Intramolecular charge transfer (ICT) is an important factor in the nonlinear optical (NLO) properties of organic molecules. In order to study the effect of ICT on two-photon absorption (TPA) and excited-state absorption (ESA), three chalcone derivatives (1, 2 and 3) with different electron push–pull systems were designed and synthesized. The ICT performance of these chalcone derivatives depends on the electron push–pull systems and mainly includes ultrafast ICT in the femtosecond time domain and long-lived charge transfer state (CTS) in the picosecond time domain, which dominate the performance of molecular TPA and ESA respectively. Hole–electron analysis and femtosecond Z-scan experiment indicate that the TPA cross section of these chalcone derivatives can be effectively enhanced by introducing stronger ultra-fast ICT in the case of little difference in ground-state absorption and expanding the molecular π-conjugated structure. Transient absorption spectrum (TAS) experiments of these compounds in solvents of varying polarities were conducted to visualize the establishment of CTS. The local excited state (LES) and charge transfer state (CTS)-based ESA of these chalcone derivatives are extremely dependent on the strength of ICT. Our experimental results show that the superposition of LES and CTS by enhancing ICT performance can effectively improve the ESA, which offers us a practical method to improve the long-impulse response of organic materials.

Intramolecular charge transfer (ICT) and π-electron delocalization are two key factors affecting the nonlinear optical absorption of organic molecules. To clarify the different influences of ICT and π-electron delocalization on two-photon absorption (TPA) and excited-state absorption (ESA), monomeric coumarin C1 and dimeric coumarin C2 are synthesized and studied. Transient absorption spectroscopy (TAS) analysis of these coumarin derivatives in solvents of varying polarities describes the polarity-dependent excited-state dynamics and reveals the ESA signals of the charge transfer state (CTS) and local excited state (LES) with different spectral features. Femtosecond broadband Z-scan experiments indicate that dimeric coumarin C2 has a more significant TPA response than monomeric coumarin C1 in the near-infrared region. Natural transition orbital (NTO) analysis further theoretically characterizes the electron transition feature induced by TPA. Our results reveal that the TPA of these coumarin derivatives can be significantly enhanced by expanding π-electron delocalization, but their ESA is mainly dominated by ICT performance. This study indicates that coumarin derivatives will exhibit extremely broad application prospects in the field of ultrafast optical limiting (OL) through reasonable molecular design.