Theoretical and Physical Chemistry Institute, National Hellenic Research Foundation, 48 Vassileos Constantinou Avenue, 11635 Athens, Greece.
Chemphyschem. 2012 Apr 10;13(5):1246-54. doi: 10.1002/cphc.201101029. Epub 2012 Feb 28.
The synthesis of a new azafullerene C(59)N-phthalocyanine (Pc) dyad is described. The key step for the synthesis of the C(59)N-Pc dyad was the formation of the C(59)N-based carboxylic acid, which was smoothly condensed with hydroxy-modified Pc. The structure of the C(59)N-Pc dyad was verified by (1)H and (13)C NMR spectroscopy, IR spectroscopy, UV/Vis spectroscopy and MS measurements. The photophysical and electrochemical properties of the C(59)N-Pc dyad were investigated in both polar and non-polar solvents by steady state and time-resolved photoluminescence and absorption spectroscopy, as well as by cyclic voltammetry. Different relaxation pathways for the photoexcited C(59)N-Pc dyad, as a result of changing the solvent polarity, were found, thus giving rise to energy-transfer phenomena in non-polar toluene and charge-transfer processes in polar benzonitrile. Finally, the detailed quenching mechanisms were evaluated and compared with that of a C(60)-Pc dyad, which revealed that the different excited-state energies and reduction potentials of the two fullerene spheres (i.e. C(59)N vs. C(60)) strongly diverged in the deactivation pathways of the excited states of the corresponding phthalocyanine dyads.
描述了一种新型氮杂富勒烯 C(59)N-酞菁（Pc）偶联物的合成。该 C(59)N-Pc 偶联物合成的关键步骤是形成基于 C(59)N 的羧酸，该羧酸与羟基修饰的 Pc 顺利缩合。C(59)N-Pc 偶联物的结构通过（1）H 和（13）C NMR 光谱、IR 光谱、UV/Vis 光谱和 MS 测量得到验证。通过稳态和时间分辨光致发光和吸收光谱以及循环伏安法，研究了 C(59)N-Pc 偶联物在极性和非极性溶剂中的光物理和电化学性质。由于溶剂极性的变化，发现了光激发 C(59)N-Pc 偶联物的不同弛豫途径，从而导致非极性甲苯中的能量转移现象和极性苯腈中的电荷转移过程。最后，评估了详细的猝灭机制并与 C(60)-Pc 偶联物进行了比较，结果表明两个富勒烯球（即 C(59)N 与 C(60)）的不同激发态能量和还原电位在相应酞菁偶联物的激发态失活途径中强烈偏离。
