We report here a new expanded tetrathiafulvalene-(exTTF)-porphyrin scaffold, 2, that acts as a ball and socket receptor for C60 and C70. Supramolecular interactions between 2 and these fullerenes serve to stabilize three-dimensional (3D) supramolecular organic frameworks (SOFs) in the solid state formally comprising peapod-like linear assemblies. The SOFs prepared via self-assembly in this way act as "tunable functional materials" where-in the complementary geometry of the components and the choice of fullerene play crucial roles in defining the conductance properties. The highest electrical conductivity (σ = 1.3 x 10-8 S cm-1 at 298 K) was observed in the case of the C70-based SOF. In contrast low conductivity was seen for the SOF based on pristine 2 (σ = 5.9 x 10-11 S cm-1 at 298 K). The conductivity seen for the C70-based SOF approaches that seen for other TTF- and fullerene-based supramolecular materials in spite of the fact that the present systems are metal-free and con-structed entirely from neutral building blocks. Transient absorption spectroscopic (TAS) measurements cor-roborated the formation of charge transfer (CT) states (i.e., 2δ+/C60δ- and 2δ+/C70δ-, respectively), rather than fully charge separated states (i.e., 2•+/C60•- and 2•+/C70•-, respectively) both in solution (toluene and benzonitrile) and in the solid state at 298 K. Such findings are considered consistent with an ability to transfer charges effectively over long distances within the present SOFs, rather than, e.g., the formation of energetically trapped ionic species.

中文翻译：

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由近红外荧光大环探针和富勒烯组装的半导体超分子有机框架

我们在此报告了一种新的扩展四硫富瓦烯-(exTTF)-卟啉支架 2，它充当 C60 和 C70 的球窝受体。2 和这些富勒烯之间的超分子相互作用用于稳定固态的三维 (3D) 超分子有机框架 (SOF)，形式上包括豌豆状线性组件。以这种方式通过自组装制备的 SOF 充当“可调功能材料”，其中组件的互补几何形状和富勒烯的选择在定义电导特性方面起着至关重要的作用。在基于 C70 的 SOF 的情况下，观察到最高的电导率（σ = 1.3 x 10-8 S cm-1 在 298 K）。相比之下，基于原始 2 的 SOF 的电导率较低（σ = 5.9 x 10-11 S cm-1 在 298 K）。尽管本系统不含金属并且完全由中性构件构成，但 C70 基 SOF 方法的电导率与其他 TTF 和富勒烯基超分子材料的电导率相同。瞬态吸收光谱 (TAS) 测量证实了电荷转移 (CT) 状态（即分别为 2δ+/C60δ- 和 2δ+/C70δ-）的形成，而不是完全电荷分离状态（即，2•+/ C60•- 和 2•+/C70•-）分别在溶液（甲苯和苄腈）和 298 K 的固态中。这些发现被认为与在当前 SOF 内长距离有效转移电荷的能力一致，而不是，例如，形成能量捕获的离子物质。