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

Sen S, Ishiwari F, Kaur R, Ishida M, Ray D, Kikuchi K, Mori T, Bähring S, Lynch VM, Saeki A, Guldi DM, Sessler JL, Jana A (2023)

Publication Type: Journal article

Publication year: 2023

Journal

Journal of the American Chemical Society American Chemical Society

Book Volume: 145

Pages Range: 1031-1039

Journal Issue: 2

DOI: 10.1021/jacs.2c10555

Abstract

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.

Authors with CRIS profile

Ramandeep Kaur Lehrstuhl für Physikalische Chemie I Dirk Michael Guldi Lehrstuhl für Physikalische Chemie I

Additional Organisation(s)

FAU Profilzentrum Licht.Materie.Quantentechnologien (FAU LMQ)

Involved external institutions

University of Texas at Austin US United States (USA) (US) Osaka University JP Japan (JP) Tokyo Metropolitan University (TMU) / 首都大学東京 JP Japan (JP) University of Minnesota (UMN) US United States (USA) (US) Tokyo Institute of Technology JP Japan (JP) University of Southern Denmark / Syddansk Universitet DK Denmark (DK) Gandhi Institute of Technology and Management (GITAM) IN India (IN)

How to cite

APA:

Sen, S., Ishiwari, F., Kaur, R., Ishida, M., Ray, D., Kikuchi, K.,... Jana, A. (2023). Supramolecular Recognition within a Nanosized “Buckytrap” That Exhibits Substantial Photoconductivity. Journal of the American Chemical Society, 145(2), 1031-1039. https://doi.org/10.1021/jacs.2c10555

MLA:

Sen, Sajal, et al. "Supramolecular Recognition within a Nanosized “Buckytrap” That Exhibits Substantial Photoconductivity." Journal of the American Chemical Society 145.2 (2023): 1031-1039.

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