CN102453034A - Green synthesis method of copper phthalocyanine - Google Patents

Abstract

The invention discloses a green synthesis method of copper phthalocyanine, belonging to the technical field of organic synthesis and relating to a synthesis method of copper phthalocyanine. The green synthesis method comprises the following steps of: (1) taking 0.1mmol of copper salt and 0.4mmol of indole as initial materials, putting the initial materials into a steel bomb with a polytetrafluoroethylene lining, and adding 10mmol of dimethylformamide (DMF) solvent; (2) tightening the steel bomb; (3) putting the steel bomb in an oven, controlling the temperature to be lower than 80 DEG C, reacting for 50-70 minutes, and then cooling to room temperature; and (4) filtering after cooling, and then washing with methanol to obtain purple acicular copper phthalocyanine. The method disclosed by the invention greatly shortens the single crystal growth time and has a very high success ratio; a single crystal of which the length is about 10.5mm can be grown in a very short time, and simultaneously, the success ratio is 100%; and moreover, the equipment is simple, and the cost is low.

Description

The green synthesis method of CuPc

Technical field

The invention belongs to technical field of organic synthesis, relate to the contract method of CuPc, be specifically related to the green synthesis method of CuPc.

Background technology

Phthalocyanine is the aroma system with two dimension 18 πDian Zis of high stability, existing more than 70 kind of different metallic and the nonmetal central atom that can be used as phthalocyanine.Usually; The conjugated system of phthalocyanine refers to be made up of 18-πDian Zi fragrance cloud delocalization system; The system of forming by nine carbon nitrogen conjugated double bonds; These nine carbon nitrogen or carbon carbon conjugated double bond " surround " phthalocyanine and divide the subcenter hole, and phthalocyanine or metal phthalocyanine specific molecular structure have determined them to be replaced by different way by multiple group, and existing so far more than 5000 kind of phthalocyanine-like compound is synthesized out.

The phthalocyanines title complex has similar skeleton structure with natural porphyrin, chlorophyll, protoheme etc., is one type of compound with π-electron conjugated system, has unique physicochemical property such as light, electricity, magnetic and catalysis.According to this character, phthalocyanine is applied at many sciemtifec and technical spheres, electrochemical apparatus for example, the nonlinear optical electric material, the special material of photovoltaic, the organic effect thin film sensor, etc. the aspect application is all arranged.Find nearly 5000 kinds of phthalocyanine derivates now, had only the CuPc material in industrial production, to be able to widespread use.

The CuPc crystal is confirmed the structure of molecular crystal with XRD, is divided into eight kinds in proper order according to the crystal formation of finding crystalline structure, α-, β-, γ-, δ-, ε-. R-, p-, X-type.Since in the crystal Intermolecular Forces very a little less than, therefore loosely organized, thermal expansion percentage coupling and poor heat stability.Just be transformed into β-type so surpass 200 ℃ of other crystal formations, and except the p-type, the crystal formation of other types can directly or indirectly prepare from β-type with chemical process.

At present, the phthalocyanine-like compound monocrystalline can't directly obtain from synthetic, cultivates the phthalocyanine-like compound monocrystalline and often adopts the concentrated sulfuric acid solution recrystallization method; Gas phase physical deposition method, gas phase physical deposition method growing single-crystal is shorter, and the longest is 5mm; The solution gradient falling temperature method, the method growth cycle of liquid gradient cooling is long, about 80 hours.In a word; All there is the long shortcoming of growth cycle in this several method; Dissolve and crystalline size is little, success ratio is low owing to obtaining, be accompanied by the reasons such as loss, crystal and medium separation difficulty of solution or current-carrying gas in the crystal growing process, and make troubles to crystal growth.

Summary of the invention

The objective of the invention is for a kind of green synthesis method of CuPc is provided.

The present invention realizes through following technical scheme:

The green synthesis method of CuPc may further comprise the steps:

(1) is starting raw material with 0.1mmol mantoquita and 0.4mmol indoles, is put into starting raw material and has in the teflon-lined steel bomb, add the 10mmLDMF solvent;

(2) tighten steel bomb;

(3) be placed on steel bomb in the baking oven, controlled temperature behind the reaction 50-70min, is cooled to room temperature at 60-80 ℃;

(4) cooled and filtered is used washed with methanol then, promptly gets the acicular CuPc of purple.

Further, described mantoquita is a copper sulfate.

The present invention is a raw material with mantoquita and indoles, in water in heating, directly synthetic metal phthalocyanine compound, chemical equation is as follows:

Its molecular formula of the acicular CuPc of purple is C ₃₂H ₁₆CuN ₈, productive rate can reach 65%, and monocrystalline is about 10.5mm.

The inventive method solves the problem that the phthalocyanine-like compound crystal growth cycle is long, success ratio is low and cost is high, so for the relevant organic functional molecular material single crystal samples of preparation how monocrystalline be that the photoelectric device of material provides new approach.

The inventive method has shortened the single crystal growing time greatly, and success ratio is very high; Just can grow the monocrystalline about 10.5mm with very short time, success ratio 100% simultaneously, equipment is simple, and cost is low.

Description of drawings

Fig. 1 is the single crystal samples picture;

Fig. 2 is the single crystal samples molecular structure;

Fig. 3 is a single crystal samples packing of molecules structure iron;

Fig. 4 is the X-ray polycrystalline diffraction spectra of single crystal samples;

Fig. 5 is the standard card of the X-ray polycrystalline diffraction spectra of single crystal samples.

Embodiment

Embodiment 1

The green synthesis method of CuPc may further comprise the steps:

(1) is starting raw material with 0.1mmol copper sulfate and 0.4mmol indoles, is put into starting raw material and has in the teflon-lined steel bomb, add the 10mmLDMF solvent;

(2) tighten steel bomb;

(3) be placed on steel bomb in the baking oven, controlled temperature behind the reaction 70min, is cooled to room temperature at 80 ℃;

(4) cooled and filtered is used washed with methanol then, promptly gets the acicular CuPc of purple.

Figure is as shown in Figure 1 for the gained single crystal samples, wherein obtains maximum crystal: 10.5 mm ', 50 mm ', 30 mm.

The single crystal samples molecular structure is as shown in Figure 2, and the CuPc molecular formula is CuN ₈C ₃₂H ₁₆, the monocrystalline spacer is P2 (1)/n, parameter is: and a=14.668 (3), b=4.8109 (10), c=19.515 (7), α=90, β=121.04 (2), γ=90, unit volume is 1179.91 () ³, according to above parameter, this crystal formation belongs to the β type.

Single crystal samples packing of molecules structure iron is as shown in Figure 3.

The X-ray polycrystalline diffraction spectra of single crystal samples is as shown in Figure 4, and the standard card of the X-ray polycrystalline diffraction spectra of single crystal samples is as shown in Figure 5, and wherein the position at each peak and intensity are as shown in table 1,

Table 1

Can find out that from table 1 peak position and intensity and standard shown in Figure 5 are relatively blocked identical fine.

Embodiment 2

The green synthesis method of CuPc may further comprise the steps:

(1) is starting raw material with 0.1mmol mantoquita and 0.4mmol indoles, is put into starting raw material and has in the teflon-lined steel bomb, add the 10mmLDMF solvent;

(2) tighten steel bomb;

(3) be placed on steel bomb in the baking oven, controlled temperature behind the reaction 80min, is cooled to room temperature at 70 ℃;

(4) cooled and filtered is used washed with methanol then, promptly gets the acicular CuPc of purple.

Embodiment 3

The green synthesis method of CuPc may further comprise the steps:

(1) is starting raw material with 0.1mmol mantoquita and 0.4mmol indoles, is put into starting raw material and has in the teflon-lined steel bomb, add the 10mmLDMF solvent;

(2) tighten steel bomb;

(3) be placed on steel bomb in the baking oven, controlled temperature behind the reaction 60min, is cooled to room temperature at 60 ℃;

(4) cooled and filtered is used washed with methanol then, promptly gets the acicular CuPc of purple.

Claims (1)

1. the green synthesis method of a CuPc is characterized in that may further comprise the steps:

(1) is starting raw material with 0.1mmol mantoquita and 0.4mmol indoles, is put into starting raw material and has in the teflon-lined steel bomb, add the 10mmLDMF solvent;

(2) tighten steel bomb;

(3) be placed on steel bomb in the baking oven, controlled temperature behind the reaction 50-70min, is cooled to room temperature below 80 ℃;

(4) cooled and filtered is used washed with methanol then, promptly gets the acicular CuPc of purple.

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