Twisted intramolecular motion arrested in aggregated state emission and the nonlinear optical properties of pyrene pyrazoline derivatives

Heterocyclic pyrene pyrazoline moieties containing similar structures but with differences in thiophene (PPT), furan (PPF) and pyridine (PPP) substitutions at the terminal molecules were synthesized. Their aggregation behaviour in THF-water mixtures was investigated and results demonstrated that PPT and PPP exhibited aggregation-induced emission (AIE), whereas PPF exhibited aggregation-induced blue-shifted emission (AIBSE). PPT and PPP provided red-shifted emission, while PPF had observed blue-shifted emission at high water fractions of 70-90%, confirming that aggregation effects played a major role in the molecular structure. Two emission peaks from locally excited and twisted intramolecular charge transfer confirmed the twisted nature from the dihedral angle values of the free reorganized molecules that were completely restricted in high water fractions due to molecular aggregation. This was further confirmed from colour Commission Internationale de l'Eclairage values as well as dynamic light scattering analysis. Third-order nonlinear optical properties were studied using a Nd:Yag laser beam Z-scan technique at 532 nm. The open aperture Z-scan revealed that PPT and PPF towards the peak point endured strong saturable absorption, whereas PPP indicated a strong reverse saturable absorption process. The AIE and AIBSE mechanisms from undergoing restricted twisting intramolecular motion in the aggregated luminogens provide great insight into new developments in AIEgen materials for these optoelectronic materials.

Automated summary

In this study, molecules containing heterocyclic pyrene pyrazoline moieties with different thiophene (PPT), furan (PPF), and pyridine (PPP) substitutions at the terminal molecules were synthesized and their aggregation behavior in THF-water mixtures was investigated. It was found that PPT and PPP exhibited aggregation-induced emission (AIE), while PPF exhibited aggregation-induced blue-shifted emission (AIBSE), demonstrating the significant role of aggregation effects in the molecular structure. Additionally, the molecules displayed strong nonlinear optical properties, with PPT and PPF showing strong saturable absorption and PPP indicating a strong reverse saturable absorption process.