10.1002/anie.201914070
Angewandte Chemie International Edition
RESEARCH ARTICLE
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Conclusion
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In summary, two naphthyl units with ortho-methoxy group (NM)
were introduced into two of the bay positions of a perylene
bisimide (PBI) structure (PBI-2NM) via rotational and
conjugatable alkynyl bonds. The fluorescence emission intensity
and lifetime of the resulting molecule in solvents such as THF
increase upon raising temperature from -20 ºC to 60 ºC, a
phenomenon rarely found in conventional fluorescent
chromophores. The property was ascribed to the presence of
the C-C triple bond, which allows free rotation and conjugation of
NM units and PBI core. 1H NMR and theoretical calculation
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formation of a weak H-bond (~5 kcal·mol-1, upper limit) between
the methoxy group of the NM unit and a nearby hydrogen atom
of the PBI core, i.e., an Ar-H…O H-bond. The lowest lying
excited state of coplanar PBI-2NM possesses ICT property with
rather low emission efficiency, while LE state with strong
emission contributes to the lowest excited state of the twisted
conformers. The relative population between co-planar and
ensemble of the twisted conformers, hence the interplay
between ICT and LE states, manifests the positive temperature
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effect. Our observation provides not only
a
precious
experimental evidence for existence of a weak H-bond of Ar-
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The related experimental details are provided in the Supporting
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Acknowledgements
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This work was supported by the Natural Science Foundation of
China (21527802, 21673133, 21820102005), 111 project
(B14041), Program for Changjiang Scholars and Innovative
Research Team in University (IRT-14R33) and the Fundamental
Research Funds for the Central Universities of China
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Keywords: perylene bisimide (PBI) • intramolecular hydrogen
bond • intramolecular charge transfer (ICT) • positive
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