Publication 122

    1. Sakai, N.; Sisson, A. L.; Bürgi, T.; Matile, S. “Zipper Assembly of Photoactive Rigid-Rod Naphthalenediimide π-Stack Architectures on Gold Nanoparticles and Gold Electrodes” J. Am. Chem. Soc. 2007, 129, 15758-15759 

We introduce zipper assembly as a simple and general concept to create complex functional architectures on conducting surfaces. Rigid-rod π-stack architecture composed of p-oligophenyl rods and blue naphthalenediimide (NDI) stacks is selected as an example. First, short p-quaterphenyl initiators with four anionic NDIs are deposited on gold. Then, long p-octiphenyl propagators with eight cationic NDIs are added. The lower half of the propagator π-stacks with the initiator, whereas the upper half of the molecule remains free. These cationic sticky-ends zip up with anionic propagators to produce anionic sticky-ends, and so on. Zipper assembly on gold nanoparticles is demonstrated by the appearance of the absorption of face-to-face NDI π-stacks and the shift of the surface plasmon resonance band with increasing layer thickness. Complete inhibition by zipper capping demonstrates that zipper assembly affords complex architectures that are more ordered than those obtained by conventional layer-by-layer (LBL) approaches. Zipper assembly on gold electrodes produces increasing photocurrents with increasing number of zipped layers. The photocurrents obtained by this method are much higher than those obtained by conventional LBL controls; zipper termination by capping cleanly stops any increase in photocurrent.

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