Comparative
Analysis of the Hydrazine Interaction
with Arylene Diimide Derivatives: Complementary Approach Using First
Principles Calculation and Experimental Confirmation
posted on 2024-05-15, 17:37authored byAditya Tiwari, Rikitha S. Fernandes, Nilanjan Dey, Sayan Kanungo
Suitable functional group-engineered π-conjugated
aromatic
dimides based on perylene (PDI) and naphthyl scaffolds (NDI) demonstrated
excellent sensitivity toward different gaseous analytes. However,
to date, no methodical analysis has been performed to rationalize
molecular-level interactions in the context of optical transduction,
which is essential for systematic performance optimization of NDI/PDI-based
molecular sensors. Therefore, in this present work, NDI/PDI scaffolds
have been designed with amino acid functional groups (alanine, ALA
and glutamic acid, GLU) at the terminal positions, and we subsequently
compared the efficacy of four different imide derivatives as model
hosts for hydrazine adsorption. Specifically, the adsorption of hydrazine
at different interaction sites has been thoroughly investigated using
ab initio calculations, where the adsorption energy, charge transfer,
and recovery time have been emphasized. Theoretical results exhibit
that irrespective of host specification the COOH groups offer a primary
interaction site for hydrazine through the hydrogen bonding interaction.
The presence of more COOH groups and relatively stronger interaction
with secondary edge oxygen ensure that GLU functional moieties are
a superior choice over ALU for efficient hydrazine binding. The molecular
energy spectrum analysis exhibits more favorable HOMO/LUMO gap variations
after hydrazine interaction in the case of PDI derivatives irrespective
to the nature of the amino acid residues. Therefore, by a combination
of both factors, PDI-GLU has been identified as the most
suitable host molecule for hydrazine among four derivatives. Finally,
the key theoretical predictions has been later experimentally validated
by analyzing UV–visible spectroscopy and NMR studies, wherein
the mechanism of interaction has also been experimentally verified
by EPR analysis and FT-IR studies.