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Novel Ferrocene-Appended β-Ketoimines and Related BF₂ Derivatives with Significant Aggregation-Induced Emission and

Ezhumalai David¹, Alessia Colombo², Claudia Dragonetti²

¹Centre for Functional Materials, Department of Chemistry, School of Advanced Sciences, Vellore Institute of Technology, Vellore, 632014, Tamilnadu, India.

Chemistry (Weinheim an Der Bergstrasse, Germany)

|January 22, 2021

Abstract:

A series of new β-ketoimines containing a ferrocene moiety and their BF₂ complexes have been synthesized and structurally characterized. The solvatochromism of the β-ketoimines was studied, putting in evidence a redshift with increasing solvent polarity. This positive solvatochromism can be attributed to a more polarized excited state compared with the ground state, due to intramolecular charge transfer (ICT) transitions. The β-ketoimines exhibited weak emission, attributable to the excited-state intramolecular proton transfer (ESIPT) phenomenon. This ESIPT effect is suppressed upon restriction of the keto-enamine tautomerism, induced upon addition of BF₃ ⋅OEt₂ , which afforded the related BF₂ complexes, characterized by an enhancement of the fluorescence through the ICT effect. Both the β-ketoimines and BF₂ complexes exhibited significant aggregation-induced emission behavior in mixtures of CH₃ CN/H₂ O, due to restriction of intramolecular rotation in the aggregated state. The frontier molecular orbital levels, ground- and excited-state dipole moments (μ_g and μ_e ), and the origin of electronic absorption spectra were studied by time-dependent DFT calculations. The second-order nonlinear optical (NLO) properties were determined by the electric-field-induced second-harmonic generation technique. The μβ₁₉₀₇ values of the β-ketoimines increased upon the formation of the related BF₂ complexes, mainly due to an enhancement of the ground-state dipole moment. The results presented here reveal that some of these novel compounds are excellent multifunctional candidates for NLO and luminescence applications.

Keywords:

aggregation-induced emission density functional calculations nonlinear optics photophysics

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