Theoretical Insights into the Structural and Optical Properties of D−π–A-based Cyanostilbene Systems of α and β Variants

High Resolution Image Download MS PowerPoint Slide The π-conjugated organic molecules containing cyanostilbene motifs have been extensively investigated due to their great potential applications in several optoelectronic and biological fields. Developing efficient molecules in this respect requires strategic structural engineering and a deep understanding of the structure–property relationship at the molecular level. In this context, understanding the impact of positional isomerism in cyanostilbene systems is a fundamental aspect of designing desired materials with improved photophysical properties. Herein, we designed ten donor–π–acceptor (D−π–A) type cyanostilbene derivatives ( P 1 – P 10 ) with different π linkers and compared their structural and optoelectronic properties arising from the positional variations of the –CN group (α and β- variations) through the utilization of density functional theory (DFT) and time-dependent DFT (TDDFT) methods. The topological analyses of the electron density are used to explain the relatively high stability of α isomer compared to that of β. Frontier molecular orbital analysis reveals that 17 molecules tend to show a reduced highest occupied molecular orbital–lowest unoccupied molecular orbital gap, and most of them showed a greater nonlinear optical (NLO) character compared to the parent molecule. TDDFT calculations indicate that β isomers show higher absorption maxima compared to their α counterparts. Among all the scrutinized molecules, the absorption maximum extended up to 602 nm for P 9 and it possesses the highest first-order hyperpolarizability. This study sheds light on positional isomers and their reactivity, absorption spectra, and NLO properties of D−π–A type architecture that can be suitably tuned by appropriating the π-bridge for practical applications.