|標題:||A Supramolecular "Double-Cable" Structure with a 129(44) Helix in a Columnar Porphyrin-C-60 Dyad and its Application in Polymer Solar Cells|
Van Horn, Ryan M.
Kulkarni, Rahul R.
Cheng, Stephen Z. D.
Department of Applied Chemistry
|關鍵字:||fullerenes;hierarchical structures;self-assembly;solar cells;supramolecular materials|
|摘要:||A novel porphyrin-C-60 dyad (PCD1) is designed and synthesized to investigate and manipulate the supramolecular structure where geometrically isotropic [such as fullerene (C-60)] 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 degrees C with a latent heat (Delta H) of 18.5 kJ mol(-1). The phase formation is majorly driven by the cooperative intermolecular PorPor and C60C60 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 C-60 peripheral channels. These double-cable columns further pack into a hexagonal lattice with a = b = 4.65 nm, c = 41.3 nm, alpha = beta = 90 degrees and gamma = 120 degrees. The column repeat unit is determined to possess a 129(44) helix. With both donor (D; Pro) and acceptor (A; C-60) units having their own connecting channels as well as the large D/A interface within the supramoleculassr double-cable structure, PCD1 has photogenerated carriers with longer lifetimes compared to the conventional electron acceptor [6,6]-phenyl-C-61-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.|
|期刊:||ADVANCED ENERGY MATERIALS|