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. 2024 Apr 4;30(5):122.
doi: 10.1007/s00894-024-05912-5.

DFT and TDDFT exploration on electronic transitions and bonding aspect of DPA and PTDC ligated transition metal complexes

Mukhtar Ahmed  1 , Sumit Sahil Malhotra  1 , Oval Yadav  1 , Monika  1 , Charu Saini  1 , Neha Sharma  2 , Manoj Kumar Gupta  1 , Ranjan Kumar Mohapatra  3 , Azaj Ansari  4
Affiliations

DFT and TDDFT exploration on electronic transitions and bonding aspect of DPA and PTDC ligated transition metal complexes

Mukhtar Ahmed et al. J Mol Model. .

Abstract

Context: In this study, we have investigated the structure, reactivity, bonding, and electronic transitions of DPA and PDTC along with their Ni-Zn complexes using DFT/TD-DFT methods. The energy gap between the frontier orbitals was computed to understand the reactivity pattern of the ligands and metal complexes. From the energies of FMO's, the global reactivity descriptors such as electron affinity, ionization potential, hardness (η), softness (S), chemical potential (μ), electronegativity (χ), and electrophilicity index (ω) have been calculated. The complexes show a strong NLO properties due to easily polarization as indicated by the narrow HOMO-LUMO gap. The polarizability and hyperpolarizabilities of the complexes indicate that they are good candidates for NLO materials. Molecular electrostatic potential (MEP) maps identified electrophilic and nucleophilic sites on the surfaces of the complexes. TDDFT and NBO analyses provided insights into electronic transitions, bonding, and stabilizing interactions within the studied complexes. DPA and PDTC exhibited larger HOMO-LUMO gaps and more negative electrostatic potentials compared to their metal complexes suggesting the higher reactivity. Ligands (DPA and PDTC) had absorption spectra in the range of 250 nm to 285 nm while their complexes spanned 250 nm to 870 nm. These bands offer valuable information on electronic transitions, charge transfer and optical behavior. This work enhances our understanding of the electronic structure and optical properties of these complexes.

Methods: Gaussian16 program was used for the optimization of all the compounds. B3LYP functional in combination with basis sets, such as LanL2DZ for Zn, Ni and Cu while 6-311G** for other atoms like C, H, O, N, and S was used. Natural bond orbital (NBO) analysis is carried out to find out how the filled orbital of one sub-system interacts with the empty orbital of another sub-system. The ORCA software is used for computing spectral features along with the zeroth order regular approximation method (ZORA) to observe its relativistic effects. TD-DFT study is carried out to calculate the excitation energy by using B3LYP functional.

Keywords: Bonding; DFT/TD-DFT; DPA/PDTC ligands; Electronic transitions; MEP; NBO; Zinc/nickel/copper complexes.

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References

    1. Haas KL, Franz KJ (2009) Application of Metal Coordination Chemistry to Explore and Manipulate Cell Biology. Chem Rev 109:4921–4960. https://doi.org/10.1021/cr900134a - DOI - PubMed - PMC
    1. Garin AB, Rakarić D, Andrić EK et al (2019) Synthesis of monosubstituted dipicolinic acid hydrazide derivative and structural characterization of novel Co(III) and Cr(III) complexes. Polyhedron 166:226–232. https://doi.org/10.1016/j.poly.2019.03.059 - DOI
    1. Arabieh M, Iglesias CP (2016) A density functional theory study on the interaction of dipicolinic acid with hydrated Fe2+ cation. Comput Theor Chem 1090:134–146. https://doi.org/10.1016/j.comptc.2016.06.010 - DOI
    1. Tamer Ö, Sarıboğa B, Uçar İ, Büyükgüngör O (2011) Spectroscopic characterization, X-ray structure, antimicrobial activity and DFT calculations of novel dipicolinate copper(II) complex with 2,6-pyridinedimethanol. Spectrochim Acta A Mol Biomol Spectrosc 84:168–177. https://doi.org/10.1016/j.saa.2011.09.025 - DOI - PubMed
    1. Das B, Baruah JB (2010) Coordinated cations in dipicolinato complexes of divalent metal ions. Inorganica Chim Acta 363:1479–1487. https://doi.org/10.1016/j.ica.2010.01.025 - DOI

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