A ferrocene (Fc) functionalized bis-porphyrin molecule has been synthesized as a host for fullerenes. The porphyrin used in these studies was prepared using a mixed boronic acid Suzuki reaction, which gives A2BC type porphyrins in high yield. The bis-porphyrin was characterized through 1H NMR spectroscopy, high-resolution mass spectroscopy and analyzed via molecular modeling studies. Complexation experiments with fullerenes utilizing both UV-visible and fluorescence spectroscopy demonstrated formation of strong complexes for the bis-porphyrin. A short-lived charge transfer luminescent state is detected for the fullerene adducts. Owing to the tight coupling of the fullerene and porphyrin partners, the host-appended Fc moiety does not show a direct role in the pattern of photoinduced processes upon excitation of either chromophores, but causes blue-shift of the NIR CT luminescence compared to previously investigated systems without appended fragments. Instead, the active role of Fc in photoinduced processes is observed for the guest molecules alone, where photoinduced energy transfer from the porphyrin to the ferrocene occurs.
一种
二茂铁(Fc)官能化双
卟啉分子已被合成为
富勒烯的宿主。这些研究中使用的
卟啉是通过混合
硼酸铃木反应制备的,该反应能以高产率得到 A2BC 型
卟啉。通过 1H NMR 光谱和高分辨率质谱对双
卟啉进行了表征,并通过分子建模研究对其进行了分析。利用紫外可见光谱和荧光光谱与
富勒烯进行的络合实验表明,双
卟啉形成了强络合物。检测到
富勒烯加合物具有短暂的电荷转移发光状态。由于
富勒烯和
卟啉伙伴的紧密耦合,宿主添加的 Fc 分子在激发任一发色团时并不直接参与光诱导过程,但与之前研究的没有添加片段的系统相比,会导致近红外 CT 发光蓝移。相反,仅在客体分子中就能观察到 Fc 在光诱导过程中的积极作用,即发生从
卟啉到
二茂铁的光诱导能量转移。