CN113461715A

CN113461715A - Tetraperylene diimide based phenyl tetraphenanthrene ring conjugated porphyrin derivative and preparation method thereof

Info

Publication number: CN113461715A
Application number: CN202110878116.5A
Authority: CN
Inventors: 徐海军; 宗轩莱; 卫婷; 宋宇婷
Original assignee: Nanjing Forestry University
Current assignee: Nanjing Forestry University
Priority date: 2021-07-30
Filing date: 2021-07-30
Publication date: 2021-10-01

Abstract

The invention discloses a structure of a tetraperylene diimide phenyl tetraphenanthrene ring conjugated porphyrin derivative shown in a formula (I) and a preparation method thereof. The method is realized by the following steps: the phenanthrene ring conjugated pyrrole shown in the formula (II) and perylene diimide aromatic aldehyde shown in the formula (III) are subjected to boron trifluoride ether catalysis and 2, 3-dichloro-5, 6-dicyano-1, 4-benzoquinone (DDQ) oxidation one-pot reaction at room temperature by using trichloromethane as a solvent to synthesize the tetraperylene diimide phenyl tetraphenanthrene ring conjugated porphyrin derivative. The preparation method has the advantages of simple reaction steps, mild reaction conditions, good selectivity, high yield and the like. The conjugated porphyrin derivative has strong absorption in visible and near red regions, and can be used for photodynamic therapy, solar cells, light absorption antennas and the like.

Description

Tetraperylene diimide based phenyl tetraphenanthrene ring conjugated porphyrin derivative and preparation method thereof

Technical Field

The invention belongs to the technical field of organic synthesis and the field of organic photoelectric functional materials, and relates to a tetraperylene diimide based phenyl tetraphenanthrene ring conjugated porphyrin derivative and a preparation method thereof.

Background

Porphyrin compounds have unique photoelectric properties, good light and thermal stability and larger molar absorption coefficient in a visible light range, so that the porphyrin compounds have wide attention and application in the fields of biochemistry, medicine and pharmacology, analytical chemistry, photocatalysis, material science and the like. In recent years, the research and development of designing and synthesizing photoelectric functional materials and photoelectric devices by using the unique electronic structure and photoelectric properties of porphyrin molecules have become very active research fields at home and abroad, for example, in the aspects of simulating photoinduced charges and energy transfer of biological photosynthesis centers, the porphyrin molecules are used as light absorption units in model compounds to realize light-induced charge separation; in addition, the porphyrin compound has wide application prospects in the aspects of Organic Field Effect Tubes (OFETs), molecular switches, molecular logic gates, molecular leads, organic solar cells, nonlinear optical materials, molecular recognition, medicines and the like.

Perylene diimide is an industrial dye with wide application, and is commonly used as a high-grade dye for automobile decoration. The gulf site of the perylene diimide molecule is easy to modify, characteristic structure modification can be carried out through gulf site coupling reaction, and the red region of the visible spectrum can be extended. In addition, the perylene diimide and the derivative thereof also have a series of excellent photoelectric properties such as higher molar extinction coefficient, high fluorescence quantum yield, stronger electronic affinity, good light stability and the like, and the properties enable the perylene diimide to be applied to various fields including n-type semiconductor materials, solar cells, organic light emitting diodes, field effect transistors and the like.

Porphyrin and perylene diimide are common light absorption units, have a large conjugated system and high molar extinction coefficient and high charge mobility, and are easily modified by a common chemical method to change the physical and chemical properties of the porphyrin and perylene diimide. Perylene diimide groups are introduced into meso sites of the porphyrin, so that the porphyrin derivative has excellent photoelectric properties of both the porphyrin and the perylene diimide. And phenanthrene ring groups are introduced into beta positions of porphyrin, so that molecules have a larger conjugated system, the energy level difference between the ground state and the excited state of the molecules is effectively reduced, and the porphyrin compound can generate a strong electron absorption spectrum and a strong fluorescence emission spectrum in a near-infrared region. However, no report has been made on this compound. In addition, the near-infrared dye molecule plays an important role in a plurality of fields such as optical imaging, tumor diagnosis, military reconnaissance, infrared camouflage, nonlinear optical materials, photodynamic therapy and the like. However, the synthesis of the compounds is less researched due to more steps and difficult separation of meso-site group modification and beta-site phenanthrene ring conjugated porphyrin, and the compounds can have strong absorption and fluorescence emission in the near infrared region after chemical modification, so that the compounds have wide application prospects in the aspects of organic solar cells, nonlinear optical materials, light absorption antennas, photodynamic therapy 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 tetraperylene diimide based phenyl tetraphenanthrene ring conjugated porphyrin derivative and a preparation method thereof.

The technical scheme is as follows: in order to achieve the purpose of the invention, the invention adopts the technical scheme that:

the structure of the tetraperylene diimide phenyl tetraphenanthrene ring conjugated porphyrin derivative provided by the invention is as follows:

the invention relates to a synthetic route of a tetraperylene diimide phenyl tetraphenanthrene ring conjugated porphyrin derivative, which comprises the following steps:

the preparation process of the tetraperylene diimide phenyl tetraphenanthrene ring conjugated porphyrin derivative comprises the following steps:

step 1: adding perylene diimide aromatic aldehyde (II), phenanthrene ring conjugated pyrrole (III), boron trifluoride diethyl etherate and trichloromethane into a reaction vessel, reacting for 24 hours at room temperature under the protection of argon and in a dark condition, and then adding 2, 3-dichloro-5, 6-dicyano-1, 4-benzoquinone (DDQ) for reacting for 2 hours;

step 2: distilling under reduced pressure to remove solvent, separating the residue by silica gel column chromatography, and separating by CHCl₃-CH₃OH is recrystallized to obtain a tetraperylene diimide phenyl tetraphenanthrene ring conjugated porphyrin derivative;

in the reaction step 1, the molar ratio of the perylene diimide aromatic aldehyde to the phenanthrene ring conjugated pyrrole is 1: 1;

in the reaction step 1, trichloromethane is used as a solvent, and boron trifluoride diethyl etherate is used as a catalyst;

in the reaction step 1, the reaction condition is under the protection of argon and at room temperature;

in the reaction step 2, silica gel column chromatography separation and a diffusion method are adopted for recrystallization purification;

the invention has the advantages of

Compared with the prior art, the tetraperylene diimide phenyl tetraphenanthrene ring conjugated porphyrin derivative and the preparation method thereof have the advantages that: (1) the method can lead perylene diimide substituent groups to meso position of porphyrin and lead phenanthrene ring to beta position of porphyrin to prepare the tetraperylene diimide phenyl tetraphenanthrene ring conjugated porphyrin derivative which has the structural characteristics and photoelectric properties of perylene diimide and phenanthrene ring conjugated porphyrin; (2) the reaction operation is simple and convenient, the selectivity is good, the reaction condition is mild, and the yield is high; (4) the ultraviolet-visible absorption spectrum of the prepared tetraperyleneimide phenyl tetraphenanthrene ring conjugated porphyrin derivative has wide absorption ranges in visible and near infrared regions; (5) the prepared tetraperylene diimide phenyl tetraphenanthrene ring conjugated porphyrin derivative has potential application prospects in the aspects of organic solar cell receptor materials, light absorption antennas, photodynamic therapy and the like.

Drawings

FIG. 1 is a UV-VIS absorption spectrum of a compound of formula I;

FIG. 2 is a MALDI-TOF mass spectrum of a compound of formula 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 spectroscopy, characterized the structure of the compound and investigated the photophysical properties of the compound. The detection instrument is as follows: matrix-assisted laser desorption ionization time-of-flight mass spectrometer, Shimadzu UV-3100 model ultraviolet-visible spectrophotometer (scanning range 400-800 nm, light path slit 2 nm).

Example 1

Conjugated phenanthrene ring pyrrole (0)217g, 1mm0l) and perylene diimide aromatic aldehyde (0.859g, 1mm0l) were dissolved in 350mL of chloroform, reacted at room temperature under argon protection in the dark for 24h, and then added with DDQ and reacted for 2 h. After the solvent is removed by reduced pressure distillation, the residue is subjected to silica gel column chromatography separation, the eluent is dichloromethane-petroleum ether and chloroform, and then the tetraperylenediimidoyl phenyl tetraphenanthrene ring conjugated porphyrin derivative is obtained after recrystallization of methanol and chloroform, and the yield is as follows: 52 percent. MALDI-TOF MASS Cal.For [ C₂₉₂H₂₉₄N₁₂O₁₆]：4227.6320，Found：4228.064[M+H⁺]。UV-vis：500nm，529nm，590nm，820nm。

Claims

1. A tetraperylene diimide based phenyl tetraphenanthrene ring conjugated porphyrin derivative is characterized in that the structural formula is shown as the formula (I):

2. the preparation method of the perylenediimide-phenylphenanthrene ring conjugated porphyrin derivative represented by the formula (I) as claimed in claim 1, wherein the preparation method comprises the following steps: carrying out a boron trifluoride diethyl etherate catalytic reaction on phenanthrene ring conjugated pyrrole shown in a formula (II) and perylene diimide aromatic aldehyde shown in a formula (III) at room temperature by using trichloromethane as a solvent, and carrying out a DDQ oxidation one-pot reaction to generate a tetraperylene diimide phenyl tetraphenanthrene ring conjugated porphyrin derivative (I);

3. the method of claim 2, wherein the method comprises the steps of:

step 1: under the conditions of argon protection and light shielding, adding phenanthrene ring conjugated pyrrole (II), perylene diimide aromatic aldehyde (III), boron trifluoride diethyl etherate and trichloromethane into a reaction vessel, and stirring at room temperature for reaction for 24 hours. Then DDQ is added for reaction for 2 hours. Wherein, the mol ratio of the perylene diimide aromatic aldehyde (III) to the phenanthrene ring conjugated pyrrole (II) is 1: 1;

step 2: distilling under reduced pressure to remove solvent, separating and purifying the residue with silica gel chromatography column, eluting with dichloromethane-petroleum ether and chloroform, and purifying with CHCl₃-CH₃Recrystallization of OH gave the pure product.

4. The method according to claim 2, wherein in step 1, chloroform is used as a solvent and boron trifluoride ethyl etherate is used as a catalyst.

5. The method according to claim 2, wherein in step 1, the molar ratio of the perylene diimide aromatic aldehyde to the phenanthrene ring conjugated pyrrole is 1: 1.