CN115232161B - A trimeric indenyl-BODIPY-perylene diimide ternary system molecule and preparation method thereof - Google Patents

Abstract

The invention discloses a trimeric indenyl-BODIPY-perylene diimide ternary system molecular structure shown in a formula (V) and a preparation method thereof. The method is realized by the following steps: the meso-bromo-trimeric indenyl BODIPY shown in the formula (I) and p-methoxybenzaldehyde are reacted through Knoevenagel to generate a meso-bromo-trimeric indenyl BODIPY derivative shown in the formula (II), then the meso-borate trimeric indenyl BODIPY derivative shown in the formula (III) is obtained through Miyaura boric acid esterification, and then the meso-borate trimeric indenyl BODIPY derivative shown in the formula (III) and the bay-position monobromoperylene diimide derivative shown in the formula (IV) are subjected to Suzuki coupling reaction to obtain the trimeric indenyl-BODIPY-perylene diimide ternary system molecule shown in the formula (V). The synthesis method is simple, the reaction condition is mild, and the separation and purification are simple. Different groups in the ternary system can perform intermolecular high-energy transfer after being excited by light, and can be applied to the fields of light molecular absorption antennas, artificial simulated photosynthesis and the like.

Description

A trimeric indenyl-BODIPY-perylene diimide ternary system molecule and its preparation method

Technical Field

The invention belongs to the technical field of organic synthesis and the field of molecular-based photoelectric materials, and relates to a trimerized indenyl-BODIPY-perylene diimide ternary system molecule and a preparation method thereof.

Background technique

The application research of molecular models based on the light-induced energy/electron transfer mechanism in optical molecular devices, solar cells and artificial photosynthesis has become a very active research field at home and abroad. Dye molecules with electron/energy donor/acceptor properties have shown broad application prospects in organic optoelectronic functional materials. Among the molecular models of different structural types, the unique three-dimensional star-shaped structure of ternary system molecules is conducive to regulating the optoelectronic properties and morphological characteristics of molecules, and multiple outwardly extending arms can improve the efficiency of charge transfer and energy transfer, which has received widespread attention. However, ternary system molecules with donor-acceptor structures still have shortcomings such as many synthesis steps, complex reactions, and low yields. Therefore, it is of great significance to design and synthesize easy-to-synthesize ternary system molecules with efficient energy/electron transfer processes.

Perylene diimide derivatives have excellent light, heat and chemical stability, strong absorption and emission in the visible light region, and high fluorescence quantum yield. Since perylene has a large conjugated plane in the molecule, perylene diimide derivatives usually have π-π stacking between molecules, which promotes the formation of two-dimensional structures between molecules and molecules. With good conductivity and suitable electron affinity, perylene diimide molecules have a wide range of uses in organic field effect transistors, organic light-emitting diodes, solar cells and other fields. Truxene has a large rigid conjugated structure and is a three-fold symmetric planar rigid polycyclic aromatic hydrocarbon, which is conducive to intramolecular charge transfer. Its three end groups 2, 7 and 12 are easy to be functionalized and modified, and have been proven to be one of the ideal compounds for preparing ternary system molecules. In addition, fluoroboron dipyrrole (BODIPY) is also a class of fluorescent dyes with excellent performance, which has the advantages of high photothermal stability, molar absorption coefficient, fluorescence quantum yield, long fluorescence lifetime, moderate redox potential, negligible triplet state, etc. Moreover, the fluoroboron dipyrrole fluorescent molecule mother core is relatively stable and has certain chemical activity, the structure is easy to modify, and the absorption and emission wavelengths can be adjusted to the near-infrared region, which can be used in optoelectronic materials, fluorescence imaging and other fields. Based on the excellent properties and structural diversity of perylene diimide, trimerized indene and fluoroboron dipyrrole molecules, it is of great significance to synthesize trimerized indene-BODIPY-perylene diimide ternary system molecules with efficient charge transfer or energy transfer through simple chemical synthesis methods, which is conducive to promoting applications in organic field effect transistors, light molecular absorption antennas and artificial simulated photosynthesis.

Summary of the invention

Purpose of the invention: In view of the deficiencies in the prior art, the purpose of the present invention is to provide a trimerized indenyl-BODIPY-perylene diimide ternary system molecule and a preparation method thereof.

Technical solution: In order to achieve the above-mentioned invention object, the technical solution adopted by the present invention is:

The structure of a trimerized indenyl-BODIPY-perylene diimide ternary system molecule of the present invention is as follows:

The synthesis route of a trimerized indenyl-BODIPY-perylene diimide ternary system molecule of the present invention is:

The preparation process of a trimerized indenyl-BODIPY-perylene diimide ternary system molecule of the present invention comprises the following steps:

Step 1: dissolving bromotrimeric indenyl BODIPY (I), p-methoxybenzaldehyde and p-toluenesulfonic acid (PTSA) in dry toluene, adding piperidine, reacting at 140° C. for 5 h, diluting with dichloromethane after the reaction, washing the organic phase with distilled water, separating the organic phase, drying over anhydrous sodium sulfate, and distilling off the solvent under reduced pressure, and then separating and purifying by silica gel column chromatography to obtain bromotrimeric indenyl BODIPY derivative (II);

Step 2: Mix and dissolve the bromotrimerized indenyl BODIPY derivative (II), potassium acetate, biphenylboronic acid pinacol ester, and [1,1-bis(diphenylphosphino)ferrocene] palladium dichloride (Pd(dPPf)Cl ₂ ) in dry toluene under argon protection, and react at 100° C. for 4 hours with stirring. After the reaction is completed, dilute with dichloromethane, wash the organic phase with distilled water, separate the organic phase, dry it over anhydrous sodium sulfate, and evaporate the solvent under reduced pressure, and then separate and purify it by silica gel column chromatography to obtain the meso-phenylboronic acid ester trimerized indenyl BODIPY derivative (III);

Step 3: dissolving the meso-phenylboronic acid ester trimerized indenyl BODIPY derivative (III) and the bay-position monobrominated perylene diimide derivative (IV), potassium carbonate and tetrakistriphenylphosphine palladium in tetrahydrofuran, distilled water and methanol, reacting them at 65° C. for 12 hours under argon protection. After the reaction, dilute with dichloromethane, wash the organic phase with distilled water, combine the organic layers and dry with anhydrous sodium sulfate, separate the organic phase, dry with anhydrous sodium sulfate, evaporate the solvent under reduced pressure, and then separate and purify with silica gel column chromatography to obtain the trimerized indenyl-BODIPY-perylene diimide ternary system molecule represented by formula (V).

In the above reaction step, the amount of the catalyst tetrakistriphenylphosphine palladium is 10% of the amount of the meso-phenyl borate trimerized indenyl BODIPY derivative (III);

In the above reaction step, the molar ratio of the meso-phenylboronic acid ester trimerized indenyl BODIPY derivative represented by formula (III) to the bay-position monobrominated perylene diimide derivative represented by formula (IV) is 1:3.

Beneficial Effects of the Invention

Compared with the prior art, the trimeric indenyl-BODIPY-perylene diimide ternary system molecule and its preparation method in the present invention have the following advantages: (1) The same molecule has a BODIPY group and a perylene diimide group, has strong electronic absorption in the ultraviolet region, visible light region and near infrared region, has a wide light absorption range, and has high fluorescence emission intensity in the near infrared region, and is a near infrared fluorescent dye with excellent performance. (2) The compound is in a three-arm star shape, which can effectively weaken the π-π interaction between molecules, and form a ternary system molecule of multiple energy donors and energy acceptors. The energy transfer process can occur in the same molecular system, which is beneficial to improve the photoelectric conversion efficiency, and has a high light-induced energy transfer efficiency, and can be used for light absorption antennas, artificial simulation of biological photosynthesis, field effect transistors, etc. (3) The synthesis route is simple, the reaction conditions are mild, the reaction selectivity is good, and it has universality, and can be promoted and applied to the synthesis of similar ternary system molecules.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG1 is the UV-visible absorption spectra of meso-brominated trimerized indenyl BODIPY derivative (II), bay-position monobrominated perylene diimide derivative (IV) and trimerized indenyl-BODIPY-perylene diimide ternary system molecule (V) in dichloromethane;

FIG. 2 is the fluorescence emission spectra of the meso-brominated trimerized indenyl BODIPY derivative (II), the bay-position monobrominated perylene diimide derivative (IV) and the trimerized indenyl-BODIPY-perylene diimide ternary system molecule (V) in dichloromethane.

Detailed ways

The present invention is further explained below in conjunction with specific examples, which do not limit the present invention in any way.

The structures of the compounds were characterized by ¹ H-NMR, UV-visible spectroscopy and fluorescence spectroscopy and the photophysical properties of the compounds were studied. The instruments used for the detection were: Bruker ARX500 nuclear magnetic resonance instrument (TMS as internal standard, deuterated chloroform as solvent), Shimadzu UV-3100 UV-visible spectrophotometer (scanning range 400-800nm, light path slit 2nm), PE LS-55 fluorescence spectrophotometer (wavelength range: excitation light 200-800nm, emission light 200-900nm; variable slit: excitation light path 2.5-15nm, emission light path 2.5-20nm; step size: 0.1nm).

Example 1

Bromotrimer BODIPY (I) (100 mg, 0.11 mmol), p-methoxybenzaldehyde (45 mg, 0.33 mmol) and p-toluenesulfonic acid (PTSA) (20 mg, 0.1 mmol) were dissolved in 20 mL of dry toluene, and 0.2 mL of piperidine was added. The mixture was stirred under reflux at 140°C using a Dean-Stark apparatus. The reaction was monitored by thin layer chromatography. After the reaction of the raw materials was completed, the toluene in the reaction was evaporated through a water separator. The reaction was cooled to room temperature, 100 mL of dichloromethane was added, and the organic phase was washed with distilled water. The organic phase was separated and dried over anhydrous sodium sulfate, and the solvent was evaporated under reduced pressure. The organic phase was separated by silica gel column chromatography using dichloromethane-petroleum ether (V:V=1:1) as an eluent to obtain 80 mg of bromotrimer BODIPY derivative (II) with a yield of 64%. ¹ H NMR (600 MHz, CDCl ₃ ): δ=8.43 (d, J=7.8 Hz, 1H), 8.19 (d, J=8.4 Hz, 2H), 7.67-7.58 (m, 8H), 7.55-7.51 (m, 2H), 7.48-7.47 (m, 1H), 7.37-7.36 (m, 1H), 7.25-7.23 (m, 2H), 6.95-6.94 (m, 4H), 6.65 (s, 2H), 3.87 (s, 6H), 3.03-2.92 (m, 6H), 2.17-2.13 (m, 6H), 1.55 (s, 6H), 0.28-0.22 (m, 18H).

Example 2

The trimeric indenyl bromide BODIPY derivative (II) (80 mg, 0.07 mmol), potassium acetate (52 mg, 0.53 mmol), biboronic acid pinacol ester (81 mg, 0.31 mmol), [1,1-bis(diphenylphosphino)ferrocene] palladium dichloride (Pd(dPPf)Cl ₂ ) (6 mg, 0.01 mmol) were dissolved in dry toluene (4 mL) under argon protection, stirred, and heated to 100°C for reaction. After TLC monitoring showed that there was no raw material in the reaction, the reaction flask was cooled to room temperature, 100 mL of dichloromethane was added, and the organic phase was washed with distilled water. The organic phase was separated and dried over anhydrous sodium sulfate, and the solvent was evaporated under reduced pressure. The organic phase was separated by silica gel column chromatography using dichloromethane-petroleum ether (V:V=4:1) as an eluent to obtain 65 mg of meso-phenylboronic acid ester trimeric indenyl BODIPY derivative (III), with a yield of ⁷⁵ %; H-NMR (600 MHz, CDCl ₃ ): δ=8.48 (d, J=8.4 Hz, 1H), 8.40 (d, J=8.4 Hz, 1H), 8.34 (d, J=7.8 Hz, 1H), 7.91-7.87 (m, 4H), 7.64 (d, J=16.8 Hz, 2H), 7.60 (d, J=8.4 Hz, 4H), 7.47-7.46 (m, 1H), 7.36-7.35 (m, 1H), 7. 25-7.22 (m, 2H), 6.95-6.94 (m, 4H), 6.95-6.94 (m, 4H), 6.65 (s, 2H), 3.87 (s, 6H), 3.03-3.0 (m, 6H), 2.31-2.13 (m, 6H), 1.55 (s, 6H), 1.41 (s, 12H), 1.40 (s, 12H), 0.26-0.17 (m, 18H).

Example 3

The meso-phenylboronic acid ester BODIPY derivative (III) (65 mg, 0.05 mmol), the bay-position monobrominated perylene diimide derivative (IV) (130 mg, 0.16 mmol), potassium carbonate (55 mg, 0.39 mmol), tetrakistriphenylphosphine palladium (7 mg, 0.01 mmol) were dissolved in a mixed solvent of dry tetrahydrofuran (20 mL), distilled water (2 mL) and methanol (MeOH) (2 mL) under argon protection, heated to 65°C and stirred for reaction for 12-14 hours. After the reaction, the reaction flask was cooled to room temperature, 100 mL of dichloromethane was added, and the organic phase was washed with distilled water. The organic phase was separated and dried over anhydrous sodium sulfate, and the solvent was evaporated under reduced pressure. The organic phase was separated by silica gel column chromatography using dichloromethane-petroleum ether (V: V=4: ¹ ) as an eluent to obtain 76 mg of the trimerized indenyl-BODIPY-perylene diimide ternary system molecule (V), with a yield of 58%; H-NMR (400 MHz, CDCl ₃ ): δ=8.69-8.67 (m, 10H), 8.55-8.43 (m, 3H), 8.20-8.10 (m, 4H), 7.68-7.51 (m, 11H), 7.37-7.35 (m, 1H), 7.23-7.22 (m, 2H), 6.96-6.94 (m, 4H), 6.66-6.64 (m, 5H). m, 2H), 5.22-5.12 (m, 4H), 3.87 (s, 6H), 3.14-2.96 (m, 6H), 2.27-1.83 (m, 22H), 1.55 (s, 6H), 1.31-1.19 (m, 64H), 0.83-0.79 (m, 24H), 0.43-0.28 (m, 18H).

Example 4

UV-Vis absorption spectra of solutions of meso-bromotrimeric indenyl BODIPY derivatives (II), bay-monobromoperylene diimide derivatives (IV) and the trimeric indenyl-BODIPY-perylene diimide ternary system (V)

The meso-brominated trimerized indenyl BODIPY derivative (II), the bay-position monobrominated perylene diimide derivative (IV) and the trimerized indenyl-BODIPY-perylene diimide ternary system molecule (V) were dissolved in dichloromethane to prepare a solution with a concentration of 1×10 ^-5 mol/L, and its UV-visible absorption spectrum was measured. FIG1 is the UV-visible absorption spectrum of the solution of the meso-brominated trimerized indenyl BODIPY derivative (II), the bay-position monobrominated perylene diimide derivative (IV) and the trimerized indenyl-BODIPY-perylene diimide ternary system molecule (V) in the present invention.

Example 5

Fluorescence emission spectra of solutions of meso-bromotrimerized indenyl BODIPY derivatives (II), bay-monobromoperylene diimide derivatives (IV) and the trimerized indenyl-BODIPY-perylene diimide ternary system (V)

The meso-bromotrimer indenyl BODIPY derivative (II), the bay-position monobromoperylene diimide derivative (IV) and the trimer indenyl-BODIPY-perylene diimide ternary system molecule (V) were dissolved in dichloromethane to a concentration of 1×10 ^-5 mol/L solution, using a wavelength of 644nm to excite the meso-brominated trimerized indenyl BODIPY derivative (II), using a wavelength of 500nm to excite the bay-position monobrominated perylene diimide derivative (IV), and measuring their fluorescence emission spectra; using wavelengths of 500nm and 644nm to excite the trimerized indenyl-BODIPY-perylene diimide ternary system molecule (V), respectively, both emit characteristic emission peaks of the BODIPY group, indicating that efficient energy transfer can occur from the perylene diimide group to the BODIPY group; Figure 2 is the fluorescence emission spectra of the solutions of the meso-brominated trimerized indenyl BODIPY derivative (II), the bay-position monobrominated perylene diimide derivative (IV) and the trimerized indenyl-BODIPY-perylene diimide ternary system molecule (V) in the present invention.

Claims (5)

1. A trimeric indenyl-BODIPY-perylene diimide ternary system molecule of formula (V):

2. A process for the preparation of a trimeric indenyl-BODIPY-perylene diimide ternary system molecule of formula (V) as defined in claim 1, characterized in that said process comprises: the meso-bromo-trimeric indenyl BODIPY shown in the formula (I) and p-methoxybenzaldehyde are reacted through Knoevenagel to generate a meso-bromo-trimeric indenyl BODIPY derivative shown in the formula (II), then the meso-borate trimeric indenyl BODIPY derivative shown in the formula (III) is obtained through Miyaura boric acid esterification reaction, and then the meso-borate trimeric indenyl BODIPY derivative and the bay-position monobromoperylene diimide derivative shown in the formula (IV) are subjected to Suzuki coupling reaction to obtain the trimeric indene-BODIPY-perylene diimide ternary system molecule shown in the formula (V);

3. the preparation method according to claim 2, characterized in that the preparation method comprises the following experimental steps:

Step 1: dissolving bromotrimeric indenyl BODIPY (I), p-methoxybenzaldehyde and p-toluenesulfonic acid (PTSA) in dry toluene, adding piperidine, reacting for 5 hours at 140 ℃, diluting with dichloromethane after the reaction, washing an organic phase with distilled water, separating the organic phase, drying the organic phase by anhydrous sodium sulfate, evaporating the solvent under reduced pressure, and separating and purifying by silica gel column chromatography to obtain a bromotrimeric indenyl BODIPY derivative (II);

Step 2: mixing and dissolving bromotrimeric indenyl BODIPY derivative (II), potassium acetate, bisboronic acid pinacol ester, [1, 1-bis (diphenylphosphine) ferrocene ] palladium dichloride (Pd (dPPf) Cl ₂) in dry toluene under the protection of argon, stirring, reacting for 4 hours at 100 ℃, diluting with dichloromethane after the reaction, washing an organic phase with distilled water, separating the organic phase, drying the organic phase by anhydrous sodium sulfate, evaporating the solvent under reduced pressure, and separating and purifying by silica gel column chromatography to obtain the meso-borate trimeric indenyl BODIPY derivative (III);

Step 3: dissolving a meso-borate trimeric indene BODIPY derivative (III) and a bay monobromoperylene diimide derivative (IV), potassium carbonate and tetraphenylphosphine palladium in tetrahydrofuran, distilled water and methanol, reacting for 12 hours at 65 ℃ under the protection of argon, diluting with methylene dichloride after the reaction is finished, washing an organic phase with distilled water, combining organic layers and drying with anhydrous sodium sulfate, separating the organic phase, drying with anhydrous sodium sulfate, evaporating under reduced pressure to remove a solvent, and separating and purifying by silica gel column chromatography to obtain the trimeric indene-BODIPY-perylene diimide ternary system molecule shown in the formula (V).

4. A process according to claim 3, characterized in that in the experimental step the catalyst tetrakis triphenylphosphine palladium is used in an amount of 10% of the mass of the meso-borate trimeric indenyl BODIPY derivative (III).

5. The process according to claim 3, wherein the ratio of the amount of the meso-borate trimeric indenyl BODIPY derivative represented by the formula (III) to the amount of the substance of the bay-position monobromoperylene diimide derivative represented by the formula (IV) in the experimental step is 1:3.