有机化学 ›› 2013, Vol. 33 ›› Issue (08): 1810-1816.DOI: 10.6023/cjoc201301074 上一篇    下一篇

研究论文

5,10,15,20-四-[4-(N-咔唑)丁烷氧苯基]卟啉及其过渡金属配合物的合成及光电性质研究

王彬彬a,b, 单凝a, 夏爱清a, 王运方a, 于苗a, 师同顺a   

  1. a 吉林大学化学学院 长春 130021;
    b 长春师范大学化学学院 长春 130032
  • 收稿日期:2013-01-29 修回日期:2013-03-15 发布日期:2013-03-22
  • 通讯作者: 师同顺 E-mail:tsshi@jlu.edu.cn
  • 基金资助:

    国家自然科学基金(No. 20801022)资助项目.

Synthesis and Photoelectrical Properties of 5,10,15,20-Tetra{4-[(N-carbazyl)butyloxyphenyl]}porphyrin and Its Transition Metal Complexes

Wang Binbina,b, Shan Ninga, Xia Aiqinga, Wang Yunfanga, Yu Miaoa, Shi Tongshuna   

  1. a College of Chemistry, Jilin University, Changchun 130021;
    b College of Chemistry, Changchun Normal University, Changchun 130032
  • Received:2013-01-29 Revised:2013-03-15 Published:2013-03-22
  • Supported by:

    Project supported by the National Natural Science Foundation of China (No. 20801022).

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-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24发生荧光淬灭. 卟啉25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.

关键词: 卟啉, 过渡金属, 配合物, 合成, 荧光, 表面光电压

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 D4h, 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 metallporphyrin 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 of porphyrin 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 photovoltage 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 used for photovoltaic materials.

Key words: porphyrin, transition metal, complex, synthesis, fluorescence, surface photovoltage