Sen Sajal, Ishiwari Fumitaka, Kaur Ramandeep, Ishida Masatoshi, Ray Debmalya, Kikuchi Koichi, Mori Takehiko, Bähring Steffen, Lynch Vincent M, Saeki Akinori, Guldi Dirk M, Sessler Jonathan L, Jana Atanu
Department of Chemistry, The University of Texas at Austin, 105 East 24th Street Stop A 5300, Austin, Texas 78712-1224, United States.
Department of Applied Chemistry, Graduate School of Engineering, Osaka University, 2-1 Yamadaoka, Suita, Osaka 565-0871, Japan.
J Am Chem Soc. 2023 Jan 18;145(2):1031-1039. doi: 10.1021/jacs.2c10555. Epub 2023 Jan 6.
We report here a nanosized "buckytrap", , constructed from two bis-zinc(II) expanded-TTF (exTTF) porphyrin subunits. Two forms, and , differing in the axial ligands, HO vs tetrahydrofuran (THF), were isolated and characterized. Discrete host-guest inclusion complexes are formed upon treatment with fullerenes as inferred from a single-crystal X-ray structural analyses of with C. The fullerene is found to be encapsulated within the inner pseudohexagonal cavity of . In contrast, the corresponding free-base derivative () was found to form infinite ball-and-socket type supramolecular organic frameworks (3D-SOFs) with fullerenes, (C) or (•C). This difference is ascribed to the fact that in and the axial positions are blocked by a HO or THF ligand. Emission spectroscopic studies supported a 1:1 host-guest binding stoichiometry, allowing association constants of (2.0 ± 0.5) × 10 M and (4.3 ± 0.9) × 10 M to be calculated for C and C, respectively. Flash-photolysis time-resolved microwave conductivity (FP-TRMC) studies of solid films of the Zn-complex revealed that the intrinsic charge carrier transport, i.e., pseudo-photoconductivity (ϕ∑μ), increases upon fullerene inclusion (e.g., ϕ∑μ = 1.53 × 10 cm V s for C⊂() and ϕ∑μ = 1.45 × 10 cm V s for C⊂() vs ϕ∑μ = 2.49 × 10 cm V s for ) at 298 K. These findings provide support for the notion that controlling the nature of self-assembly supramolecular constructs formed from exTTF-porphyrin dimers through metalation or choice of fullerene can be used to regulate key functional features, including photoconductivity.
我们在此报告一种由两个双锌（II）扩展四硫富瓦烯（exTTF）卟啉亚基构建的纳米级“巴基陷阱”。分离并表征了两种形式，即轴向配体不同的 和 ，分别为羟基（HO）和四氢呋喃（THF）。通过 与C的单晶X射线结构分析推断，用富勒烯处理时会形成离散的主客体包合物。发现富勒烯被封装在 的内部准六边形空腔内。相比之下，发现相应的游离碱衍生物（）与富勒烯（C）或（•C）形成无限的球窝型超分子有机框架（3D - SOF）。这种差异归因于在 和 中轴向位置被HO或THF配体阻断这一事实。发射光谱研究支持1:1的主客体结合化学计量比，分别计算出C和C的缔合常数为(2.0 ± 0.5) × 10 M和(4.3 ± 0.9) × 10 M。对锌配合物 的固体薄膜进行的闪光光解时间分辨微波电导率（FP - TRMC）研究表明，在298 K时，富勒烯包合后本征电荷载流子传输，即假光导率（ϕ∑μ）增加（例如，对于C⊂()，ϕ∑μ = 1.53 × 10 cm V s，对于C⊂()，ϕ∑μ = 1.45 × 10 cm V s，而对于 ，ϕ∑μ = 2.49 × 10 cm V s）。这些发现支持了这样一种观点，即通过金属化或富勒烯的选择来控制由exTTF - 卟啉二聚体形成的自组装超分子结构的性质，可用于调节包括光电导率在内的关键功能特性。
