A Supramolecular “Double-Cable” Structure with a 12944 Helix in a Columnar Porphyrin-C60 Dyad and its Application in Polymer Solar Cells

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Abstract

A novel porphyrin-C60 dyad (PCD1) is designed and synthesized to investigate and manipulate the supramolecular structure where geometrically isotropic [such as [60]fullerene (C60)] and anisotropic [such as porphyrin (Por)] units coexist. It is observed that PCD1 possesses an enantiomeric phase behavior. The melting temperature of the stable PCD1 thermotropic phase is 160 °C with a latent heat (ΔH) of 18.5 kJ mol−1. The phase formation is majorly driven by the cooperative intermolecular Por–Por and C60–C60 interactions. Structural analysis reveals that this stable phase possesses a supramolecular “double-cable” structure with one p-type Por core columnar channel and three helical n-type C60 peripheral channels. These “double-cable” columns further pack into a hexagonal lattice with a = b = 4.65 nm, c = 41.3 nm, α = β = 90°, and γ = 120°. The column repeat unit is determined to possess a 12944 helix. With both donor (D; Pro) and acceptor (A; C60) units having their own connecting channels as well as the large D/A interface within the supramolecular “double-cable” structure, PCD1 has photogenerated carriers with longer lifetimes compared to the conventional electron acceptor [6,6]-phenyl-C61-butyric acid methyl ester. A phase-separated columnar morphology is observed in a bulk-heterojunction (BHJ) material made by the physical blend of a low band-gap conjugated polymer, [poly[2,6-(4,4-bis-(2-ethylhexyl)-4H-cyclopenta [2,1-b;3,4-b′]-dithiophene)-alt-4,7-(2,1,3-benzothia-diazole)] (PCPDTBT), and PCD1. With a specific phase structure in the solid state and in the blend, PCD1 is shown to be a promising candidate as a new electron acceptor in high performance BHJ polymer solar cells.

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