Synthesis and properties of fullerene (C70) complexes of 2,6-bis(porphyrin)-substituted pyrazine derivatives bound to a Pd(II) ion
Synthesis and properties of fullerene (C70) complexes of 2,6-bis(porphyrin)-substituted pyrazine derivatives bound to a Pd(II) ion
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DOI：
10.1080/10610278.2010.487566
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发表时间：
2010-06
影响因子：
3.3
通讯作者：
Y. Eda;Kennosuke Itoh;Yoshio N. Ito;M. Fujitsuka;T. Majima;T. Kawato
中科院分区：
文献类型：
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作者：
Y. Eda;Kennosuke Itoh;Yoshio N. Ito;M. Fujitsuka;T. Majima;T. Kawato
2,6-双（卟啉）取代的3,5-二甲基吡嗪及其锌配合物结合C70生成1:1的包合物，并用ESI-MS、UV-vis、荧光和核磁共振光谱对其进行了表征。通过荧光光谱和核磁共振光谱分析确定了C70配合物的缔合常数。在C70的作用下，吡嗪衍生物的Soret波段吸光度降低，表明C70与卟啉之间存在电荷转移相互作用。通过核磁共振方法获得了实验可靠的缔合常数值，其值约为相应C60配合物的6倍。发现卟啉-吡嗪配体的钯络合增强了与富勒烯的结合。测定了2,6-双（卟啉- zn）-取代3,5-二甲基吡嗪- pd （II）配合物与C70的缔合常数为8400±900 M−1。通过对缔合常数的比较，发现Pd（II）配合物保持了C70的包涵空间，并置在与吡嗪配体相对侧的卟啉之间。
2,6-Bis(porphyrin)-substituted 3,5-dimethylpyrazine and its zinc complex bound C70 to yield 1:1 inclusion complexes, which were characterised by ESI-MS, UV–vis, fluorescence and NMR spectroscopies. Association constants of the C70 complexes were determined by fluorescence and NMR spectral analyses. A decrease in absorbance of the Soret band of the pyrazine derivative by the effect of C70 was observed, suggesting the existence of a charge transfer interaction between C70 and porphyrin. Experimentally reliable values for the association constants were obtained by the NMR method and were about six times larger than those of the corresponding C60 complexes. Palladium complexation of the porphyrin–pyrazine ligand was found to enhance the association with fullerene. The association constant of 2,6-bis(porphyrin-Zn)-substituted 3,5-dimethylpyrazine-Pd(II) complex with C70 was determined to be 8400 ± 900 M− 1. From the comparison of the association constants, it was found that inclusion room for C70 in the Pd(II) complex was maintained, juxtaposed between porphyrins attached to the opposite sides of the pyrazine ligands.