Proton-Coupled Self-Assembly of a Porphyrin-Naphthalenediimide Dyad

• Published in: Chemphyschem Vol. 14; no. 8; pp. 1609 - 1617
• Main Authors: Tu, Siyu, Kim, Se Hye, Joseph, Jojo, Modarelli, David A., Parquette, Jon R.
• Format: Journal Article
• Language: English
• Published: Weinheim WILEY-VCH Verlag 03.06.2013; WILEY‐VCH Verlag; Wiley; Wiley Subscription Services, Inc
• Subjects: amino acids; Chemistry; Colloidal state and disperse state; electron transfer; Exact sciences and technology; General and physical chemistry; Membranes; nanostructures; self-assembly; semiconductors; Vesicle; Self assembly; Atomic force microscopy; Semiconductor materials; Nitrogen heterocycle; Charge separation; Proton transfer; amino acids; Electron transfer; Nanostructure; nanostructures; semiconductors; Aggregation; self-assembly; Transmission electron microscopy; Lysine; Porphyrin; Aminoacid; Proton; Rate constant; Structure; Nanorod
• ISSN: 1439-4235; 1439-7641
• DOI: 10.1002/cphc.201300023

The construction of an n–p heterojunction through the self‐assembly of a dyad based on tetraphenylporphyrin (TPP) and 1,4,5,8‐naphthalenedimide (NDI) (1) is described. Proton transfer from the lysine head group of 1 to the porphyrin ring occurs concomitantly with self‐assembly into 1D nanorods in CHCl3. TEM and AFM studies showed that the nanorods are formed by the lateral and vertical fusion of multilameller vesicles into networks and hollow ribbons, respectively. These intermediate structures transitioned to nanorods over the course of 4–6 days. Time‐resolved spectroscopy revealed that photoinduced charge separation occurs with rate constants that depend on the nature of the aggregation. Proton‐coupled 1D assembly: The amphiphilic self‐assembly of a porphyrin–NDI dyad into 1D nanorods proceeds with concomitant proton transfer in CHCl3. The nanorods engage in π–π contacts that improve photoinduced charge‐transfer rate constants, in contrast to the short‐range aggregates in THF that lack these contacts.