Enhanced Nonlinear Optical Absorption in Fused-Ring Aromatic Donor-Acceptor-Donor Core Units of Y6 Derivatives

This fundamental understanding of molecular structure-NLO property relationships provides critical design principles for next-generation optical limiting materials, quantum photonic devices, and ultrafast nonlinear optical switches, addressing the growing demand for high-performance organic optoelectronic materials in laser protection and photonic computing applications. In this study, it was observed that selenophene-incorporated fused D-A-D architectures exhibit a remarkable enhancement in two-photon absorption characteristics. By strategically modifying the heteroatomic composition of the Y6-derived fused-ring core, replacing thiophene (BDS) with selenophene (BDSe), the optimized system achieves unprecedented NLO performance. BDSe displays a nonlinear absorption coefficient (β) of 3.32 × 10^-10 m/W and an effective two-photon absorption cross-section (σ_TPA) of 2428.2 GM under 532 nm with ns pulse excitation. Comprehensive characterization combining Z-scan measurements, transient absorption spectroscopy, and DFT calculations reveals that the heavy atom effect of selenium induces enhanced spin-orbit coupling, optimized intramolecular charge transfer dynamics and stabilized excited states, collectively contributing to the superior reverse saturable absorption behavior. It is believed that this molecular engineering strategy establishes critical structure-property relationships for the rational design of organic NLO materials.