aggregation-induced emission molecule containing the halogen bond;
wherein, the intermediate product,
Figure 619255DEST_PATH_IMAGE026
The mass ratio of 2-potassium propoxide is 4.1:1: 16; the volume ratio of 2-propanol, dried tetrahydrofuran, tetrabutylammonium hydroxide and acetic acid acidified methanol is 1:0.8:0.08: 8.
The hydrogen spectrogram of the prepared piezochromic aggregation-induced emission molecule containing the halogen bond is shown in figure 7, and the structural formula of the prepared piezochromic aggregation-induced emission molecule consists of a core structure and 4 branch structures connected with the core structure; the structures of all branch structures connected with the same core structure are the same; the core structure is
Figure 135687DEST_PATH_IMAGE010
The branch structure is
Figure 851970DEST_PATH_IMAGE017
；R1is-Br, R3is-OCH3(ii) a Wherein represents the position where the core structure and the branch structure are connected; the piezochromic aggregation-induced emission molecule containing the halogen bond has the characteristic of generating near infrared light under the pressure effect of 8-15 GPa; the piezochromic aggregation-induced emission molecule containing the halogen bond has no fluorescence emission in tetrahydrofuran, and has fluorescence emission in a mixed solution of tetrahydrofuran and water with the volume ratio of 9-99: 1; as shown in fig. 19, when the applied pressure is 12GPa, the maximum emission peak position of the piezochromic aggregation-induced emission molecule containing the halogen bond is 730nm, and the emission intensity decreases with the pressure action time, and the pressure and the change of the maximum emission peak position are in a linear relationship; after the external pressure is removed, the maximum emission peak position and the emission intensity of the piezochromic aggregation-induced emission molecule containing the halogen bond are restored to the initial state; when the applied pressure is 15.5MPa, the crystal structure of the piezochromic aggregation-induced emission molecule containing the halogen bond is changed; remove the outsideAfter the pressure intensity is reached, the crystal structure of the piezochromic aggregation-induced emission molecule containing the halogen bond is restored to the initial state after 33 min; the light-emitting efficiency of the piezochromic aggregation-induced emission molecule containing the halogen bond is 65%, and the light-emitting efficiency is still 55% after more than 20 times of cyclic tests.
Example 8
The preparation method of the piezochromic aggregation-induced emission molecule containing the halogen bond comprises the following specific steps:
(1) adding carbazole, p-iodobenzoyl chloride, potassium carbonate, 18-crown-6, cuprous iodide and o-dichlorobenzene into a round-bottom flask, vacuumizing and introducing nitrogen for 4 times under a freezing condition of-25 ℃, and stirring and refluxing for 88 hours at 190 ℃;
Figure 453852DEST_PATH_IMAGE017
after the reaction is finished, repeatedly washing the reaction system by using acid liquor with the mass concentration of 5%, extracting for 3 times by using dichloromethane, drying by using a drying agent, then carrying out rotary evaporation to remove the solvent, and carrying out column chromatography separation to obtain an intermediate product;
wherein the mass ratio of carbazole, p-iodobenzoyl chloride, potassium carbonate, 18-crown-6, cuprous iodide and drying agent is 1:1.2:20:0.2:0.2: 30; the volume ratio of the o-dichlorobenzene to the acid solution to the dichloromethane is 1:16.5: 16.5; the acid solution is hydrochloric acid; the drying agent is anhydrous magnesium sulfate;
(2) adding the intermediate product prepared in the step (1)
Figure 913784DEST_PATH_IMAGE027
Putting the mixture into a round-bottom flask, vacuumizing and introducing nitrogen for 4 times, adding 2-propanol and a tetrahydrofuran solution with the water content of 0.004%, heating to 66 ℃ under stirring, injecting the tetrahydrofuran solution of potassium 2-propoxide with the concentration of 7mmol/L, and reacting with tetrabutylammonium hydroxide for 2 hours; pouring the system into acetic acid acidified methanol after the reaction is finished, and performing suction filtration and column chromatography separation to obtain the final piezochromic aggregation-induced emission molecule containing the halogen bond;
wherein, the intermediate product,
Figure 446176DEST_PATH_IMAGE027
The amount ratio of the 2-potassium propoxide is 51: 10; the volume ratio of 2-propanol, dried tetrahydrofuran, tetrabutylammonium hydroxide and acetic acid acidified methanol is 1:1.1:0.12: 15.
The hydrogen spectrogram of the prepared piezochromic aggregation-induced emission molecule containing the halogen bond is shown in figure 8, and the structural formula of the prepared piezochromic aggregation-induced emission molecule consists of a core structure and 4 branch structures connected with the core structure; the structures of all branch structures connected with the same core structure are the same; the core structure is
Figure 457994DEST_PATH_IMAGE011
The branch structure is
Figure 422539DEST_PATH_IMAGE017
，R1is-Cl, R3is-H; wherein represents the position where the core structure and the branch structure are connected; the piezochromic aggregation-induced emission molecule containing the halogen bond has the characteristic of generating near infrared light under the pressure effect of 8-15 GPa; the piezochromic aggregation-induced emission molecule containing the halogen bond has no fluorescence emission in tetrahydrofuran, and has fluorescence emission in a mixed solution of tetrahydrofuran and water with the volume ratio of 9-99: 1; as shown in fig. 20, when the applied pressure was 11.6GPa, the maximum emission peak position of the piezochromic aggregation-inducing luminescent molecule containing a halogen bond was 738nm, and the emission intensity decreased with the pressure action time, the pressure varied linearly with the maximum emission peak position; after the external pressure is removed, the maximum emission peak position and the emission intensity of the piezochromic aggregation-induced emission molecule containing the halogen bond are restored to the initial state; when the applied pressure is 14MPa, the crystal structure of the piezochromic aggregation-induced emission molecule containing the halogen bond is changed; after the external pressure is removed, the crystal structure of the piezochromic aggregation-induced emission molecule containing the halogen bond is recovered to the initial state after 30 min; the light-emitting efficiency of the piezochromic aggregation-induced emission molecule containing the halogen bond is 70%, and the light-emitting efficiency is still 60% after more than 20 times of cyclic tests.
Example 9
The preparation method of the piezochromic aggregation-induced emission molecule containing the halogen bond comprises the following specific steps:
(1) adding 3, 6-dimethylcarbazole, p-iodobenzoyl chloride, potassium carbonate, 18-crown-6, cuprous iodide and o-dichlorobenzene to a round-bottom flask, vacuumizing and introducing nitrogen for 4 times under a refrigeration condition of-25 ℃, and stirring and refluxing for 100 hours at 195 ℃; after the reaction is finished, repeatedly washing the reaction system by using acid liquor with the mass concentration of 5%, extracting for 3 times by using dichloromethane, drying by using a drying agent, then removing the solvent by rotary evaporation, and obtaining an intermediate product by column chromatography separation;
wherein the mass ratio of the 3, 6-dimethylcarbazole, the p-iodobenzoyl chloride, the potassium carbonate, the 18-crown-6, the cuprous iodide, the 2,3,5, 6-tetrachloro-1, 4-diazine and the drying agent is 1:1.6:60:0.6:0.6: 120; the volume ratio of the o-dichlorobenzene to the acid solution to the dichloromethane is 1:17: 17; the acid solution is hydrochloric acid; the drying agent is anhydrous magnesium sulfate;
(2) the intermediate product prepared in the step (1),
Figure 810795DEST_PATH_IMAGE028
Adding into a round-bottom flask, vacuumizing and introducing nitrogen for 4 times, adding 2-propanol and a tetrahydrofuran solution with the water content of 0.004%, heating to 55 ℃ under stirring, injecting the tetrahydrofuran solution of potassium 2-propoxide with the concentration of 7mmol/L, and reacting with tetrabutylammonium hydroxide for 3 hours; pouring the system into acetic acid acidified methanol after the reaction is finished, and performing suction filtration and column chromatography separation to obtain the final piezochromic aggregation-induced emission molecule containing the halogen bond;
wherein, the intermediate product,
Figure 177185DEST_PATH_IMAGE028
The mass ratio of 2-potassium propoxide is 4.4:1: 8.5; the volume ratio of 2-propanol, dried tetrahydrofuran, tetrabutylammonium hydroxide and acetic acid acidified methanol is 1:0.8:0.12: 20.
The hydrogen spectrogram of the prepared piezochromic aggregation-induced emission molecule containing the halogen bond is shown in figure 9, and the structural formula of the prepared piezochromic aggregation-induced emission molecule consists of a core structure and 4 branch structures connected with the core structure; the structures of all branch structures connected with the same core structure are the same; the core structure is
Figure 235271DEST_PATH_IMAGE012
The branch structure is
Figure 218271DEST_PATH_IMAGE016
，R1is-Cl, R2is-CH3(ii) a Wherein represents the position where the core structure and the branch structure are connected; the piezochromic aggregation-induced emission molecule containing the halogen bond has the characteristic of generating near infrared light under the pressure effect of 8-15 GPa; the piezochromic aggregation-induced emission molecule containing the halogen bond has no fluorescence emission in tetrahydrofuran, and has fluorescence emission in a mixed solution of tetrahydrofuran and water with the volume ratio of 9-99: 1; as shown in fig. 21, when the applied pressure is 11GPa, the maximum emission peak position of the piezochromic aggregation-inducing luminescent molecule containing a halogen bond is 742nm, and the emission intensity decreases with the time of the pressure action, and the pressure and the change of the maximum emission peak position are in a linear relationship; after the external pressure is removed, the maximum emission peak position and the emission intensity of the piezochromic aggregation-induced emission molecule containing the halogen bond are restored to the initial state; when the applied pressure is 13.8MPa, the crystal structure of the piezochromic aggregation-induced emission molecule containing the halogen bond is changed; after the external pressure is removed, the crystal structure of the piezochromic aggregation-induced emission molecule containing the halogen bond is recovered to the initial state after 25 min; the light-emitting efficiency of the piezochromic aggregation-induced emission molecule containing the halogen bond is 72%, and the light-emitting efficiency is still 62% after more than 20 times of cyclic tests.
Example 10
The preparation method of the piezochromic aggregation-induced emission molecule containing the halogen bond comprises the following specific steps:
(1) adding 2,4,5, 7-tetramethoxycarbazole, p-iodobenzoyl chloride, potassium carbonate, 18-crown-6, cuprous iodide and o-dichlorobenzene into a round-bottom flask, vacuumizing at-25 deg.C under refrigeration, introducing nitrogen for 4 times, and stirring at 193 deg.C under reflux for 60 hr; after the reaction is finished, repeatedly washing the reaction system by using acid liquor with the mass concentration of 5%, extracting for 3 times by using dichloromethane, drying by using a drying agent, then carrying out rotary evaporation to remove the solvent, and carrying out column chromatography separation to obtain an intermediate product;
wherein the mass ratio of the 2,4,5, 7-tetramethoxycarbazole to the p-iodobenzoyl chloride to the potassium carbonate to the 18-crown-6 to the cuprous iodide to the drying agent is 1:1.5:50:0.5:0.5: 50; the volume ratio of the o-dichlorobenzene to the acid solution to the dichloromethane is 1:16: 16; the acid solution is hydrochloric acid; the drying agent is anhydrous magnesium sulfate;
(2) the intermediate product prepared in the step (1),
Figure 551163DEST_PATH_IMAGE029
Adding into a round-bottom flask, vacuumizing and introducing nitrogen for 4 times, adding 2-propanol and a tetrahydrofuran solution with the water content of 0.004%, heating to 58 ℃ while stirring, injecting a tetrahydrofuran solution of potassium 2-propoxide with the concentration of 7.5mmol/L, and reacting with tetrabutylammonium hydroxide for 2.5 hours; pouring the system into acetic acid acidified methanol after the reaction is finished, and performing suction filtration and column chromatography separation to obtain the final piezochromic aggregation-induced emission molecule containing the halogen bond;
wherein, the intermediate product,
Figure 568798DEST_PATH_IMAGE029
The mass ratio of 2-potassium propoxide is 4.8:1: 7.5; the volume ratio of 2-propanol, dried tetrahydrofuran, tetrabutylammonium hydroxide and acetic acid acidified methanol is 1:0.6:0.065: 7.
The hydrogen spectrogram of the prepared piezochromic aggregation-induced emission molecule containing the halogen bond is shown in figure 10, and the structural formula of the prepared piezochromic aggregation-induced emission molecule consists of a core structure and 4 branch structures connected with the core structure; the structures of all branch structures connected with the same core structure are the same; the core structure is
Figure 263697DEST_PATH_IMAGE013
The branch structure is
Figure 140517DEST_PATH_IMAGE017
，R1is-Cl, R3is-CH3(ii) a Wherein represents the position where the core structure and the branch structure are connected; the piezochromic aggregation-induced emission molecule containing the halogen bond has the characteristic of generating near infrared light under the pressure effect of 8-15 GPa; the piezochromic aggregation-induced emission molecule containing the halogen bond has no fluorescence emission in tetrahydrofuran, and has fluorescence emission in a mixed solution of tetrahydrofuran and water with the volume ratio of 9-99: 1; as shown in FIG. 22, the piezochromic aggregation-induced emission of light containing a halogen bond was observed when the applied pressure was 10GPaThe maximum emission peak position of the molecule is 748nm, the emission intensity is reduced along with the action time of the pressure intensity, and the pressure intensity and the change of the maximum emission peak position are in a linear relation; after the external pressure is removed, the maximum emission peak position and the emission intensity of the piezochromic aggregation-induced emission molecule containing the halogen bond are restored to the initial state; when the applied pressure is 13MPa, the crystal structure of the piezochromic aggregation-induced emission molecule containing the halogen bond is changed; after the external pressure is removed, the crystal structure of the piezochromic aggregation-induced emission molecule containing the halogen bond is recovered to the initial state after 20 min; the light-emitting efficiency of the piezochromic aggregation-induced emission molecule containing the halogen bond is 74%, and the light-emitting efficiency is still 65% after more than 20 times of cyclic tests.
Example 11
The preparation method of the piezochromic aggregation-induced emission molecule containing the halogen bond comprises the following specific steps:
(1) adding 3, 6-dimethoxycarbazole, p-iodobenzoyl bromide, potassium carbonate, 18-crown-6, cuprous iodide and o-dichlorobenzene into a round-bottom flask, vacuumizing at-25 deg.C under refrigeration, introducing nitrogen for 4 times, and stirring at 193 deg.C under reflux for 80 hr; after the reaction is finished, repeatedly washing the reaction system by using acid liquor with the mass concentration of 5%, extracting for 3 times by using dichloromethane, drying by using a drying agent, then carrying out rotary evaporation to remove the solvent, and carrying out column chromatography separation to obtain an intermediate product;
wherein the mass ratio of the 3, 6-dimethoxycarbazole, the p-iodobenzoyl bromide, the potassium carbonate, the 18-crown-6, the cuprous iodide and the desiccant is 1:1.38:38:0.38:0.38: 88; the volume ratio of the acid solution to the dichloromethane is 1:13.8: 13.8; the acid solution is hydrochloric acid; the drying agent is anhydrous magnesium sulfate;
(2) the intermediate product prepared in the step (1),
Figure 73838DEST_PATH_IMAGE030
Adding into a round-bottom flask, vacuumizing and introducing nitrogen for 4 times, adding 2-propanol and a tetrahydrofuran solution with the water content of 0.004%, heating to 54 ℃ while stirring, injecting the tetrahydrofuran solution of potassium 2-propoxide with the concentration of 6mmol/L, and reacting with tetrabutylammonium hydroxide for 3.5 hours; pouring the system into acetic acid acidified methanol after the reaction is finished, and performing suction filtration and column chromatography separation to obtain the final productA piezochromic aggregation-induced emission molecule containing a halogen bond;
wherein, the intermediate product,
Figure 86924DEST_PATH_IMAGE030
The mass ratio of 2-potassium propoxide is 2.8:1: 6; the volume ratio of 2-propanol, dried tetrahydrofuran, tetrabutylammonium hydroxide and acetic acid acidified methanol is 1:0.68:0.048: 15.
The hydrogen spectrogram of the prepared piezochromic aggregation-induced emission molecule containing the halogen bond is shown in figure 11, and the structural formula of the prepared piezochromic aggregation-induced emission molecule consists of a core structure and 3 branch structures connected with the core structure; the structures of all branch structures connected with the same core structure are the same; the core structure is
Figure 221233DEST_PATH_IMAGE014
The branch structure is
Figure 847999DEST_PATH_IMAGE016
，R1is-Br, R2is-OCH3(ii) a Wherein represents the position where the core structure and the branch structure are connected; the piezochromic aggregation-induced emission molecule containing the halogen bond has the characteristic of generating near infrared light under the pressure effect of 8-15 GPa; the piezochromic aggregation-induced emission molecule containing the halogen bond has no fluorescence emission in tetrahydrofuran, and has fluorescence emission in a mixed solution of tetrahydrofuran and water with the volume ratio of 9-99: 1; as shown in fig. 23, when the applied pressure was 9.3GPa, the maximum emission peak position of the piezochromic aggregation-inducing luminescent molecule containing a halogen bond was 750nm, and the emission intensity decreased with the pressure action time, the pressure and the change of the maximum emission peak position were in a linear relationship; after the external pressure is removed, the maximum emission peak position and the emission intensity of the piezochromic aggregation-induced emission molecule containing the halogen bond are restored to the initial state; when the applied pressure is 11.4MPa, the crystal structure of the piezochromic aggregation-induced emission molecule containing the halogen bond is changed; after the external pressure is removed, the crystal structure of the piezochromic aggregation-induced emission molecule containing the halogen bond is recovered to the initial state after 12 min; the light-emitting efficiency of the piezochromic aggregation-induced emission molecule containing the halogen bond is 78 percent, and the light-emitting molecule is tested and emitted after more than 20 times of circulationThe light efficiency is still 66%.
Example 12
The preparation method of the piezochromic aggregation-induced emission molecule containing the halogen bond comprises the following specific steps:
(1) adding carbazole, p-iodobenzoyl chloride, potassium carbonate, 18-crown-6, cuprous iodide and o-dichlorobenzene into a round-bottom flask, vacuumizing and introducing nitrogen for 4 times under a freezing condition of-25 ℃, and stirring and refluxing for 240 hours at 210 ℃; after the reaction is finished, repeatedly washing the reaction system by using acid liquor with the mass concentration of 5%, extracting for 3 times by using dichloromethane, drying by using a drying agent, then carrying out rotary evaporation to remove the solvent, and carrying out column chromatography separation to obtain an intermediate product;
wherein the mass ratio of carbazole, p-iodobenzoyl chloride, potassium carbonate, 18-crown-6, cuprous iodide and drying agent is 1:2:64:0.64:0.64: 120; the volume ratio of the o-dichlorobenzene to the acid solution to the dichloromethane is 1:17: 17; the acid solution is hydrochloric acid; the drying agent is anhydrous magnesium sulfate;
(2) the intermediate product prepared in the step (1),
Figure 929219DEST_PATH_IMAGE031
Adding the mixture into a round-bottom flask, vacuumizing and introducing nitrogen for 4 times, adding 2-propanol and a tetrahydrofuran solution with the water content of 0.004%, stirring, heating to 70 ℃, injecting the tetrahydrofuran solution of potassium 2-propoxide with the concentration of 12mmol/L, and reacting with tetrabutylammonium hydroxide for 6 hours; pouring the system into acetic acid acidified methanol after the reaction is finished, and performing suction filtration and column chromatography separation to obtain the final piezochromic aggregation-induced emission molecule containing the halogen bond;
wherein, the intermediate product,
Figure 187025DEST_PATH_IMAGE031
The mass ratio of 2-potassium propoxide is 4.4:1: 8; the volume ratio of 2-propanol, dried tetrahydrofuran, tetrabutylammonium hydroxide and acetic acid acidified methanol is 1:0.88:0.24: 20.
The hydrogen spectrogram of the prepared piezochromic aggregation-induced emission molecule containing the halogen bond is shown in figure 12, and the structural formula of the prepared piezochromic aggregation-induced emission molecule consists of a core structure and 4 branch structures connected with the core structure; with the same core structureThe structures of all the connected branch structures are the same; the core structure is
Figure 226656DEST_PATH_IMAGE015
The branch structure is
Figure 405965DEST_PATH_IMAGE017
，R1is-Cl, R3is-H; wherein represents the position where the core structure and the branch structure are connected; the piezochromic aggregation-induced emission molecule containing the halogen bond has the characteristic of generating near infrared light under the pressure effect of 8-15 GPa; the piezochromic aggregation-induced emission molecule containing the halogen bond has no fluorescence emission in tetrahydrofuran, and has fluorescence emission in a mixed solution of tetrahydrofuran and water with the volume ratio of 9-99: 1; as shown in fig. 24, when the applied pressure was 8GPa, the maximum emission peak position of the piezochromic aggregation-inducing luminescent molecule containing a halogen bond was 755nm, and the emission intensity decreased with the pressure action time, the pressure and the change of the maximum emission peak position were in a linear relationship; after the external pressure is removed, the maximum emission peak position and the emission intensity of the piezochromic aggregation-induced emission molecule containing the halogen bond are restored to the initial state; when the applied pressure is 10MPa, the crystal structure of the piezochromic aggregation-induced emission molecule containing the halogen bond is changed; after the external pressure is removed, the crystal structure of the piezochromic aggregation-induced emission molecule containing the halogen bond is recovered to the initial state after 10 min; the light-emitting efficiency of the piezochromic aggregation-induced emission molecule containing the halogen bond is 80%, and the light-emitting efficiency is still 70% after more than 20 times of cyclic tests.

Claims (7)

1. The piezochromic aggregation-induced emission molecule containing the halogen bond is characterized in that the structural formula consists of a core structure and at least two branch structures connected with the core structure;
the core structure is
Figure 849923DEST_PATH_IMAGE001
、
Figure 470261DEST_PATH_IMAGE002
、
Figure 606319DEST_PATH_IMAGE003
、
Figure 628502DEST_PATH_IMAGE004
、
Figure 421009DEST_PATH_IMAGE005
、
Figure 810533DEST_PATH_IMAGE006
、
Figure 422386DEST_PATH_IMAGE007
、
Figure 299076DEST_PATH_IMAGE008
、
Figure 324800DEST_PATH_IMAGE009
、
Figure 936041DEST_PATH_IMAGE010
、
Figure 603783DEST_PATH_IMAGE011
Or
Figure 866137DEST_PATH_IMAGE012
(ii) a The branch structure is
Figure 328343DEST_PATH_IMAGE013
Or
Figure 426880DEST_PATH_IMAGE014
Wherein R is1=
Figure 898312DEST_PATH_IMAGE015
X is F, Cl or Br; r2Is composed of
Figure 280752DEST_PATH_IMAGE016
、
Figure 648280DEST_PATH_IMAGE017
、
Figure 499692DEST_PATH_IMAGE018
Or
Figure 509236DEST_PATH_IMAGE019
；R3Is composed of
Figure 480603DEST_PATH_IMAGE016
、
Figure 550191DEST_PATH_IMAGE017
、
Figure 354811DEST_PATH_IMAGE018
Or
Figure 168046DEST_PATH_IMAGE019
；
In each formula, the position of the connection of the core structure and the branch structure is represented;
the piezochromic aggregation-induced emission molecule containing the halogen bond has the characteristic of generating near infrared light under the pressure effect of 8-15 GPa.
2. The piezochromic aggregation-inducing luminescent molecule comprising a halogen bond of claim 1 wherein each branch structure connected to the same core structure has the same structure.
3. The piezochromic aggregation-induced emission molecule comprising a halogen bond of claim 2 wherein the core structure is
Figure 993920DEST_PATH_IMAGE001
The branch structure is
Figure 499987DEST_PATH_IMAGE013
，R1is-Cl, R2is-CH3(ii) a Alternatively, the core structure is
Figure 919468DEST_PATH_IMAGE002
The branch structure is
Figure 146181DEST_PATH_IMAGE013
，R1is-Br, R2is-OCH3；
Alternatively, the core structure is
Figure 967506DEST_PATH_IMAGE003
The branch structure is
Figure 503530DEST_PATH_IMAGE013
，R1is-Cl, R2Is composed of
Figure 410306DEST_PATH_IMAGE019
(ii) a Alternatively, the core structure is
Figure 440710DEST_PATH_IMAGE004
The branch structure is
Figure 116542DEST_PATH_IMAGE013
，R1is-Cl, R2is-CH3(ii) a Alternatively, the core structure is
Figure 823467DEST_PATH_IMAGE005
The branch structure is
Figure 217539DEST_PATH_IMAGE014
，R1is-F, R3Is composed of
Figure 786055DEST_PATH_IMAGE019
(ii) a Alternatively, the core structure is
Figure 581972DEST_PATH_IMAGE006
The branch structure is
Figure 459798DEST_PATH_IMAGE014
，R1is-Cl, R3is-CH3(ii) a Alternatively, the core structure is
Figure 341167DEST_PATH_IMAGE012
The branch structure is
Figure 710444DEST_PATH_IMAGE014
，R1is-Br, R3is-OCH3(ii) a Alternatively, the core structure is
Figure 360868DEST_PATH_IMAGE008
The branch structure is
Figure 409595DEST_PATH_IMAGE014
，R1is-Cl, R3is-H;
alternatively, the core structure is
Figure 778260DEST_PATH_IMAGE009
The branch structure is
Figure 813212DEST_PATH_IMAGE013
，R1is-Cl, R2is-CH3；
Alternatively, the core structure is
Figure 459088DEST_PATH_IMAGE010
The branch structure is
Figure 554083DEST_PATH_IMAGE014
，R1is-Cl, R3is-CH3；
Alternatively, the core structure is
Figure 269098DEST_PATH_IMAGE011
The branch structure is
Figure 107741DEST_PATH_IMAGE013
，R1is-Br, R2is-OCH3；
Alternatively, the core structure is
Figure 608124DEST_PATH_IMAGE012
The branch structure is
Figure 874020DEST_PATH_IMAGE014
，R1is-Cl, R3is-H.
4. The piezochromic aggregation-induced emission molecule containing a halogen bond according to claim 3, wherein the piezochromic aggregation-induced emission molecule containing a halogen bond has no fluorescence emission in tetrahydrofuran and has fluorescence emission in a mixed solution of tetrahydrofuran and water at a volume ratio of 9-99: 1.
5. The piezochromic aggregation-inducing luminescent molecule containing the halogen bond as claimed in claim 3, wherein the maximum emission peak position of the piezochromic aggregation-inducing luminescent molecule containing the halogen bond is 700-755 nm when the applied pressure is 8-15 GPa, and the emission intensity decreases with the action time of the pressure, and the pressure and the change of the maximum emission peak position are in a linear relationship; after the external pressure is removed, the maximum emission peak position and the emission intensity of the piezochromic aggregation-induced emission molecule containing the halogen bond are restored to the initial state.
6. The piezochromic aggregation-induced emission molecule containing a halogen bond according to claim 3, wherein the crystal structure of the piezochromic aggregation-induced emission molecule containing a halogen bond is changed when the applied pressure is 10 to 20 MPa; after the external pressure is removed, the crystal structure of the piezochromic aggregation-induced emission molecule containing the halogen bond is recovered to the initial state after 10-60 min.
7. The piezochromic aggregation-induced emission molecule containing the halogen bond of claim 3, wherein the piezochromic aggregation-induced emission molecule containing the halogen bond has a luminous efficiency of 50% -80%, and the luminous efficiency is still 40% -70% after more than 20 times of cyclic tests.
CN202210393876.1A 2022-04-15 2022-04-15 Halogen bond-containing piezochromic aggregation-induced emission molecule Active CN114478357B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210393876.1A CN114478357B (en) 2022-04-15 2022-04-15 Halogen bond-containing piezochromic aggregation-induced emission molecule

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210393876.1A CN114478357B (en) 2022-04-15 2022-04-15 Halogen bond-containing piezochromic aggregation-induced emission molecule

Publications (2)

Publication Number Publication Date
CN114478357A true CN114478357A (en) 2022-05-13
CN114478357B CN114478357B (en) 2022-07-05

Family

ID=81489336

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210393876.1A Active CN114478357B (en) 2022-04-15 2022-04-15 Halogen bond-containing piezochromic aggregation-induced emission molecule

Country Status (1)

Country Link
CN (1) CN114478357B (en)

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103965865A (en) * 2014-05-05 2014-08-06 吉林大学 Preparation method and application of piezochromic material
CN104312576A (en) * 2014-09-01 2015-01-28 吉林大学 Piezochromic material, preparation method and applications thereof
CN106187817A (en) * 2016-07-29 2016-12-07 陕西师范大学 There is aggregation-induced emission character and the fluorescent material of piezallochromy character
CN108003859A (en) * 2017-12-19 2018-05-08 南京工业大学 Piezochromic fluorescent molecule and preparation method and application thereof
CN109336872A (en) * 2018-11-19 2019-02-15 天集化工助剂（沧州）有限公司 One kind has the preparation of the gathering induced luminescence material of light stability
CN113307727A (en) * 2021-05-26 2021-08-27 河北科技大学 Piezochromic tetraphenyl vinyl compound and preparation method and application thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103965865A (en) * 2014-05-05 2014-08-06 吉林大学 Preparation method and application of piezochromic material
CN104312576A (en) * 2014-09-01 2015-01-28 吉林大学 Piezochromic material, preparation method and applications thereof
CN106187817A (en) * 2016-07-29 2016-12-07 陕西师范大学 There is aggregation-induced emission character and the fluorescent material of piezallochromy character
CN108003859A (en) * 2017-12-19 2018-05-08 南京工业大学 Piezochromic fluorescent molecule and preparation method and application thereof
CN109336872A (en) * 2018-11-19 2019-02-15 天集化工助剂（沧州）有限公司 One kind has the preparation of the gathering induced luminescence material of light stability
CN113307727A (en) * 2021-05-26 2021-08-27 河北科技大学 Piezochromic tetraphenyl vinyl compound and preparation method and application thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
PARTHASARATHY GAYATHRI等: "Aggregation-enhanced emissive mechanofluorochromic carbazole-halogen positional isomers: tunable fluorescence via conformational polymorphism and crystallizationinduced fluorescence switching", 《CRYSTENGCOMM》 *
ZHONGWEI MAN等: "Highly Sensitive and Easily Recoverable Excitonic Piezochromic Fluorescent Materials for Haptic Sensors and Anti-Counterfeiting Applications", 《ADV. FUNCT. MATER.》 *

Also Published As

Publication number Publication date
CN114478357B (en) 2022-07-05

Similar Documents

Publication Publication Date Title
Gong et al. Twisted D–π–A solid emitters: efficient emission and high contrast mechanochromism
Zhu et al. A polymorphic fluorescent material with strong solid state emission and multi-stimuli-responsive properties
Fan et al. Organic luminogens bearing alkyl substituents: design flexibility, adjustable molecular packing, and optimized performance
Liang et al. Versatile functionalization of trifluoromethyl based deep blue thermally activated delayed fluorescence materials for organic light emitting diodes
CN111320638B (en) Star-shaped blue thermal activity delayed fluorescent material based on triazolotriazine and application thereof
Wang et al. Recent advances in mechanism of AIE mechanochromic materials
CN111808602A (en) Carbon quantum dot, method for synthesizing same, thin film, and electronic device
CN114478357B (en) Halogen bond-containing piezochromic aggregation-induced emission molecule
Bai et al. Extending the molecular conjugation of phosphorescence units to accurately modulate ultralong organic room temperature phosphorescence
Qu et al. Helically Chiral Donor–Acceptor Double Hetero [4] helicenes with Circularly Polarized Thermally Activated Delayed Fluorescence
Liu et al. A quinoxaline-based charge-transfer compound for efficient deep-red organic light emitting diodes
Mei et al. Accelerating PLQY and RISC rates in deep-blue TADF materials with the acridin-9 (10 H)-one acceptor by tuning the peripheral groups on carbazole donors
CN115745974A (en) Chiral near ultraviolet organic electroluminescent material, preparation method thereof and application thereof in CP-OLED
CN112266357A (en) Fluorescent material with space charge transfer effect and application thereof
CN104073247B (en) A kind of pendant aryl conjugation luminous organic material and preparation method thereof
CN107501164B (en) Bis-carbazole compound containing tetraphenylethylene structure and preparation and application thereof
CN115322291A (en) Organic ultralong room temperature phosphorescent nanofiber material and preparation method thereof
CN103951607B (en) A kind of steric hindrance type fluorenyl small molecule host material and preparation method
KR102415709B1 (en) Luminescent Liquid Crystalline Compounds with Chiral Flexible Spacer and Method for preparing the same
CN113493445B (en) Imidazolyl spiro derivative with aggregation-induced emission property and application thereof
CN114751900A (en) D-A type organic luminescent material and preparation method and application thereof
CN108530387B (en) Phenyl bridged and carboxyl terminated A1-π-A-D-A-π-A1BT type derivatives and preparation method thereof
CN111925391A (en) Organic long afterglow material containing triphenyl phosphine (oxide) and its preparation method and use method
CN114195699B (en) Organic small molecule chiral main material and application thereof
CN104725369A (en) Binary phenothiazine imidazole derivative, preparation method and organic light emitting device

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant
PE01 Entry into force of the registration of the contract for pledge of patent right

Denomination of invention: Photoluminescence Molecules Induced by Photochromic Aggregation Containing Halogen Bond

Effective date of registration: 20230222

Granted publication date: 20220705

Pledgee: Bank of Communications Co.,Ltd. Suzhou Yangtze River Delta integration Demonstration Zone Branch

Pledgor: Jiangsu new vision advanced functional fiber Innovation Center Co.,Ltd.

Registration number: Y2023980033198

PE01 Entry into force of the registration of the contract for pledge of patent right