CN111233753A - Preparation method of AIE metal organogel - Google Patents

Preparation method of AIE metal organogel Download PDF

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CN111233753A
CN111233753A CN202010094668.2A CN202010094668A CN111233753A CN 111233753 A CN111233753 A CN 111233753A CN 202010094668 A CN202010094668 A CN 202010094668A CN 111233753 A CN111233753 A CN 111233753A
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compound
metal
gel
aie
stirring
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肖唐鑫
刁凯
吴可慧
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Changzhou University
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/14—Macromolecular compounds
    • C09K2211/1441—Heterocyclic
    • C09K2211/1466—Heterocyclic containing nitrogen as the only heteroatom
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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
    • C09K2211/18—Metal complexes
    • C09K2211/185—Metal complexes of the platinum group, i.e. Os, Ir, Pt, Ru, Rh or Pd

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Abstract

A preparation method of an AIE active metal organic material, in particular to a novel bipyridyl compound based on bridging TPE, which forms the AIE active metal organic material through metal coordination-driven self-assembly. The gel shows strong heat repairability and degradability due to excellent dynamic reversibility of metal coordinate bonds. The invention has the following beneficial effects: the fluorescent material is formed by metal coordination-driven self-assembly, has simple preparation process and high yield, and also has a fluorescent effect; the AIE active metal organogel takes metal coordination acting force as a connecting point, so that the gel has thermal repair performance; due to the excellent dynamic reversibility of the metal coordination bond, the gel is degraded by adding triphenylphosphine.

Description

Preparation method of AIE metal organogel
Technical Field
The invention belongs to the field of synthesis of supramolecular luminescent materials, and particularly relates to a preparation method of AIE metal organogel.
Background
Conventional fluorescence chromophores exhibit reduced or no fluorescence when in the aggregate state, a phenomenon known as "concentration quenching" effect. The main cause of concentration quenching is related to the formation of aggregates, so the concentration quenching effect is often also called aggregation-induced fluorescence quenching (ACQ). In 2001, the Tang Ben faith topic group discovered a unique phenomenon: some silacyclopentadiene derivatives hardly emit light in solution, and the light emission is greatly enhanced in an aggregated state or after forming a solid. Since this luminescence enhancement is caused by aggregation, I have figuratively defined this phenomenon as "Aggregation Induced Emission (AIE)". Among them, TPE (tetraphenylethylene) is a classical AIE unit, widely used in many fields, and its structure is as follows:
Figure BDA0002384951420000011
in the present invention, we have selectively designed and synthesized a novel class of bipyridyl compounds based on bridged TPEs, which were found to still have AIE effects. And an AIE metal organogel is formed by metal coordination driven self-assembly. The gel shows strong heat repairability and degradability due to excellent dynamic reversibility of metal coordinate bonds.
Disclosure of Invention
The invention aims to synthesize a novel bipyridyl compound based on bridged TPE, and an AIE active metal organogel is formed through metal coordination-driven self-assembly. The gel has strong heat repairability and degradability.
The compound is a bipyridyl compound (denoted as compound E) based on bridged TPE, having the following chemical structure:
Figure BDA0002384951420000012
the synthetic route is as follows:
Figure BDA0002384951420000021
the synthesis method of the compound E comprises the following steps:
step 1, synthesis of compound a: adding 9-fluorenone into a three-neck flask under the atmosphere of nitrogen, adding dichloromethane, stirring for dissolving, and adding CBr4Slowly adding PPh3The addition of dichloromethane was continued, at which point the solution was brown in color. The reaction was stirred at 40 ℃ for 24 h. After the reaction was complete, stirring was stopped. Adding a large amount of petroleum ether into the liquid obtained by the reaction, and stirring while adding until the insoluble solid substances are not increased any more. Adding diatomite into the solid-liquid mixture, performing suction filtration, continuously washing the filter residue with petroleum ether until the filter residue does not contain the product, and spin-drying the collected filter liquorAnd (3) carrying out dry-method sample loading and column chromatography to obtain a faint yellow paper scrap sample solid, namely the compound A.
Step 2, synthesis of compound B: adding compound A, 4-methoxyphenylboronic acid into a three-neck flask under the atmosphere of nitrogen, stirring and dissolving the compound A, 4-methoxyphenylboronic acid and toluene, and adding K2CO3Adding appropriate amount of phase transfer catalyst methyl trioctyl ammonium chloride aqueous solution, stirring for 1 hr, adding catalyst Pd (PPh)3)4And reacting for 18 h. After the reaction was complete, the stirring was stopped. Adding DCM and a proper amount of water into the reaction solution for extraction until no yellow substance exists in the water phase, combining the organic phases, washing once again with water, collecting the organic phases, drying the organic phases with anhydrous sodium sulfate, carrying out rotary evaporation, carrying out dry-method sample loading, and carrying out column chromatography to obtain a yellow powdery solid, namely the compound B.
Step 3, synthesis of compound C: adding the compound B into a three-neck flask under the nitrogen atmosphere, drying dichloromethane, stirring and dissolving, and slowly dropwise adding BBr under an ice salt bath3And reacting at room temperature overnight, wherein the reaction solution is changed from bright yellow to reddish brown in the reaction process. After the reaction was complete, the stirring was stopped. Adding water for quenching, adding ethyl acetate for extraction, washing an organic phase with water, washing with a saturated sodium chloride aqueous solution, drying with anhydrous sodium sulfate, and spin-drying to obtain a yellow powdery solid, namely the compound C.
Step 4, synthesis of compound D: adding the compound C and dichloromethane into a three-neck flask under the nitrogen atmosphere, stirring, dropwise adding pyridine under ice bath, dissolving the solid, and then slowly dropwise adding Tf into the reaction solution2And O, raising the temperature to 25 ℃, and stirring for 12 hours. After the reaction was complete, stirring was stopped. Adding water and dichloromethane into the reaction solution, continuously washing the organic phase with water, collecting the organic phase, performing rotary evaporation, loading the sample by a dry method, and performing column chromatography to obtain a white acicular solid, namely the compound D.
Step 5, synthesis of compound E: under the nitrogen atmosphere, compound D, 4-pyridine boric acid is added into a three-neck flask, and toluene is stirred and dissolved. Then adding potassium carbonate aqueous solution and catalyst TBAB, Pd (PPh)3)4After the reaction was completed for 2 days, the stirring was stopped. Washing with water, washing with saturated sodium chloride aqueous solution, drying with anhydrous sodium sulfate, filtering, and rotary steamingAnd (4) carrying out dry loading. And eluting by column chromatography to obtain a light yellow powdery compound, namely the compound E.
The AIE active metal organogels are formed by metal coordination driven self-assembly, having the following structure:
Figure BDA0002384951420000031
the AIE metal organogel has thermal repairing performance due to the reversible effect of metal coordination acting force, can be changed into sol by heating and can be changed into gel by cooling, and has strong application prospect in thermal repairing materials.
As the coordination ability of the phosphorus ions and the metal ions is stronger, the linear structure of the gel can be destroyed and degraded by adding triphenyl phosphorus into the gel, so that the gel has degradability.
Through the synthesis of the steps, the beneficial effects of the invention are embodied in that:
(1) the AIE active metal organogel provided by the invention is formed by a bipyridyl compound based on bridged TPE through metal coordination-driven self-assembly, and has the advantages of simple preparation process, high yield and fluorescence effect.
(2) The compound E has aggregation-induced emission (AIE) phenomenon, does not fluoresce in a dilute solution state, and when metal ions Pd are slowly added2+Then, the metal ion coordinates with the compound E to inhibit the rotation of the benzene ring, and fluorescence appears in the solution state, and the fluorescence intensity also increases as the concentration of the metal ion and the compound E increases.
(3) The AIE active metal organogel takes metal coordination acting force as a connecting point, so that the gel has thermal repair performance and has strong application prospect in thermal repair materials.
(4) Due to the excellent dynamic reversibility of the metal coordination bond, the gel is degraded by adding triphenylphosphine.
Detailed Description
The invention will now be further described with reference to specific examples, which are intended to illustrate, but not to limit the invention further.
Example 1
Preparation of compound a: under nitrogen atmosphere, 3.60g of 9-fluorenone was added to a 500mL three-necked flask, 50mL of methylene chloride was added thereto, the mixture was dissolved by stirring, and 13.27g of CBr was added4Slowly adding 21.00g of PPh3An additional 130mL of methylene chloride was added, and the solution was brown. The reaction was stirred at 40 ℃ for 24 h. After the reaction was completed, the stirring was stopped, followed by post-treatment. Adding a large amount of petroleum ether into the liquid obtained by the reaction, and stirring while adding until the insoluble solid substances are not increased any more. And adding diatomite into the solid-liquid mixture, performing suction filtration, continuously washing filter residues with petroleum ether until the filter residues do not contain products, spin-drying the collected filter liquor, loading the filter liquor by a dry method, and performing column chromatography (eluent pure PE) to obtain 4.5g of light yellow paper scrap sample solid with the yield of 67%.
Preparation of compound B: under nitrogen atmosphere, a 500mL three-necked flask was charged with 4.20g of Compound A, 4.18g of 4-methoxyphenylboronic acid, and 50mL of toluene, 30mL of an aqueous solution containing 9.20g of potassium carbonate was added, an appropriate amount of an aqueous solution of phase transfer catalyst methyltrioctylammonium chloride was then added, and after stirring for 1 hour, the catalyst Pd (PPh)3)4And reacting for 18 h. After the reaction was complete, the stirring was stopped. DCM was added to the reaction solution and extracted with an appropriate amount of water until the aqueous phase was free of yellow material, the combined organic phases were washed once more with water, the organic phases were collected, dried over anhydrous sodium sulfate, rotary evaporated, dry loaded, and column chromatographed (eluent PE: DCM ═ 30:1 → 25:1 → 10:1) to give 4.20g of yellow powdery solid in 86% yield.
Preparation of compound C: under nitrogen atmosphere, 4.20g of Compound B was added to a 500mL three-necked flask, 200mL of dry dichloromethane was dissolved with stirring, and 6.70g of BBr was slowly added dropwise under ice salt bath3And reacting at room temperature overnight, wherein the reaction solution is changed from bright yellow to reddish brown in the reaction process. After the reaction was complete, the stirring was stopped. After quenching with water, ethyl acetate was added for extraction, and the organic phase was washed with water (50 mL. times.3), washed with saturated aqueous sodium chloride (50 mL. times.1), dried over anhydrous sodium sulfate, and spin-dried to give 3.70g of a yellow powdery solid in 95% yield.
Preparation of compound D: under nitrogen atmosphere, 725mg of compound C and 20mL of dichloromethane are added into a 250mL three-neck flask, stirring is carried out, 410mg of pyridine is dropwise added under ice bath, solid is dissolved, and then 1241mg of Tf is slowly and dropwise added into the reaction liquid2And O, raising the temperature to 25 ℃, and stirring for 12 hours. After the reaction was complete, stirring was stopped. Water and dichloromethane were added to the reaction solution, the organic phase was washed with water (50mL × 4) successively, the organic phase was collected, rotary evaporated, dry loaded, and column chromatographed (eluent PE: DCM ═ 10:1) to give 0.88g of white needle solid in 60% yield.
Preparation of compound E: under a nitrogen atmosphere, 0.60g of Compound D, 0.44g of 4-pyridineboronic acid and 50mL of toluene were charged into a 100mL three-necked flask and dissolved with stirring. 6mL of an aqueous solution containing 0.75g of potassium carbonate, 29.0mg of TBAB as a catalyst, and 0.10g of Pd (PPh)3)4After the reaction was completed for 2 days, the stirring was stopped. Water washing (25mL × 3), saturated sodium chloride aqueous solution washing (25mL × 1), drying over anhydrous sodium sulfate, filtration, rotary evaporation, dry loading, column chromatography (eluent PE: DCM ═ 2:1) gave 0.28g of the compound as a pale yellow powder with a yield of 70%.
Preparation of AIE active metal organogel: and (3) putting palladium acetate and the compound E into a chloroform solution (60mM) according to a molar ratio of 1:1, stirring at 45 ℃ to generate a viscous polymer solution, and cooling to room temperature to convert the viscous polymer solution into gel, thereby obtaining the target AIE active metal organic gel.
Although the embodiments of the present invention have been specifically described in the above examples, it will be understood by those skilled in the art that these are for illustration only and that various changes or modifications of the technical solution of the present invention and its embodiments may be made without departing from the spirit and scope of the present invention. The scope of the invention may be defined by the following claims.

Claims (3)

1. A novel bipyridyl compound based on bridged TPE has the following structure:
Figure FDA0002384951410000011
2. the compound can form an AIE active metal organic gel through metal coordination driven self-assembly, and has the following structure:
Figure FDA0002384951410000012
3. the gel of claim 2, wherein the gel emits bluish fluorescent light when excited by 365nm ultraviolet light.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115746321A (en) * 2022-11-01 2023-03-07 华中科技大学 Metal organic gel, preparation method and application thereof

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107325036A (en) * 2017-07-13 2017-11-07 长春海谱润斯科技有限公司 A kind of electroluminescent organic material and its organic luminescent device

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107325036A (en) * 2017-07-13 2017-11-07 长春海谱润斯科技有限公司 A kind of electroluminescent organic material and its organic luminescent device

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
HONGMIAO LI，等: "Coordination-Driven Terpyridyl Phosphine Pd(II) Gels", 《CHIN. J. CHEM.》 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115746321A (en) * 2022-11-01 2023-03-07 华中科技大学 Metal organic gel, preparation method and application thereof
CN115746321B (en) * 2022-11-01 2023-08-01 华中科技大学 Metal organic gel, preparation method and application thereof

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Application publication date: 20200605