Department of Chemistry and Pharmacy, Interdisciplinary Center for Molecular Materials (ICMM), Friedrich-Alexander-Universität Erlangen-Nürnberg, Egerlandstr. 3, 91058 Erlangen, Germany.
Department of Chemistry, The University of Texas at Austin, 105 East 24th Street, Stop A 5300, Austin, Texas 78712-1224, United States.
J Am Chem Soc. 2020 Jul 1;142(26):11497-11505. doi: 10.1021/jacs.0c03699. Epub 2020 Jun 22.
We report here a new extended tetrathiafulvalene (exTTF)-porphyrin scaffold, , that acts as a ball-and-socket receptor for C and C. Supramolecular interactions between and these fullerenes serve to stabilize 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", wherein 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 × 10 S cm at 298 K) was observed in the case of the C-based SOF. In contrast, low conductivity was seen for the SOF based on pristine (σ = 5.9 × 10 S cm at 298 K). The conductivity seen for the C-based SOF approaches that seen for other TTF- and fullerene-based supramolecular materials despite the fact that the present systems are metal-free and constructed entirely from neutral building blocks. Transient absorption spectroscopic measurements corroborated the formation of charge-transfer states (i.e., /C and /C, respectively) rather than fully charge separated states (i.e., /C and /C, 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, for example, the formation of energetically trapped ionic species.
我们在此报告了一种新的扩展四硫富瓦烯（exTTF）-卟啉支架 ，它作为 C 和 C 的球窝受体。 和这些富勒烯之间的超分子相互作用有助于在固态中稳定 3D 超分子有机框架（SOF），这些 SOF 正式由豆荚状线性组装体组成。通过这种自组装方式制备的 SOF 充当“可调谐功能材料”，其中组件的互补几何形状和富勒烯的选择在定义电导率性质方面起着关键作用。基于 C 的 SOF 的电导率最高（在 298 K 时为 1.3×10 S cm）。相比之下，基于原始 的 SOF 的电导率较低（在 298 K 时为 5.9×10 S cm）。尽管本系统是无金属的并且完全由中性构建块构建，但基于 C 的 SOF 的电导率接近其他 TTF 和富勒烯基超分子材料的电导率。瞬态吸收光谱测量证实了电荷转移态（即 /C 和 /C，分别）的形成，而不是完全分离的电荷态（即 /C 和 /C，分别），无论是在溶液（甲苯和苯腈）中还是在 298 K 下的固态中。这些发现被认为与在当前 SOF 中有效长距离转移电荷的能力一致，而不是例如形成能量捕获的离子物种。
