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 (μg and μe ), 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.

Novel Ferrocene-Appended β-Ketoimines and Related BF2 Derivatives with Significant Aggregation-Induced Emission and Second-Order Nonlinear Optical Properties / E. David, A. Colombo, C. Dragonetti, N. Palanisami. - In: CHEMISTRY. - ISSN 1521-3765. - 27:24(2021 Apr 26), pp. 7124-7137. [10.1002/chem.202005059]

Novel Ferrocene-Appended β-Ketoimines and Related BF2 Derivatives with Significant Aggregation-Induced Emission and Second-Order Nonlinear Optical Properties

A. Colombo
Secondo
;
C. Dragonetti
Penultimo
;
2021-04-26

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 (μg and μe ), 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.
aggregation-induced emission; density functional calculations; nonlinear optics; photophysics;
Settore CHIM/03 - Chimica Generale e Inorganica
mar-2021
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Utilizza questo identificativo per citare o creare un link a questo documento: http://hdl.handle.net/2434/859731
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