Preparation and application of center modified porphyrin derivatives with two different kinds of aromatic ring conjugation

A derivative, a technology of dithioporphyrin, is applied in the preparation and application of a class of center-modified porphyrin derivatives with two different aromatic ring conjugates, to achieve the effect of improving absorption efficiency and conversion efficiency

Inactive Publication Date: 2008-08-06
NANJING UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0004] For meso-tetraphenyldithioporphyrin, there are far fewer studies than protoporphyrin compounds, and there are only two international patents at present [see Detty, M.R.; Gollnick, S.O., PCT Int.Appl. (2003 ), 64; Hurley, L.H.; Lu, T., PCT Int.Appl.(2002), 119.], in addition, most of the dithioporphyrin compounds reported in the literature are those with different phenyl substituents in the middle molecule, while the β-substituted S 2 Only 6 documents were reported on TPP

Method used

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  • Preparation and application of center modified porphyrin derivatives with two different kinds of aromatic ring conjugation
  • Preparation and application of center modified porphyrin derivatives with two different kinds of aromatic ring conjugation
  • Preparation and application of center modified porphyrin derivatives with two different kinds of aromatic ring conjugation

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0035] Example 1: Synthesis of meso-circular (4-fluorophenyl)-diphenanthrene-two bicyclo-dithioporphyrin derivatives (2b):

[0036] In a 250ml round bottom flask, add 1mmol (410mg) 2,5-bis((4-fluorophenyl)hydroxymethyl)-bicyclothiophene (1b), 1mmol (217mg) phenanthropyrrole and 100ml anhydrous dichloromethane , put in a magnet and start stirring, put the reaction bottle into a cryogenic device under the protection of argon and avoid light, control the reaction temperature at -30°C, add a total of 80 μl of BF 3 ·Et 2 O, make it react at low temperature for 1 hour, then allow it to naturally heat up to 25° C., and continue the reaction for 48 hours. 1 mmol (227 mg) of DDQ was added to the reaction solution and reacted for 2 hours. The solvent was distilled off under reduced pressure for chromatographic separation, and the purple-black product 2b was obtained after recrystallization from methanol and chloroform. Yield: 10%; melting point > 120°C (decomposition); UV-vis (CHCl ...

Embodiment 2

[0037] Example 2: 5,10,19,28-Tetrakis(4-fluorophenyl)-diphenanthrene[9,10-b:9,10-l]-dibenzo[g:q]-30,32 - Synthesis of dithioporphyrin (3b):

[0038] In a 25ml round-bottomed flask filled with 0.1mmol (118mg) of compound 2b, vacuumize with an oil pump and heat to 220°C. After 30 minutes, compound 2b is completely converted into compound 3b, with a yield of 100%, and a melting point > 300°C; UV -vis(CHCl 3 ): λ max (ε×10 4 )=543(2.1), 645(0.23), 712(0.53), 869(0.15)nm( Figure 4) ; 1 H NMR (500MHz, CDCl 3 , 25°C, TMS) δ7.039(m, 8H), 7.295(m, 8H), 7.591(m, 8H), 7.759(m, 4H), 8.113(m, 4H), 8.539(m, 4H), 8.996(m, 4H); HRMS m / z experimental value: 1121.2660, [M+H] + , C 76 h 41 f 4 N 2 S 2 Theoretical value: 1121.2642 ( Figure 6) .

Embodiment 3

[0039] Example 3: Synthesis of meso-tetraphenyl-diphenanthrene-two bicyclo-dithioporphyrin derivatives (2a):

[0040] The preparation method is the same as in Example 1, except that 1 mmol (374 mg) of 2,5-diphenylhydroxymethyl-bicyclothiophene (1a) is added. Yield: 9%; Melting point > 200°C (decomposition); UV-vis (CHCl 3 ): λ max (ε×10 4 )=534(3.04), 608(0.56), 672(0.33), 862(0.22)nm; HRMSm / z experimental value: 1105.3690, [M+H] + , C 80 h 53 N 2 S 2 Theoretical value: 1105.3668.

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Abstract

The invention provides a new porphyrin derivative which beta position has two different conjugated aromatic rings (phenanthrene ring and benzene ring), wherein the strong absorption band of the conjugated porphyrin derivative is above 540nm which is the center decorative porphyrin derivative with maximum adsorption wavelength heretofore, which can improve the absorption efficiency on visible light. The compound has wide application in molecule antenna, molecule logic gate, molecule wire, solar battery, optical storage, molecule recognition and photodynamic auxiliary treatment.

Description

1. Technical field [0001] The present invention relates to 5,10,19,28-tetraphenyl-diphenanthrene[9,10-b:9,10-l]-dibenzo[g:q]-30,32-dithioporphyrin Derivatives and their preparation and application. 2. Background technology [0002] Porphyrin compounds have many unique photoelectric properties, good light and thermal stability, and have a large molar absorptivity in the visible light range, so they have been widely used in biochemistry, medicine, analytical chemistry, photocatalysis, and material science. It has received extensive attention and application. In recent years, using the unique electronic structure and photoelectric properties of porphyrin molecules, the design and synthesis of photoelectric functional materials and the development of photoelectric devices have become very active research fields at home and abroad. In terms of energy transfer, porphyrin molecules, as light-absorbing units in model compounds, can realize light-induced charge separation [(a) Gust...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D495/22H01L51/00H01L51/30H01L51/46
CPCY02E10/549
Inventor 沈珍吴迪游效曾
Owner NANJING UNIV
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