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Exploration of Chromone-Based Thiosemicarbazone Derivatives: SC-XRD/DFT, Spectral (IR, UV-Vis) Characterization, and Quantum Chemical Analysis.

ABSTRACT: By the condensation of thiosemicarbazide with coumarin aldehyde, two novel substituted thiosemicarbazones with chemical formulae C₂₄H₂₅N₃O₃S (3a) and C₂₆H₂₃N₃O₃S (3b) have been synthesized. The synthesized compounds were resolved using SC-XRD, and structure elucidation was carried out using ¹H NMR, ¹³C NMR, UV-visible, and FT-IR spectroscopic analyses. Computational calculations at the B3LYP/6-311+G(d,p) level of theory were performed to countercheck the experimental (UV-vis, FT-IR) findings and explore the electronic (FMO, NBO, MEP) properties of 3a-b. The nonlinear optical (NLO) properties of 3a-b were estimated using B3LYP, HF, LC-BLYP, CAM-B3LYP, M062X, and M06 functionals in combination with the 6-311+G(d,p) basis set. The crystallographic data revealed that compounds were crystallized as an orthorhombic crystal lattice with the Pbcn space group and the triclinic crystal lattice with the P?1 space group. A good concurrence among experimental SC-XRD-generated bond lengths, bond angles, FT-IR, UV-vis, and corresponding DFT results was found, which confirms the purity of both compounds. The NBO analysis confirmed the presence of intramolecular hydrogen bonding and hyperconjugative interactions, which not only were the pivotal cause of stability of the investigated compounds but also led to an overwhelming NLO response. The energy differences calculated for HOMO/LUMO are 3.053 and 3.118 eV in 3a and 3b, respectively. The crystal 3b showed a higher value of first-order polarizability at all levels of theory than 3a. Overall results show that the crystals under investigation are polarized in nature with a good dipole moment. A comparative analysis with urea molecules clearly indicates that the studied compounds are acceptable NLO candidates and they can be used for future technological applications.

SUBMITTER: Basri R

PROVIDER: S-EPMC7689885 | biostudies-literature | 2020 Nov

REPOSITORIES: biostudies-literature

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Exploration of Chromone-Based Thiosemicarbazone Derivatives: SC-XRD/DFT, Spectral (IR, UV-Vis) Characterization, and Quantum Chemical Analysis.

Basri Rabia R Khalid Muhammad M Shafiq Zahid Z Tahir Muhammad Suleman MS Khan Muhammad Usman MU Tahir Muhammad Nawaz MN Naseer Muhammad Moazzam MM Braga Ataualpa Albert Carmo AAC

ACS omega 20201110 46

By the condensation of thiosemicarbazide with coumarin aldehyde, two novel substituted thiosemicarbazones with chemical formulae C24H25N3O3S (3a) and C26H23N3O3S (3b) have been synthesized. The synthesized compounds were resolved using SC-XRD, and structure elucidation was carried out using 1H NMR, 13C NMR, UV-visible, and FT-IR spectroscopic analyses. Computational calcula ...[more]

PMID: 33251452

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Project description:A methodological survey of density functional theory (DFT) methods for the prediction of UV-visible (vis)-near-infrared (NIR) spectra of phthalocyanines is reported. Four methods, namely, full time-dependent (TD)-DFT and its Tamm-Dancoff approximation (TDA), together with their simplified modifications (sTD-DFT and sTDA, respectively), were tested by using the examples of unsubstituted and alkoxy-substituted metal-free ligands and zinc complexes. The theoretical results were compared with experimental data derived from UV-visible absorption and magnetic circular dichroism spectroscopy. Seven popular exchange-correlation functionals (BP86, B3LYP, TPSSh, M06, CAM-B3LYP, LC-BLYP, and ωB97X) were tested within these four approaches starting at a relatively modest level using 6-31G(d) basis sets and gas-phase BP86/def2-SVP optimized geometries. A gradual augmentation of the computational levels was used to identify the influence of starting geometry, solvation effects, and basis sets on the results of TD-DFT and sTD-DFT calculations. It was found that although these factors do influence the predicted energies of the vertical excitations, they do not affect the trends predicted in the spectral properties across series of structurally related substituted free bases and metallophthalocyanines. The best accuracy for the gas-phase vertical excitations was observed in the lower-energy Q-band region for calculations that made use of range-separated hybrids for both full and simplified TD-DFT approaches. The CAM-B3LYP functional provided particularly accurate results in the context of the sTD-DFT approach. The description of the higher-energy B-band region is considerably less accurate, and this demonstrates the need for further advances in the accuracy of theoretical calculations. Together with a general increase in accuracy, the application of simplified TD-DFT methods affords a 2-3 orders of magnitude speedup of the calculations in comparison to the full TD-DFT approach. It is anticipated that this approach will be widely used on desktop computers during the interpretation of UV-vis-NIR spectra of phthalocyanines and related macrocycles in the years ahead.

Dataset Information

Exploration of Chromone-Based Thiosemicarbazone Derivatives: SC-XRD/DFT, Spectral (IR, UV-Vis) Characterization, and Quantum Chemical Analysis.

Publications

Exploration of Chromone-Based Thiosemicarbazone Derivatives: SC-XRD/DFT, Spectral (IR, UV-Vis) Characterization, and Quantum Chemical Analysis.

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