设计合成了未见报道的5,10,15,20-四-[4-(N-咔唑)丁烷氧苯基]卟啉(1)及其过渡金属配合物[M=Co(2),Ni(3),Cu(4),Zn(5)].通过核磁共振氢谱、紫外一可见光谱、元素分析、红外光谱以及拉曼光谱对过渡金属卟啉配合物进行了表征,并研究了卟啉样品的荧光性质和表面光电压性质.卟啉1,3,5具有较强的荧光,其中卟啉5的荧光量子效率超过了ZnTPP,卟啉2和4发生荧光淬灭.卟啉2~5的表面光电压测试结果表明,外加电场性质对光电压信号都有比较明显的影响.
A novel 5,10,15,20-tetra {4-[(N-carbazyl)butyloxyphenyl] }porphyrin and its transition metal complexes [M= Co (2), Ni (3), Cu (4), Zn (5)] were prepared and characterized by UV-Vis, 1H NMR, IR, Raman spectra and elemental analyses. Compared with the porphyrin ligand, the number of the absorption bands of the metalloporphyrin complexes decrease, the most remarkable difference was the absence of some Q bands. When the metal ions substituted the protons on the N atoms in pyrrole rings, the symmetry of the molecule was changed from D2h to Dah, therefore their absorption spectra were changed to some extent. The IR bands at 3315 and 966 cm-1 in the free base porphyrin ligand are assigned to the N--H stretching and bending vibration of the porphyrin core, respectively. The N--H stretching and bending vibration disappear in the metallpor- phyrin complexes, since hydrogen atom in N--H bonding is replaced by transition metal ion. There were high fluorescence intensity and fluorescence quantum yield of the porphyrin ligand and its zinc complex. Fluorescence quantum yield ofporphyrin zinc complex was higher than that of ZnTPP. The fluorescence intensity of porphyrin nickel complex was quenched partly but the fluorescence intensity of porphyrin cobalt complex and porphyrin copper complex were quenched completely. This indicates fairly certainly that the spin forbidden process S1-→Tn is predominant for radiationless deactivation of S1 in porphyrin compounds. Contrary to the results of the fluorescence intensity of porphyrin complexes, there were high surface photowitage of porphyrin cobalt complex and porphyrin copper complex without external field. Competition process was showed between fluorescence intensity and surface photovoltage intensity. Positive external field could increase surface photovoltage intensity of porphyrin complexes. Surface photovoltage spectra of porphyrin complexes were influence by the property of external electric field which indicated that the porphyrin complexes were probably u