Abstract
New synthetic methodologies for the formation of block copolymers have revolutionized polymer science within the last two decades. However, the formation of supramolecular block copolymers composed of alternating sequences of larger block segments has not been realized yet. Here we show by transmission electron microscopy (TEM), 2D NMR and optical spectroscopy that two different perylene bisimide dyes bearing either a flat (A) or a twisted (B) core self-assemble in water into supramolecular block copolymers with an alternating sequence of (AmBB)n. The highly defined ultralong nanowire structure of these supramolecular copolymers is entirely different from those formed upon self-assembly of the individual counterparts, that is, stiff nanorods (A) and irregular nanoworms (B), respectively. Our studies further reveal that the as-formed supramolecular block copolymer constitutes a kinetic self-assembly product that transforms into thermodynamically more stable self-sorted homopolymers upon heating.
Highlights
New synthetic methodologies for the formation of block copolymers have revolutionized polymer science within the last two decades
We report our unique findings on the bicomponent system perylene bisimide (PBI) 1/PBI 2 that hydrophobic interactions lead to the formation of kinetically controlled supramolecular copolymers in water as explored by transmission electron microscopy (TEM) and two-dimensional (2D) nuclear magnetic resonance (NMR) studies as well as optical spectroscopy
Our studies showed that these co-assemblies consist of an alternating sequence of respective self-assembled blocks of PBI 1 and PBI 2 that exhibit unusual fluorescence properties, that is, depending on the excitation wavelength emission originates from either PBI 1 or PBI 2 segments, respectively
Summary
New synthetic methodologies for the formation of block copolymers have revolutionized polymer science within the last two decades. Multicomponent assembly is by far less explored, despite its high promises for the construction of novel nanosized composite materials With his pioneering work on the elucidation of mixtures of established small-sized self-assembling systems, in particular based on hydrogen-bonding-recognition patterns, Isaacs established the research field of self-sorting phenomena[4] that has gained increasingly more importance during the last decade. We report our unique findings on the bicomponent system PBI 1/PBI 2 that hydrophobic interactions lead to the formation of kinetically controlled supramolecular copolymers in water as explored by TEM and two-dimensional (2D) nuclear magnetic resonance (NMR) studies as well as optical spectroscopy These results provide novel insights into the evolution of p-stacked supramolecular structures in aqueous media[32,33,34,35,36]
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