Facile Synthesis, Spectroscopic and Nonlinear Optical Insights of Hydrazinyl-Based Functional Materials: Experimental and DFT Approach

Abstract

A series of hydrazinyl thiazol-4-one based scaffolds (EBHT1-ETHT5) had been prepared through condensation process of substituted thiosemicarbazone with ethyl bromoacetate and sodium acetate. The structure confirmation of formed compounds was done through several spectroscopic methods. Beside synthesis, quantum chemical investigations were executed at MPW1PW91/6-311G(d,p) functional to explore nonlinearity of EBHT1-ETHT5. At first, the structures of prepared chromophores were optimized to get true minima geometries. These optimized geometries were further utilized to carry out the natural bond orbitals (NBO), transition density matrix (TDMx), UV-Vis analysis, density of states (DOS), and nonlinear optic (NLO) characteristics. A minimum E_gap (4.433 eV) was achieved in EBHT1 with wider absorption spectrum (λ_max= 339 nm) than that of other yielded compounds. A significant charge transference is seen with in molecules through DOS and TDM findings. The GRPs findings explored that all the afore-said chromophores had higher value of global hardness (η = 4.433–4.657 eV) along with lower softness (σ = 0.432–0.277 eV). Significant NLO results were obtained for prepared chromophores as compared to reference urea chromophore. These organic chromophores can be considered as potential candidates in NLO-based applications.

Keywords:

• Third order NLO
• hydrazinyl-based materials
• NBO analysis
• DOS analysis
• hyper polarizabilities studies

Acknowledgment

Dr. Muhammad Khalid gratefully acknowledges the financial support of HEC Pakistan (project no. 20-14703/NRPU/R&D/HEC/2021). A.A.C.B. acknowledges the financial support of the São Paulo Research Foundation (FAPESP) [Grants 2014/25770-6 and 2015/01491-3], the Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) of Brazil for academic support [Grant 309715/2017-2], and Coordenação de Aperfeiçoamento de Pessoal de Nível Superior – Brasil (CAPES) that partially supported this work (Finance Code 001). The authors extend their sincere appreciation to Researchers Supporting Project number (RSP2023R253), King Saud University, Riyadh, Saudi Arabia.

Ethical approval

Our work is not related to human and/or animal studies therefore this section is not applicable.

Author contributions

Hasnain Mehmood: Conceptualization; methodology; software. Tashfeen Akhtar: Conceptualization; methodology. Muhammad Haroon: Data curation; formal analysis. Muhammad Khalid: Methodology; software; project administration. Simon Woodward: Conceptualization; resources. Iqra Shafiq: Data curation; formal analysis; validation. Ataualpa A. C. Braga; methodology; software, Norah Alhokbany; Conceptualization; Writing-review & editing.

Disclosure statement

No potential conflict of interest was reported by the authors.

Data availability statement

All data generated or analyzed during this study are included in this published article and its supplementary information files.

Additional information

Funding

Dr. Muhammad Khalid gratefully acknowledges the financial support of HEC Pakistan (project no. 20-14703/NRPU/R&D/HEC/2021).