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Experiment Driven Computations of HOMO-LUMO and Steric Maps to Understand the Selectivity of Sensor on Metal: Insights from Al3+-‘imine-hydroxyl Pocket’ Model
EP37776
Poster Title: Experiment Driven Computations of HOMO-LUMO and Steric Maps to Understand the Selectivity of Sensor on Metal: Insights from Al3+-‘imine-hydroxyl Pocket’ Model
Submitted on 20 Oct 2021
Author(s): K. Sivakumar (a)*, G. Parinamachivayam (a), and M. Murali Krishnan (b)
Affiliations: aSri Chandrasekharendra Saraswathi Viswa Mahavidyalaya (Deemed to be University) [SCSVMV University], Department of Chemistry, Faculty of Science, Enathur, Kanchipuram, Tamilnadu, India bBannari Amman Institute of Technology, Department of Chemistry, Sathyamangalam, Tamilnadu, India. Email : chemshiva@gmail.com, sivakumar.k@kanchiuniv.ac.in
This poster was presented at http://www.aeaci.org/CTAC-2021/ - Current Trends in Analytical Chemistry (CTAC-2021)
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Poster Information
Abstract:
The experimental results (the drive): The imine-hydroxyl chelation pocket’ of o-phenolnaphthylimine (pni) was reinforced by forming inclusion complex with β-cyclodextrin (β-cd) for strengthening the native detection of Al3+ by pni. The selectivity of pni:β-cd complex towards Al3+ was further confirmed from the observation of absence of emission enhancement of pni for different metals (M+) of similar ionic radius [Cr3+ (62pm), Fe3+ (60pm), Mg2+ (72pm), Cu2+ (73pm), Co2+ (70pm) and Zn2+ (74pm)] to Al3+ (53pm).
Theoretical investigations based on experiments: In order to gain insights on the selectivity of pni:β-cd towards Al3+, the HOMO-LUMO and steric maps of all the metals with chemosensor (i.e., pni:β-cd-M+) was computed.
Results of theoretical Investigations: The highest EHOMO/LUMO (ΔE) = 7.767eV and the lowest complexation energy EC = -5744.9 KJ/mol values for pni:β-cd-Al3+ than other metal ion complexes infers the greater extent of chelation of Al3+ with imine (C=N) moiety of pni. The maximum buried volume of pni:β-cd-Al3+ than other metal ions pni:β-cd-M+ (Fig. 1) infers the attainment of optimum rigid fit and steric effect (%Vbur=76.4)) responsible for selectivity.

Conclusion: The result of theoretical investigations correlates well with the experimental data.
Summary: Experiment Driven Computations of HOMO-LUMO and Steric Maps to Understand the Selectivity of Sensor on Metal: Insights from Al3+-‘imine-hydroxyl Pocket’ Model
References: K. Sivakumar, G. Parinamachivayam, M. Murali Krishnan, V. Ragavendran, T. Stalin, K. Premkumar, Sujay Chakravarty, A. Bharathi, Journal of Molecular Liquids, 323 (2021) 114949Report abuse »
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