| In this dissertation, we study the synthesis and optical character of new substituted Phthalocyanines (Pcs) and phthalocynine (Pc) Crystal. Due to the widely application of Pcs in the fields, such as the communication, medical treatment, chemical industry and so on, therefore, they have been a hot topic over several decades by scientists. Nowadays, scientists have prepared thousands of Pcs and their derivatives. However, along with the human society development and the progress in science and technology, the new phthalocyanine with novle characteristics are still the goal of the scientists. In this dissertion, the synthetic methods of the phthlocyanines are improved. Several novle phthalocyanines are prepared. In addition, the electroluminescent devices are fabricated based on these new materials.The synthesis and characterization of new unsymmetry substituted phthalocyanines: 2(3)-(p-tert-butylphenoxy) Phthalocyanine,2(3)-( p-tert-butylphenoxy) copper Phthalocyanine, 2(3)-(p-tert-Butylphenoxy) Zinc Phthalocyanine, 2(3),16(17)-di(p-tert-butylphenoxy) Phthalo -cyanine, 2(3),16(17)-di(p-tert-Butylphenoxy) copper Phthalocyanine, 2(3), 16 (17)-di(p -tert-butylphenoxy) Zinc Phthalocyanine, 2(3),9(10), 16(17)-tri(p-tert-butyl-phenoxy) Phtha -locyanine, 2(3),9(10), 16(17)-tri(p-tert -butylphenoxy) copper Phthalocyanine and 2(3), 9(10),16(17)-tri(p-tert -butylphenoxy) Zinc Phthalocyanine are described. The treatment of 4-( p-tert-Butylphenoxy)phthalonitrile (A) , 1,3-diiminoisoindoline (B) and metallic salts [Cu(AcO)2.2H2O or Zn(AcO)2.2H2O] was added to organic solvent [1-pentanol, quinlonine and N,N-Dimethyl -formamide (DMF)] under stirring. Then, a catalytic amount of 1,8-Diazabicyclo [5,4,0]undec-7-ene (DBU) was added, and the mixture was heated under N2 for over 24 h. After cooling under N2, anhydrous methanol was added into the reaction mixture to precipitate the solid and solvent was removed under reduced pressure. The collected solid powder were extracted with anhydrous methanol in a soxhlet extractor for 24 h and further purified twice by chromatography. The obtained unsymmetry substituted phthalocyanines were characterized by Mass spectrum (MS), ultraviolet-visible (UV/Vis) spectrum, Infrared Spectroscopy (IR) and elemental analysis. The results are agreement with the proposed structures.A novel solvothermal synthesis method for direct preparing of crystals of copper (nickel) phthalocyanine is presented in this article. Using quinoline as solvent, crystals were prepared after cooling the reaction mixture to room temperature in autoclave. The three kind of starting materials which is using phthalonitrile, Cu(AcO)2.2H2O and NH4MoO4; 1, 3-diiminoisoindoline and Cu(AcO)2.2H2O; phthalonitrile, NH4MoO4 and CuO as starting materials, were preparing CuPc single crystals. The length of CuPc single crystals were 2 mm - 10.5 mm. These high quality crystals were suitable for X-ray poly crystalline diffraction (XRD) characterization. The molecular formula of CuPc is CuN8C32H16, belong to monoclinic system, space group is P 2(l)/n, Unit cell parameters: a =14.668(3), b= 4.8109(10), c=19.515(7),α=90,β= 121.04(2),γ=90, cell volume is 1179.91 (?)3, According to the X-ray poly crystalline diffraction (XRD) spectrum, we can find that the position and the intensity of the diffraction peak were in conformity with the standard card, which proves that the crystals belong toβ-form crystalline. The influences of the different temperatures, reaction time and solvent volumes on the crystal yield were also discussed. We found that the highest CuPc crystal yield which using 1, 3-diiminoisoindoline and Cu(AcO)2.2H2O as starting materials was 52.3% under 270℃for 8 h in 10 ml quinoline.We for the first time using two kind of starting materials to synthesize single crystals of NiPc employed quinoline as solvent. The two kind of starting materials which is using phthalonitrile, Ni(AcO)2.2H2O and NH4MoO4; 1, 3-diiminoisbindoline, NH4MoO4 and Ni(AcO)2.2H2O as starting materials, were preparing single crystals of NiPc. The length of NiPc single crystals were also 2 mm-10.5 mm.These crystals were also suitable for XRD characterization. The molecular formula of ZnPc is ZnN8C32H16, belong to monoclinic system, space group is P 2(1)/n, Unit cell parameters: a =14.668(3), b= 4.8109(10), c=19.515(7),α=90,β=121.04(2),γ=90, cell volume is 1173.6 (?)3, According to the X-ray poly crystalline diffraction (XRD) spectrum, we can find that the position and the intensity of the diffraction peak were in conformity with the standard card, which proves that the crystals belong toβ-form crystalline. To search for the optimum reaction for the highest crystal yield, and the highest NiPc crystal yield which using NH4MoO4; 1, 3-diiminoisoindoline and Ni(AcO)2.2H2O as starting materials was 56.84% under 270℃for 8 h in 14 ml quinoline.Moreover, this method may be easily applied in the crystal growth for other organic materials, and acts as an important method in scientific experiment. CuPc crystals, which are directly obtained using solvothermal synthesis, will be wildly used and produced in large quantities in industry in the near future.We fabricated OLEDs employing 2(3)-( p-tert-butylphenoxy) copper Phthalocyanine, 2(3),16(17)-di(p-tert-butyl-phenoxy) copper Phthalocyanine and 2(3), 9(10), 16(17)-tri (p-tert-butylphenoxy) copper Phthalocyanine as light emitting layer.The final structures of three-layer OLEDs based on 2(3)-( p-tert-butylphenoxy) copper Phthalocyanine and 2(3),9(10), 16(17)-tri (p-tert-butylphenoxy) copper Phthalocyanine were ITO/NPB(40 nm)/Pc(30 nm)/AlQ(43.5 nm)/LiF (0.5 nm)/Al(120 nm) . Organic layers were deposited by vacuum (5.0-9.0×10-4 Pa) thermal evaporation onto a clean glass substrate precoated with an indium tin oxide (ITO) layer with a sheet resistance of 100Ω/□and a transmittance of -80% in the measurement range. A 40-nm-thick film of N,N'-di-1-naphthyl-N,N'-diphenyl benzidine (NPB) was deposited as the hole-transport layer (HTL) at a deposition rate of 20 ?/min. Next, a 30-nm-thick Pc film was deposited as light emitting light emitting layer (LEL) at a deposition rate of 3 (?)/min(1 (?)/min). Then, a 43.8-nm-thick layer of tris- (8-hydroxyquinoline) aluminum (Alq3) was deposited as electron-transport layer and electron-inject layer at a deposition rate of 20 (?)/min. A 0.5-nm-thick LiF film was deposited as contact modification layer. Finally a shadow mask with 2×2 mm2 openings was used to define the 120-nm-thick Al cathode. ITO, NPB, Alq3 and A1 were used as anode, hole-transport layer, electron-transport layer and cathode respectively.The structure of three-layer OLED based on 2(3),16(17)-di(p-tert-butyl-phenoxy copper Phthalocyanine was ITO/NPB(30 nm)/Pc(30 nm) /BCP(20 nm)/AlQ(30 nm)/LiF (0.5 nm)/Al(120 nm). Organic layers were deposited by vacuum (5.0-9.0×10-4 Pa) thermal evaporation onto a clean glass substrate precoated with an indium tin oxide (ITO) layer with a sheet resistance of 100Ω/□and a transmittance of -80% in the measurement range. A 30-nm-thick film of N,N'-di-1-naphthyl-N,N'-diphenyl benzidine (NPB) was deposited as the hole-transport layer (HTL) at a deposition rate of 20 (?)/min. Next, a 30-nm-thick Pc film was deposited as light emitting light emitting layer (LEL) at a deposition rate of 2 (?)/min. A 20-nm-thick 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP) was deposited as hole-blocking layer at a deposition rate of 15 (?)/min. Then, a 20-nm-thick layer of tris-(8-hydroxyquinoline) aluminum (Alq3) was deposited as electron-transport layer and electron-inject layer at a deposition rate of 20 (?)/min. A 0.5-nm-thick LiF film was deposited as contact modification layer. Finally a shadow mask with 2×2 mm2 openings was used to define the 120-nm-thick Al cathode. ITO, NPB, BCP, Alq3 and Al were used as anode, hole-transport layer, hole-blocking layer, electron-transport layer and cathode respectively.Room-temperature electroluminescence was observed at about 869,1062; 1050,1110 and 1095,1204 nm for 2(3)-( p-tert-butylphenoxy) copper Phthalocyanine , 2(3), 16( 17)- di(p-tert -butylphenoxy copper Phthalocyanine and 2(3),9(10), 16(17)-tri (p-tert-butylphenoxy) copper Phthalocyanine. The emission wavelengths and the half bandwidths were quite different for the phthalocyanine, which may be due to the differences of the number of substituted and the molecular aggregations in yacuum sublimed films. The difference of Stokes shift relaxation was also induced by the molecular aggregations.The synthesis and characterizations of Sub-Phthalocyanine copper are reported in this paper firstly. The mixture of 1,3-diiminoisoindoline and Cu(AcO)2-2H2O was added to quinoline under stirring. Then, a catalytic amount of DBU was added. The collected solid powder were extracted with anhydrous methanol in a soxhlet extractor and further purified by chromatography. Sub-Phthalocyanine copper is characterized by MS and elemental analysis. The results are agreement with the proposed structures. The Sub-phthalocyanine copper molecular was broken by laser which was shown in Mass Spectrum. We have analyzed this material decomposition process, and proposed the reaction mechanism through the broken of Sub- phthalocyanine copper molecular.
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