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000617132 1001_ $$aTeichmann, Ben$$b0
000617132 245__ $$a‘Invisible’ Molecular Dynamics Revealed for a Conformationally Chiral π‐Stacked Perylene Bisimide Foldamer
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000617132 520__ $$aWhilst energetic and kinetic aspects of folding processes are meanwhile well understood for natural biomacromolecules, the folding dynamics in so far studied artificial foldamer counterparts remain largely unexplored. This is due to the low energy barriers between their conformational isomers that make the dynamic processes undetectable with conventional methods such as UV/Vis absorption, fluorescence, and NMR spectroscopy, making such processes ‘invisible’. Here we present an asymmetric perylene bisimide dimer (bis-PBI 1) that possesses conformational chirality in its folded state. Owing to the large interconversion barrier (≥116 kJ mol−1), four stereoisomers could be separated and isolated. Since the interconversion between these stereoisomers requires the foldamer to first open and then to re-fold, the transformation of one stereoisomer into others allowed us to ‘visualize’ the dynamics of folding with time and determine its lifetimes and the energetic barriers associated with the folding process. Supported by quantum chemical calculations, we identified the open structure to be only a fleetingly metastable state of higher energy. Our experimental observation of the kinetics associated with the molecular dynamics in the PBI foldamer advances the fundamental understanding of folding in synthetic foldamers and paves the way for the design of smart functional materials. 
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000617132 7001_ $$aSárosi, Menyhárt$$b1
000617132 7001_ $$0P:(DE-H253)PIP1094122$$aShoyama, Kazutaka$$b2
000617132 7001_ $$0P:(DE-H253)PIP1094243$$aMundakkamattathil Abdul Salam, Niyas$$b3
000617132 7001_ $$aDubey, Rajeev K.$$b4
000617132 7001_ $$0P:(DE-H253)PIP1094247$$aWuerthner, Frank$$b5$$eCorresponding author
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