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Syntheses of variants of π(σ) aromatic modified N-methyl N-confused porphyrinoids with adaptive properties

Retrosynthetically designed and syntheses of three unprecedented core modified N-confused porphyrinoids exhibiting vis-NIR absorption with tunable aromaticity is reported. Controlled modification of types of oxidants (chloranil vs. DDQ) has led to the isolation of 18π-aromatic porphyrinoid 7 (upon c...

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Bibliographic Details
Main Authors: Panua, Anirban (Author) , Velmurugan, Gunasekaran (Author) , Comba, Peter (Author) , Rath, Harapriya (Author)
Format: Article (Journal)
Language:English
Published: February 17, 2025
In: Chemistry
Year: 2025, Volume: 20, Issue: 4, Pages: 1-8
ISSN:1861-471X
DOI:10.1002/asia.202401196
Online Access:Verlag, lizenzpflichtig, Volltext: https://doi.org/10.1002/asia.202401196
Verlag, lizenzpflichtig, Volltext: https://onlinelibrary.wiley.com/doi/abs/10.1002/asia.202401196
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Author Notes:Anirban Panua, Gunasekaran Velmurugan, Peter Comba, and Harapriya Rath
Description
Summary:Retrosynthetically designed and syntheses of three unprecedented core modified N-confused porphyrinoids exhibiting vis-NIR absorption with tunable aromaticity is reported. Controlled modification of types of oxidants (chloranil vs. DDQ) has led to the isolation of 18π-aromatic porphyrinoid 7 (upon chloranil oxidation) while DDQ oxidation has led to 18 e σ-aromatic porphyrinoids 8 and 9. All the three SN3 hybrid N-confused porphyrinoids 7-9 have been thoroughly characterized via solution state spectroscopic measurements and in-depth DFT studies for concluding π-aromaticity of 7 and σ-aromaticity of 8 and 9. While 7 could recognize the fluoride anion with high selectivity via deprotonation rather than an anion recognition based mechanism, acetate anion binding studies clearly revealed NH⋅⋅⋅AcO− H-bonding interaction in the host-guest complex [7-AcO−] supporting an anion recognition based mechanism. Porphyrinoids 8 and 9 remain unsusceptible to anion recognition. The conformational preorganization and anion induced deprotonation leading to conformational reorganization have been extensively studied by solution state spectroscopic techniques and in depth DFT level theoretical calculations.
Item Description:Zuerst veröffentlicht: 27. November 2024
Gesehen am 12.03.2025
Physical Description:Online Resource
ISSN:1861-471X
DOI:10.1002/asia.202401196

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