Unique structural effect on the fluorosolvatochromism and dual fluorescence emission of D-π-A+ cationic chromophores with furyl bridge. An approach to white light emitters

Hoda Mahmoud; Mohamed A Ismail; Hesham A A Medien; Hesham S Abdel-Samad; Ayman A Abdel-Shafi

doi:10.1016/j.saa.2023.123771

Unique structural effect on the fluorosolvatochromism and dual fluorescence emission of D-π-A⁺ cationic chromophores with furyl bridge. An approach to white light emitters

Spectrochim Acta A Mol Biomol Spectrosc. 2024 Mar 5:308:123771. doi: 10.1016/j.saa.2023.123771. Epub 2023 Dec 17.

Authors

Hoda Mahmoud¹, Mohamed A Ismail², Hesham A A Medien¹, Hesham S Abdel-Samad¹, Ayman A Abdel-Shafi³

Affiliations

¹ Department of Chemistry, Faculty of Science, Ain Shams University, Abbassia, Cairo, 11566, Egypt.
² Department of Chemistry, Faculty of Science, Mansoura University, 35516 Mansoura, Egypt.
³ Department of Chemistry, Faculty of Science, Ain Shams University, Abbassia, Cairo, 11566, Egypt. Electronic address: aaashafi@sci.asu.edu.eg.

PMID: 38150988
DOI: 10.1016/j.saa.2023.123771

Abstract

Photophysical behavior of two D - π - A⁺ cationic compounds with the same furyl bridge and nicotinamidine group as an electron acceptor moiety and two electron donating groups, namely methoxy (I) and N,N-dimethylamino (II) groups was examined using steady-state and time-resolved techniques in variety of solvents. Time-dependent density functional theory (TDDFT) calculations were performed in some representative solvents and compared with the experimental results. Steady state and time-resolved studies in different solvents reveal that fluorescence emission of (I) is ascribed to an emission from an excited state (ICT) with higher dipole moment than the ground state while the emission of (II) is a dual emission from a state with high charge transfer nature (ICT) in addition to the locally excited state (LE). The fluorescence emission spectra of (II) were found to depend on the excitation wavelength and an increase in the excitation wavelength led to the formation of a longer wavelength emission band with lower quantum yield. It has also been found that the fluorescence excitation spectra were dependent on the emission wavelength. The effect of solvent on the nature of dual emission was examined. Correlation of the photophysical properties of the excited states of (I) and (II) with the solvent polarity, ε, reveals the charge transfer nature of (I) and the long wavelength emission band of (II), while their correlation with the solvent polarity parameter (E_T^N) shows two different trends when the solvents are divided to aprotic and protic solvents. For precise investigation of the impact of each solvent parameter on each photophysical property, Catalán's and Laurence's four parametric linear solvation energy relationships were studied. We have found that the non-specific interactions of the solvent are primarily responsible for controlling the photophysical properties, as demonstrated by Catalán's and Laurence's treatments. DFT and TDDFT calculations were used to anticipate the dipole moments in the ground and excited states and geometry of both states.

Keywords: Dual emission; Fluorosolvatochromism; Push pull; Solvatochromism; Structure effect; White light emitters.