CN112442054A - Preparation method of trimeric indenyl corrole-porphyrin-BODIPY star-shaped compound - Google Patents

Preparation method of trimeric indenyl corrole-porphyrin-BODIPY star-shaped compound Download PDF

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CN112442054A
CN112442054A CN201910821677.4A CN201910821677A CN112442054A CN 112442054 A CN112442054 A CN 112442054A CN 201910821677 A CN201910821677 A CN 201910821677A CN 112442054 A CN112442054 A CN 112442054A
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porphyrin
corrole
bodipy
indenyl
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徐海军
蔡方建
蒋浩
赵越
蔡正春
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Nanjing Forestry University
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Abstract

The invention discloses a structure of trimeric indenyl corrole-porphyrin-BODIPY star-shaped compound shown in formula (I) and a preparation method thereof. The method is realized by the following steps: the trimeric indenyl corrole derivative shown in the formula (II) reacts with the porphyrin derivative shown in the formula (III) under the action of a palladium catalyst to obtain a ternary system compound shown in the formula (IV); then carrying out Suzuki coupling reaction with the BODIPY derivative shown in the formula (V) to obtain the trimeric indenyl corrole-porphyrin-BODIPY star compound shown in the formula (I). The star-shaped compound has the advantages of simple preparation method, mild reaction conditions, simple and convenient operation, strong light absorption capacity and fluorescence intensity, and can be used for light absorption antennas, solar cells, artificial simulation of photosynthesis and the like.

Description

Preparation method of trimeric indenyl corrole-porphyrin-BODIPY star-shaped compound
Technical Field
The invention belongs to the technical field of organic synthesis, and relates to a preparation method of a star-shaped compound based on truxene.
Background
Photoinduced energy/electron transfer plays an important role in photochemical reactions, solar energy utilization, photosynthesis mechanisms and the like. The application and research of molecular structure models based on light-induced energy/electron transfer mechanism in the aspects of optical molecular devices, solar cells, artificial photosynthesis and the like has become a very active research field at home and abroad. Dye molecules with electron/energy donor-acceptor performance have shown wide application prospects in the aspect of organic photoelectric functional materials. However, the star-shaped compound with the donor-acceptor structure still has the defects of multiple synthesis steps, complex reaction, low yield and the like, so that the design and synthesis of the novel star-shaped compound which has good energy/electron transfer process and is easy to synthesize is of great significance.
In molecular models with different structure types, the unique three-dimensional star-emitter structure of the star-shaped compound is beneficial to regulating and controlling the photoelectric property and morphological characteristics of molecules, and a plurality of outwardly extending support arms can improve the charge transfer or energy transfer efficiency and have been widely concerned. The truxene (truxene) has a large rigid conjugated structure, is a three-fold symmetric plane rigid condensed ring aromatic hydrocarbon, is favorable for intramolecular charge transfer, is easy to perform functional design and modification at the 2, 7 and 12 positions of three end groups, and has been proved to be one of ideal compounds for preparing star-shaped compounds. Porphyrin and Corrole (core) are macrocyclic compounds formed by conjugation of 4 pyrroles, have excellent physicochemical properties, are excellent photoelectric functional material molecules, and show wide application prospects in the design and synthesis of energy/electron donor or acceptor molecular systems. The BODIPY fluorescent dye has the advantages of high molar absorption coefficient, high fluorescence quantum yield, insensitivity of a fluorescence signal to solvent polarity and pH, narrow fluorescence spectrum peak, long fluorescence life, moderate oxidation-reduction potential, negligible triplet state and the like, and is also an excellent photoelectric functional material molecule. Therefore, different photoactive groups such as porphyrin, BODIPY, corrole and the like can be grafted on three end groups of 2, 7 and 12 of the truxene respectively through a simple chemical synthesis method to form the long-life charge separation state donor/acceptor star-shaped compound with efficient energy transfer and charge transfer, and the compound can be widely applied to application research in the aspects of light absorption antennas, solar cells, artificial simulation photosynthesis and the like.
Disclosure of Invention
The purpose of the invention is as follows: aiming at the defects in the prior art, the invention aims to provide a preparation method of a trimerization indenyl corrole-porphyrin-BODIPY star-shaped compound.
The technical scheme is as follows: in order to achieve the purpose of the invention, the invention adopts the technical scheme that:
the trimeric indenyl corrole-porphyrin-BODIPY star-shaped compound related by the invention has the following structure:
Figure BSA0000189290190000021
the synthetic route of the trimeric indenyl corrole-porphyrin-BODIPY star-shaped compound related by the invention is as follows:
Figure BSA0000189290190000022
the preparation process of the trimeric indenyl corrole-porphyrin-fullerene star-shaped compound comprises the following steps:
step 1: under the protection of argon, dissolving the trimeric indenyl corrole derivative shown in the formula (II) and the meso-phenyl borate porphyrin derivative shown in the formula (III) in tetrahydrofuran, adding a mixed solution of anhydrous potassium carbonate, water and methanol in a certain proportion into a reactor, finally adding a catalyst of tetrakis (triphenylphosphine) palladium, reacting at 75-85 ℃ for 12 hours, cooling to room temperature after the reaction is finished, adding a saturated ammonium chloride solution, extracting with dichloromethane, evaporating to dryness, and separating and purifying by silica gel column chromatography to obtain a trimeric indenyl corrole-porphyrin intermediate shown in the formula (IV);
step 2: according to the same method of the step 1, the trimerization indenyl corrole-porphyrin intermediate shown in the formula (IV) reacts with the meso-phenyl borate BODIPY derivative shown in the formula (V) under the catalysis of tetrakis (triphenylphosphine) palladium, and the trimerization indenyl corrole-porphyrin-BODIPY ternary system compound shown in the formula (I) is obtained through silica gel column chromatography separation and purification;
4. the production method according to claim 3, wherein the amount of the substance of the trimeric indenylaldehydic corrole derivative of formula ((II) and the meso-phenyl boronate porphyrin derivative of formula (III) in the step 1 is 1: 1;
5. the method according to claim 3, wherein in the step 2, the ratio of the amounts of the trimeric indenyl corrole-porphyrin intermediate represented by the formula (IV) and the meso-phenyl boronate BODIPY biological substance represented by the formula (V) is 1: 1.2;
6. the method according to claim 3, wherein in the steps 1 and 2, the amount of the catalyst tetrakis (triphenylphosphine) palladium is 20% of the amount of the reactant raw material;
the invention has the advantages of
Compared with the prior art, the preparation method of the trimeric indenyl star compound has the advantages that: (1) three different photoactive groups of carbazole, porphyrin and 8ODIPY are respectively introduced into three active positions of truxene 2, 7 and 12 to form a star-shaped molecular system of energy donor-energy acceptor and electron donor-electron acceptor, the electron/energy transfer process can be continuously generated for multiple times in the same molecule, the light absorption range is wide, and the light absorption antenna can be used as a light absorption antenna and an artificial simulation biological photosynthesis process. (2) The method has the advantages of simple synthetic route, mild reaction conditions, good reaction selectivity, simple separation method and universality, and can be popularized and applied to the synthesis of a trimeric indenyl-based star-shaped compound.
Drawings
FIG. 1 is a UV-VIS absorption spectrum of Compound II of the present invention;
FIG. 2 is a UV-VIS absorption spectrum of Compound III of the present invention;
FIG. 3 is a UV-VIS absorption spectrum of Compound V of the present invention;
FIG. 4 is a UV-VIS absorption spectrum of Compound I of the present invention;
FIG. 5 shows fluorescence emission spectra of compounds of formulae II, III, V, and I.
Detailed Description
The present invention is further explained below with reference to specific examples, which are not intended to limit the present invention in any way.
By using1H-NMR, ultraviolet-visible and fluorescence spectra characterize the structure of the compound and investigate the photophysical properties of the compound. The detection instrument is as follows: brukerarx500 nuclear magnetismA resonance instrument (TMS is an internal standard and deuterated chloroform is a solvent), an Shimadzu UV-3100 type ultraviolet-visible spectrophotometer (the scanning range is 400-800 nm and the light path slit is 2nm), a PE LS-55 type fluorescence spectrophotometer (the wavelength range is 200 nm for exciting light and 800nm and 900nm for emitting light, and the slit is variable, 2.5-15nm for exciting light path, 2.5-20nm for emitting light path and 0.1nm for step pitch).
Example 1
Adding 7, 12-dibromo truxene carbazole derivative (II) (0.12mmol, 155.9mg), meso-phenyl boronate porphyrin derivative (III) (0.1mmol, 96.3mg) and anhydrous potassium carbonate (10mmol, 138.0mg) into a reactor, adding dried tetrahydrofuran (40mL), adding methanol and water (v/v, 2.5mL/2.5mL) according to the proportion, finally adding tetrakis (triphenylphosphine) palladium (0.01mmol, 12.0mg), heating to 75-85 ℃ under argon condition, reacting for 12 hours, extracting an organic layer after the reaction is finished, washing the organic layer with dichloromethane solution, drying with anhydrous sodium sulfate, spin-drying a solvent, and purifying by silica gel column chromatography (dichloromethane-petroleum ether is used as an eluent) to obtain the trimeric indenyl carbazole Intermediate (IV) which is 51mg (yield is 25%).1H NMR:(600MHz,CDCl3)δppm 9.16(s,4H),9.01-8.76(m,12H),8.62(s,4H),8.38(dd,J=11.13,7.85Hz,4H),8.25(s,4H),8.15-8.01(m,2H),7.73-7.35(m,4H),3.50-3.08(m,6H),2.57-2.28(m,6H),0.66-0.41(m,18H),-2.77(d,J=4.01Hz,2H)。
Example 2
Adding 0.02mmol and 41.2mg of the Intermediate (IV) of the trimerization indenyl carbazole-porphyrin and 0.025mmol and 17.2mg of the meso-phenyl borate BODIPY derivative (V) into a reactor, dissolving the Intermediate (IV) of the trimerization indenyl carbazole-porphyrin and the meso-phenyl borate BODIPY derivative (V) in tetrahydrofuran (20mL), weighing anhydrous potassium carbonate (2mmol and 27.6mg), adding water and methanol (1mL/1mL) according to the proportion, adding 0.005mmol and 6.0mg of tetrakis (triphenylphosphine) palladium into the reaction under the argon condition, heating to 75-85 ℃, reacting for 12 hours, extracting an organic phase by using dichloromethane and washing by using a saturated ammonium chloride aqueous solution after the reaction is finished, drying the organic layer by using anhydrous sodium sulfate, decompressing and rotating the solvent, and carrying out chromatographic separation and purification by using dichloromethane-petroleum ether as an eluent to obtain the trimerization indenyl carbazole-BODIPY ternary systemization of the trimerization indenyl carbazole-porphyrin and the meso-BODIPYCompound (I) was 17mg (33% yield).1H NMR:(600MHz,CDCl3)δppm 9.23-9.07(m,4H),8.91(d,J=5.35Hz,12H),8.77-8.55(m,4H),8.40-8.36(m,2H),8.34-8.18(m,4H),8.18-8.07(m,2H),8.01-7.96(m,2H),7.96-7.88(m,2H),7.60(d,J=8.78Hz,12H),7.42-7.36(m,1H),7.25-7.22(m,1H),6.94(d,J=8.57Hz,4H),6.68(s,2H),3.86(d,J=5.07Hz,6H),3.52-3.20(m,6H),2.62-2.42(m,6H),1.29(dd,J=10.61,7.16Hz,15H),0.68-0.49(m,18H),-2.74(m,2H)。

Claims (7)

1. A trimeric indenyl corrole-porphyrin-BODIPY star compound shown as a formula (I):
Figure FSA0000189290180000011
2. a method for preparing trimeric indenyl corrole-porphyrin-BODIPY star-shaped compound shown in formula (I) as patent claim 1, which is characterized in that the method comprises the following steps: the trimeric indenyl corrole derivative shown in the formula (II) and the porphyrin derivative shown in the formula (III) react under the action of a palladium catalyst to obtain a trimeric indenyl-corrole-porphyrin ternary system compound shown in the formula (IV); finally, carrying out Suzuki coupling reaction on the ternary system compound shown in the formula (IV) and the BODIPY derivative shown in the formula (V) to obtain a trimeric indenyl corrole-porphyrin-BODIPY star-shaped compound shown in the formula (I);
Figure FSA0000189290180000012
3. the method of claim 2, wherein the method comprises the steps of:
step 1: under the protection of argon, dissolving a truxene carbazole derivative shown in a formula (II) and a meso-phenyl borate porphyrin derivative shown in a formula (III) in tetrahydrofuran, adding a mixed solution of anhydrous potassium carbonate and water and methanol in a certain proportion into a reactor, finally adding a catalyst of tetrakis (triphenylphosphine) palladium, reacting at 75-85 ℃ for 12 hours, cooling to room temperature after the reaction is finished, adding a saturated ammonium chloride solution, extracting and separating with dichloromethane, evaporating an organic solvent, and separating and purifying by silica gel column chromatography to obtain a truxene carbazole-porphyrin intermediate shown in a formula (IV);
step 2: according to the same method of the step 1, the trimerization indenyl corrole-porphyrin intermediate shown in the formula (IV) reacts with the meso-phenyl borate BODIPY derivative shown in the formula (V) under the catalysis of tetrakis (triphenylphosphine) palladium, and the trimerization indenyl corrole-porphyrin-BODIPY ternary system compound shown in the formula (I) is obtained through silica gel column chromatography separation and purification.
4. The production method according to claim 3, wherein the amount of the substance of the trimeric indenyl corrole derivative represented by the formula ((II) and the meso-phenyl boronate porphyrin derivative represented by the formula (III) in the step 1 is 1.2: 1.
5. The method according to claim 3, wherein in the step 2, the ratio of the amounts of the trimeric indenyl corrole-porphyrin ternary system compound represented by the formula (IV) and the meso-phenyl boronate BODIPY biological substance represented by the formula (V) is 1: 1.25.
6. The production method according to claim 3, wherein in the steps 1 and 2, tetrakis (triphenylphosphine) palladium (Pd (PPh) is used as a catalyst3)4) The using amount of the catalyst is 10-20% of the amount of the reactant raw material substances.
7. The method according to claim 3, wherein the volume ratio of methanol to water in the steps 1 and 2 is 1: 1.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113402536A (en) * 2021-06-11 2021-09-17 南京林业大学 Porphyrin bridged double BODIPY derivative and preparation method thereof
WO2022215541A1 (en) * 2021-04-09 2022-10-13 東レ株式会社 Compound, light-emitting element material, light-emitting element using same, photoelectric conversion material, and photoelectric conversion element using same
CN115232161A (en) * 2022-08-31 2022-10-25 南京林业大学 Trihydroindenyl-BODIPY-perylene diimide ternary system molecule and preparation method thereof

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022215541A1 (en) * 2021-04-09 2022-10-13 東レ株式会社 Compound, light-emitting element material, light-emitting element using same, photoelectric conversion material, and photoelectric conversion element using same
CN113402536A (en) * 2021-06-11 2021-09-17 南京林业大学 Porphyrin bridged double BODIPY derivative and preparation method thereof
CN113402536B (en) * 2021-06-11 2022-04-19 南京林业大学 Porphyrin bridged double BODIPY derivative and preparation method thereof
CN115232161A (en) * 2022-08-31 2022-10-25 南京林业大学 Trihydroindenyl-BODIPY-perylene diimide ternary system molecule and preparation method thereof
CN115232161B (en) * 2022-08-31 2024-07-02 南京林业大学 Trimerdanyl-BODIPY-perylene diimide ternary system molecule and preparation method thereof

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