Supramolecular Recognition within a Nanosized “Buckytrap” That Exhibits Substantial Photoconductivity

We report here a nanosized “buckytrap”, 1, constructed from two bis-zinc(II) expanded-TTF (exTTF) porphyrin subunits. Two forms, 1a and 1b, differing in the axial ligands, H₂O 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 1a with C₇₀. The fullerene is found to be encapsulated within the inner pseudohexagonal cavity of 1a. In contrast, the corresponding free-base derivative (2) was found to form infinite ball-and-socket type supramolecular organic frameworks (3D-SOFs) with fullerenes, (2•C₆₀)_n or (2•C₇₀)_n. This difference is ascribed to the fact that in 1a and 1b the axial positions are blocked by a H₂O or THF ligand. Emission spectroscopic studies supported a 1:1 host-guest binding stoichiometry, allowing association constants of (2.0 ± 0.5) × 10⁴ M^-1 and (4.3 ± 0.9) × 10⁴ M^-1 to be calculated for C₆₀ and C₇₀, respectively. Flash-photolysis time-resolved microwave conductivity (FP-TRMC) studies of solid films of the Zn-complex 1a revealed that the intrinsic charge carrier transport, i.e., pseudo-photoconductivity (ϕ∑μ), increases upon fullerene inclusion (e.g., ϕ∑μ = 1.53 × 10^-4 cm² V^-1 s^-1 for C₆₀⊂(1a)₂ and ϕ∑μ = 1.45 × 10^-4 cm² V^-1 s^-1 for C₇₀⊂(1a)₂ vs ϕ∑μ = 2.49 × 10^-5 cm² V^-1 s^-1 for 1a) 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.