Journal
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 133, Issue 40, Pages 16201-16211Publisher
AMER CHEMICAL SOC
DOI: 10.1021/ja2066225
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Funding
- Israel Science Foundation
- Helen and Martin Kimmel Center for Molecular Design
- Toronto, Canada
- U.S. DOE [DE-AC02-06CH11357]
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Self-assembly in aqueous medium is of primary importance and widely employs hydrophobic interactions. Yet, unlike directional hydrogen bonds, hydrophobic interactions lack directionality, making difficult rational self-assembly design. Directional hydrophobic motif would significantly enhance rational design in aqueous self-assembly, yet general approaches to such interactions are currently lacking. Here, we show that pairwise directional hydrophobic/pi-stacking interactions can be designed using well-defined sterics and supramolecular multivalency. Our system utilizes a hexasubstituted benzene scaffold decorated with 3 (compound 1) or 6 (compound 2) amphiphilc perylene diimides. It imposes a pairwise self-assembly mode, leading to well-defined supramolecular polymers in aqueous medium. the assemblies were characterized using cryogenic electron microscopy, small-angle X-ray scattering, optical spectroscopy, and EPR. Supramolecular polymerization studies in the case of 2 revealed association constants in 10(8) M-1 range, and significant enthalpic contribution to the polymerization free energy. The pairwise PDI motif enables exciton confinement and localized emission in the polymers based on 1 and 2's unique photonic behavior, untypical of the extended pi-stacked systems. Directional pairwise hydrophobic interactions introduce a novel strategy for rational design of noncovalent assemblies in aqueous medium, and bring about a unique photofunction.
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