Double Hook Perylene Diimide as a New Receptor for PAHs: An Experimental and Theoretical Study

In a one‐step reaction, we prepared a dibenzylamine perylene diimide derivative (PDI). Its double hook structure allows for self‐association with a constant of Kd ∼108 M−1 determined by fluorescence. We confirmed its ability to bind PAHs using UV/Vis, fluorescence, and 1H NMR titrations in CHCl3. Th...

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Bibliographic Details
Published in:Chemphyschem 2023-06, Vol.24 (12), p.e202300071-n/a
Main Authors: Rodríguez‐Uribe, Nadia Alejandra, Contreras‐Martínez, Rodrigo, Jaime‐Adán, Everardo, García‐Betancourt, María Luisa, Bernal‐Uruchurtu, Margarita I., Godoy‐Alcántar, Carolina
Format: Article
Language:English
Subjects:
Anthracene
aromatic molecules
binding constants
Charge transfer
Chloroform
Complex formation
Diimide
Fluorescence
Naphthalene
NMR
noncovalent interaction analysis
Nuclear magnetic resonance
perylene diimide
Phenanthrene
pi-interaction
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Summary:In a one‐step reaction, we prepared a dibenzylamine perylene diimide derivative (PDI). Its double hook structure allows for self‐association with a constant of Kd ∼108 M−1 determined by fluorescence. We confirmed its ability to bind PAHs using UV/Vis, fluorescence, and 1H NMR titrations in CHCl3. The complex formation signature in UV/vis is a new band at 567 nm. The calculated binding constants (Ka∼104 M−1) follow the trend pyrene>perylene>phenanthrene>naphthalene>anthracene. Theoretical modeling of these systems using DFT ωB97X‐D/6‐311G(d,p) proved helpful in rationalizing the complex formation and the observed association trend. The distinctive signal in UV/vis is due to a charge transfer in the complex from orbitals in the guest to the host. SAPT(DFT) confirmed that the driving forces in the complex formation are exchange and dispersion (π–π interactions). Still, the recognition ability depends on the electrostatic component of the interaction, a minor fraction. Double hook‐like molecule is prepared in a one‐step reaction that shows an excellent ability to bind PAH and exhibits interesting properties for developing sensors. Its behavior is thoroughly characterized with spectroscopic methods and supported by DFT calculations. The image shows a UV/vis titration of PDI with perylene, presenting a colorimetric change.
ISSN:1439-4235
1439-7641
DOI:10.1002/cphc.202300071