Structure–property relationship for fluorophores with favorable nonlinear optical (NLO) properties are promising topics in organic chemistry and material science. Herein, a series of terthiophene-o-carborane dyads and triads covalently linked with different end-capping styles were readily synthesized and comprehensively investigated. Quantitative values of the crystal and packing structures, photophysical parameters including aggregation-induced emission (AIE) and two-photon absorption (2PA) were provided. Significant impact of carborane unit for introducing the AIE characteristic has been investigated in contrast to the parent oligothiophene. All the obtained fluorophores exhibit maximum absorption around 370 nm in THF and emit bright reddish photoluminscence with absolute fluorescence quantum yields above 16% in solid states. Intramolecular charge communication between oligothiophene and carborane plays important roles in the related NLO properties. These results are supported well by the time-dependent DFT theoretical calculations. Effective 2PA cross sections (δ2PA = 95–355 GM@650 nm) and transition dipole moments of the derivatives are variable for different end-capping styles. Their potential applications as optical limiting materials based on the 2PA mechanism in solutions and doped PDMS films were further evaluated. Taken together, this work provides an understanding of their structure–property relationship, and flexible PDMS films as outstanding candidates for practical applications in optical limiting.

Push−pull organic structures characterized by an intramolecular charge transfer (ICT) process and π-electron delocalization are potentially interesting luminescent materials. A series of three-dimensional o-carborane-containing perylene bisimide derivatives (PBIs) were synthesized, and their optical properties were systematically investigated to illustrate the stereo effect, especially on the two-photon absorption (2PA) and optical power limiting (OPL) properties. Open-aperture Z-scan curves showed that all four PBIs displayed strong and broad two-photon absorptivities based on the resonance-enhanced phenomenon. The maximum degenerate two-photon absorption cross section (δ 2PA ) increased with the number of PBI substituents. The derivative CB-PBI possessed a δ 2PA value of ∼2400 GM at 650 nm, a significant enhancement in comparison with that of the parent PBI (∼719 GM), ascribed to the present stereo effect. When the aromatic-donating units changed from naphthyl and pyrenyl to PBI, the generated multidimensional intramolecular charge transfer (ICT) from the aromatic units to the o-carborane cage contributed to the 2PA processes. All of the fluorophores exhibited excellent optical power limiting (OPL) performances as well as a minimum limiting threshold of ∼4.98 mJ/cm 2 for CB-PBI. These significant results not only allow us to get deep insight into the nature of the fundamental stereo effect and nonlinear optical (NLO) response involved but also guide us toward the design of new multifunctional luminescent materials.

Pure-bromide quasi-2D perovskite (PBQ-2DP) promises high-performance light-emitting diodes (LEDs), while a challenge remains on control over its n-phase distribution for bright true-blue emission. Present work addresses the challenge through exploring the passivation molecule of amino acid with reinforced binding energy, which generates narrow n-phase distribution preferentially at n = 3 with true blue emission at 478 nm. Consequently, a peak external quantum efficiency of 5.52% and a record brightness of 512 cd m −2 are achieved on the PBQ-2DP-based true blue PeLED, these both values located among the top in the records of similar devices. We further reveal that the electron−phonon coupling results in the red-shifted emission in the PBQ-2DP film, suggesting that the view of n-phase distribution dominated true-blue emission in PBQ-2DP needs to be revisited, pointing out a guideline of electron−phonon coupling suppression to relieve the strait of realizing true blue or even deep blue emission in the PBQ-2DP film.

Intramolecular charge transfer and excited-state symmetry breaking have a significant effect on the nonlinear optical properties of multipolar chromophores. Rigid and nonplanar perylene bisimide derivatives (PBIs) functionalized at bay positions were comparatively and comprehensively investigated. In apolar solvents, two quadrupolar molecular rotors showed an obvious decrease of the A 0‑0/A 0‑1 ratios, suggesting strong exciton coupling with the adjacent PBI units initiated by the π–π stacking. The vanishment of the preferable dimer emission in polar solvents supported the plausible phenomena of excited-state symmetry breaking, thanks to the facile rotation around the rigid linkers. Comparative femtosecond transition absorption studies confirmed their notable differences in relaxation dynamics and the generation of radical anions (PBI•–) and cations (PBI•+). The maxima two-photon absorption (2PA) wavelengths obtained for the molecular rotors were slightly red-shifted to 670 nm with intrinsic resonance-enhanced characteristics, reflecting the synergistic effect of functional positions and molecular architectures. Meanwhile, the obvious increase of significant 2PA cross-section values in polar solvents illustrated the stabilization of the symmetry-broken dipolar states. Further femtosecond Z-scan also manifested the contribution of excited-state dynamics on the nonlinear optical properties of multipolar chromophores.

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