Remarkable enhancement of the nonlinear optical behavior towards asymmetric substituted D-π-A dithiophene-based...

Nonlinear optics (NLO) is an interesting field that discloses the interaction between intense light and matter, leading to a deeper understanding of NLO phenomena. Organic chromophores are considered as promising materials for NLO due to their exceptional structural versatility, ease of processing, and rapid response to NLO effects. Functional materials based on thiophene have been indispensable in advancing organic optoelectronics. Specifically, dithiophene-based compounds display weaker aromaticity, reduced steric hindrance, and additional sulfur-sulfur interactions. Hence, by utilizing dithieno[2,3-d:2',3'-d']benzo[1,2-b:4,5-b']dithiophene (DTBDT) as the core structure, designing of a set of organic compounds with D1-π-D2-π-A-type framework, namely ZR1D1-ZR1D8, was carried out in this study. The analysis of frontier molecular orbitals (FMOs) revealed that compound ZR1D2 has the lowest band gap of 1.922 eV among all the investigated chromophores. The correlation of global reactivity parameters (GRPs) with the band gap values indicates that ZR1D2 displays a hardness of 0.961 eV and a softness of 0.520 eV^-1. Among the studied compounds, ZR1D2 demonstrated a broad absorption spectrum that extended across the visible region. The maximum absorption wavelengths were observed at 766.470 nm for ZR1D2 and 749.783 nm for ZR1D5. These DTBDT-based dyes exhibit a remarkable NLO response with exceptionally high first hyperpolarizability (β_tot) values. Among them, compound ZR1D2 stands out with the highest average linear polarizability (⟨α⟩ = 3.0 × 10^-22 esu), first hyperpolarizability (β_tot = 4.1 × 10^-27 esu), and second hyperpolarizability (γ_tot = 7.5 × 10^-32 esu) values. In summary, this investigation offers valuable insights into the potential use of DTBDT-based organic chromophores, particularly ZR1D2, for advanced applications in NLO. These findings suggest promising opportunities for researchers to synthesize these molecules and utilize these compounds in hi-tech NLO-based applications.

The density functional theory computations were performed at the M06/6-311G(d,p) functional to explore their structural effects on electronic and NLO findings. Various analyses like highest occupied molecular orbital-lowest unoccupied molecular orbital energy gaps, absorption maxima, density of states, open circuit voltage, binding energies of electrons and holes, and transition density matrix are employed to investigate photovoltaic efficiencies of the derivatives. Different software packages like Avogadro, Multiwfn, Origin, GaussSum, PyMOlyze, and Chemcraft were used to deduce conclusions from the output files.