Ultrafast photoinduced electron transfer (PIET) dynamics of a C70-encapsulated bisporphyrin covalent organic polyhedron hybrid (C70@COP-5) is studied in a nonpolar toluene medium with fluorescence and transient absorption spectroscopies. This structurally rigid donor (D)-acceptor (A) molecular hybrid offers a new platform featuring conformationally predetermined cofacial D-A orientation with a fixed edge-to-edge separation, REE (2.8 Å), without the aid of covalent bonds. Sub-picosecond PIET (τET ≤ 0.4 ps) and very slow charge recombination (τCR ≈ 600 ps) dynamics are observed. The origin of these dynamics is discussed in terms of enhanced D-A coupling (V = 675 cm-1) and extremely small reorganization energy (λ ≈ 0.18 eV), induced by the intrinsic structural rigidity of the C70@COP-5 complex.

中文翻译：

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低介电介质中 C70 封装的双卟啉共价有机多面体的空间超快光致电子转移动力学

用荧光和瞬态吸收光谱在非极性甲苯介质中研究了 C70 封装的双卟啉共价有机多面体杂化体 (C70@COP-5) 的超快光诱导电子转移 (PIET) 动力学。这种结构刚性的供体 (D)-受体 (A) 分子混合物提供了一个新平台，该平台具有构象预先确定的共面 DA 取向，具有固定的边到边间隔，REE (2.8 Å)，无需共价键的帮助。观察到亚皮秒 PIET (τET ≤ 0.4 ps) 和非常缓慢的电荷复合 (τCR ≈ 600 ps) 动力学。这些动力学的起源通过增强的 DA 耦合（V = 675 cm-1）和极小的重组能（λ ≈ 0.18 eV）进行讨论，这是由 C70@COP-5 复合物的固有结构刚性引起的。