| The synthesis and characterization of tetraphenoxyl-substituted Pcs 8～23 are described and their electrochemistry, temperature-changed UV/Vis spectrum, PL and EL properties are studied as well. Pcs 8～23 are sufficiently characterized by MS, 1H NMR, UV/Vis spectrum, elemental analysis, which are agreement with the proposed structures. Due to the steric hindrance origining from the phenoxyl, Pcs 8～23 are not readily aggregated in solution or solid. The chemical calculation results obtained from the software Chem 3D Ultra 9.0 used for the calculation of the minimum potential energy of 8～23 indicate that phenoxyl substituents can effectively enlarge the face-to-face distance among Pc molecules, especially for the nonperipherally substituted Pcs, such as 11～13 and 19～23. Pcs 8～23 have wonderful solubilities in chloroform (CHCl3), dichloromethane(CHCl2), tetrahydrogenfuran (THF), toluene, benzene, cholorobenzne and choloronaphthalene, but present poor solubility in acetone, DMF and DMSO. The solubility of the phenoxyl in organic solvents determines the solubility of Pcs 8～23. Pcs 8～23 exist in the form of a mixture of four isomers and we fail to separate them by using common column chromatography.We study the electrochemistry of PcZn 10 by obtaining the cyclic voltammetry curves of THF solution (10-3mol/L) of PcZn 10 at the scanning rate of 50mV/s, 100 mV/s and 200mV/s. The results suggest that the redox reactions of PcZn 10 are occurred in the Pc ring and are single-electron reversible and quasi-reversible process. We also give the proposed electrochemical reaction mechanism.The UV/Vis spectra of H2Pc, CuPc, ZnPc, TiOPc, InClPc and 14 ～ 23 in choloronaphthalene at 293K, 303K, 313K, 323K and 333K, respectively, are investigated and a new temperature-induced hypochromic effect is found. This hypochromic effect stems from the conversion of Pc π conjugated system as a result of thermal vibration. The phenomena are decrease of Q band absorbance with the rise of temperature of Pc solution and the wavelength shift of Q band. The B bands don't show the hypochromic effect. The aggregate peaks have the relatively weak hypochromic effect.In this dissertation we study the PL spectra of 14～23 casting film at the quartz substrate at 10K, 1 77K and 300K and 14～23 vacuum-deposited film (200nm) at the silicon substrate at rt. For 14 and 15, their casting films show a fluorescent peak and phosphorescent peak in the PL spectra, respectively. In the cases of 14 and 16, the peaks of excimers are found around 1670nm in their PL spectra, which are related with the resistance ability of molecular...
|
PDF Full Text Request