Ultrafast Photoinduced Charge Separation Resulting from Self-assembly of a Green Perylene-based Dye into π-Stacked Arrays

Abstract

Condensation of 3,4,5-tris(n-dodecyloxy)aniline with the green chromophore 1,7-bis(N-pyrrolidinyl)perylene-3,4;9,10-tetracarboxylic dianhydride yields N,N'-bis(3,4,5-tris(n-dodecyloxy)phenyl)-1,7-bis(N-pyrrolidinyl)perylene-3,4;9,10-bis(dicarboximide), 5PDI-TAP, which absorbs light strongly from 550 to 750 nm. 5PDI-TAP dissolves readily in methylcyclohexane (MCH), resulting in self-assembly into H-aggregates. Small-angle X-ray scattering data obtained on 10(-4) M solutions of 5PDI-TAP in MCH show that the aggregates are pi-stacked monodisperse pentamers. Femtosecond transient absorption spectroscopy on solutions of (5PDI-TAP)5 in MCH shows evidence of charge separation occurring with tau < or = 150 fs between adjacent stacked members of 5PDI-TAP within the pentamer followed by charge recombination with tau = 860 ps. Transmission electron microscopy of 5PDI-TAP films cast from solution show isolated bundles of columnar aggregates. (5PDI-TAP)n is a potentially useful material for organic photovoltaics because efficient photoinduced charge generation is an intrinsic property of the assembly.

Circularly Polarized Luminescence in Supramolecular Assemblies of Chiral Bichromophoric Perylene Bisimides

“…[21,22] Owing to this strong cofacial pp-stacking interaction between PBI units, the aggregated structure of 1 exhibited a more crystalline nature at the cost of solubility of self-assembled fibers. The cofacial stacking with close distance also contributed to the effective quenching of excited state by charge separation, [22] which could be the reason for the lower emission quantum yield as well as shorter emission lifetime for the aggregated structures of 1 than those of 2. Meanwhile, a broad peak at 23.28 with a d spacing of 0.38 nm was observed for assemblies of 2, thus indicating the looser stacking interaction between PBI units than 1.…”

Enantioselective Light Harvesting with Perylenediimide Guests on Self‐Assembled Chiral Naphthalenediimide Nanofibers

“…[29] Thea rrangement of the diethoxy-substituted NDI units,w hich is devoid of strong p stacking, [30] supports efficient excitonic migration in the self-assembled nanofibers, which is in accordance with the preserved fluorescence quantum yield in the MCH-rich solvent. [29] Thea rrangement of the diethoxy-substituted NDI units,w hich is devoid of strong p stacking, [30] supports efficient excitonic migration in the self-assembled nanofibers, which is in accordance with the preserved fluorescence quantum yield in the MCH-rich solvent.…”

Alkenyl/Thiol‐Derived Metal–Organic Frameworks (MOFs) by Means of Postsynthetic Modification for Effective Mercury Adsorption

“…22 Owing to this strong cofacial π–π‐stacking interaction between PBI units, the aggregated structure of 1 exhibited a more crystalline nature at the cost of solubility of self‐assembled fibers. The cofacial stacking with close distance also contributed to the effective quenching of excited state by charge separation,22 which could be the reason for the lower emission quantum yield as well as shorter emission lifetime for the aggregated structures of 1 than those of 2 . Meanwhile, a broad peak at 23.2° with a d spacing of 0.38 nm was observed for assemblies of 2 , thus indicating the looser stacking interaction between PBI units than 1 .…”