- Sforazzini, G.; Orentas, E.; Bolag, A.; Sakai, N.; Matile, S. “Toward Oriented Surface Architectures with Three Co-Axial Charge-Transporting Pathways” J. Am. Chem. Soc. 2013, 135, 12082-12090
We report a synthetic method to build oriented architectures with three coaxial π-stacks directly on solid surfaces. The approach operates with orthogonal dynamic bonds, disulfides and hydrazones, self-organizing surface-initiated polymerization (SOSIP), and templated stack-exchange (TSE). Compatibility with naphthalenediimides, perylenediimides, squaraines, fullerenes, oligothiophenes, and triphenylamine is confirmed. Compared to photosystems composed of two coaxial channels, the installation of a third channel increases photocurrent generation up to 10 times. Limitations concern giant stack exchangers that fail to enter SOSIP architectures (e.g., phthalocyanines surrounded by three fullerenes), and planar triads that can give folded or interdigitated charge-transfer architectures rather than three coaxial channels. The reported triple-channel surface architectures are as sophisticated as it gets today, the directionality of their construction promises general access to multichannel architectures with multicomponent gradients in each individual channel. The reported approach will allow us to systematically unravel the ultrafast photophysics of molecular dyads and triads in surface architectures, and might become useful to develop conceptually innovative optoelectronic devices.
DOI: 10.1021/ja405776a
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