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.

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 (ETN) 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.

Novel preparation of metal-free carbon xerogels under acidic conditions and their performance as high-energy density supercapacitor electrodes.

The development of metal-free supercapacitor electrodes with a high energy density is a crucial requirement in the global shift towards sustainable energy sources and industrial pursuit of an optimal supercapacitor. Indeed, from an industrial perspective, time assumes a paramount role in the manufacturing process. A majority of synthesis methods employed for the fabrication of carbon xerogel-based supercapacitor electrodes are characterized by prolonged durations, and result in relatively poor energy and power density. These limitations hinder their practical applications and impede their widespread manufacturing capabilities. In this study, carbon xerogel-based supercapacitor electrodes were made in the shortest time ever reported by making the condition highly acidic with hydrochloric acid (HCl). Furthermore, the investigation of the effect of HCl concentrations (0.1 M, 0.05 M, and 0.01 M) on the morphology and electrochemical behavior of the prepared samples is reported herein. Interestingly, the highest concentration of HCl developed the highest BET surface area, 1032 m2 g-1, which enforced the capacitive behavior to deliver a specific capacitance of 402 F g-1 at 1 A g-1 and a capacitance retention of 80.8% at a current density of 2 A g-1 in an electrolyte containing 0.5 M H2SO4 + 0.5 M Na2SO4. Moreover, an impressive energy density of 45 W h kg-1 at a power density of 18.2 kW kg-1 was achieved. Interestingly, as the HCl concentration increased, the equivalent series resistance decreased to 3.9 W with carbon xerogel 0.1 M HCl (CX0.1). The superior performance of CX0.1 may be attributed to its enlarged BET surface area, pore volume, pore diameter, and smaller particle size. This work provides a facile approach for the large-scale production of metal-free carbon supercapacitor electrodes with improved performance and stability and opens novel horizons to explore the impacts of many types of catalysts during the carbon xerogel preparation.

Fractional dependence of the free energy of activation on the driving force of charge transfer in the quenching of the excited states of substituted phenanthroline homoleptic ruthenium(ii) complexes in aqueous medium.

The photophysical characteristics of some homoleptic ruthenium(ii) phenanthroline derivatives are investigated in aqueous medium. The lifetimes of the excited 3MLCT state of the studied complexes were found to be very sensitive to the type of the substituents on the phenanthroline ligand and were found to increase from about 0.96 µs in case of the parent [Ru(Phen)3]2+ complex to 2.97 µs in case of [Ru(DPPhen)3]2+. The transient absorption spectra of the current set of complexes were studied also in aqueous medium. Quenching of the excited 3MLCT states of the studied complexes by molecular oxygen were studied and quenching rate constants were found to be in the range 1.02-4.83 × 109 M-1 s-1. Values of singlet oxygen quantum yields were found to be in the range 0.01 to 0.25, and the corresponding efficiencies of singlet oxygen thereby produced, f T Δ, were in the range 0.03-0.52. The mechanism by which the excited 3MLCT state is quenched by oxygen is discussed in light of the spin statistical factor rate constants and the competition between charge transfer and non-charge transfer quenching pathways. The partial charge transfer parameters, p CT, were obtained and found to be about 0.88 for all complexes except for complexes with f T Δ values lower than 0.25. The correlation of the activation free energies ΔG ≠ of the exciplexes formation with the driving force for charge transfer, ΔG CET, gives a charge transfer character of the exciplexes of about 35.0%.

Photophysical properties of push-pull monocationic D-π-A+ thiophene based derivatives: Fluorosolvatochromism and pH studies.

Photophysical properties of two thiophene salts of the form D-π-A+ are studied in several solvents and at various pH values of the aqueous solution. The studied compounds embrace methoxy group as electron donating moiety at one end and cationic amidine group with and without fluorine atom at the ortho position of the amidine group as the electron withdrawing group at the other end of the molecules and separated by thiophene ring. The two thiophene derivatives are 4-(5-(4-methoxyphenyl)thiophen-2-yl)benzamidine hydrochloride salt (MOTB) and 2-fluoro-4-(5-(4-methoxyphenyl) thiophen-2-yl)benzamidine hydrochloride salt (FMOTB). The observed changes in the fluorescence emission spectra with the nature of the solvent were found to be much more pronounced than the corresponding absorption spectra which signify an emission from the intramolecular charge transfer state. The higher bathochromic shift in the fluorescence emission spectra than the absorption spectra indicates that the excited state dipole moment is larger than that of the ground state. It has also been observed that the presence of the fluorine atom in the electron withdrawing part does not show any changes in the absorption spectra while a clear bathochromic shift is observed in the fluorescence emission spectra indicating an enhanced strength of the electron withdrawing ability in case of FMOTB. Effect of pH was also studied and pKa values were evaluated. The observed photophysical properties were correlated to the normalized solvent polarity parameter (ETN) when solvents are classified to protic and aprotic solvents. This designates the importance of hydrogen bonding interactions. We have also applied a couple of linear solvation energy relationships for better understanding of the exact contribution of each solvent parameter on each photophysical property. We have found that both Catalán's and Laurence's treatments show that the photophysical properties are mainly controlled by the solvent's non-specific interactions. However, these models were not sufficient to interpret the observed data without the inclusion of the participation of the specific interactions.

Photophysical properties and fluorosolvatochromism of D-π-A thiophene based derivatives.

Solvation-dependent photophysical properties of two push-pull thiophene-based compounds with donor-π-acceptor (D-π-A) structures were investigated using absorption, fluorescence emission and time resolved spectroscopy, and supported by different solvation models. Intramolecular charge transfer characteristics of the structurally similar 2-fluoro-4-(5-(4-methoxyphenyl)thiophen-2-yl)benzonitrile (MOT) and 4-(5-(4-(dimethylamino)phenyl)thiophen-2-yl)-2-fluorobenzonitrile (DMAT) were investigated. Significant enhancement of intramolecular charge transfer strength has been observed through molecular structure modification of the electron donating group from a methoxy to dimethylamine group. Ground state absorption spectra show a small red shift of about 10 nm and 18 nm while the fluorescence emission spectra show a large red shift of about 66 nm and 162 nm on changing from the nonpolar cyclohexane to the aprotic polar DMSO for MOT and DMAT, respectively. Dipole moment change from the ground state to the charge transfer excited state is calculated to be 6.6 D in MOT and 9.0 D in DMAT. The fluorescence quantum yield, fluorescence lifetime and the derived radiative and non-radiative rate constants were found to be better correlated to the emission energy rather than any of the solvent properties. Three multi-parametric relationships were used in the interpretation of the specific versus non-specific solute-solvent interactions, namely, Kamlet-Taft, Catalán and Laurence et al. models. The findings of these approaches are used to extract useful information about different aspects of solvent effects on the photophysical properties of the two studied compounds. Kamlet-Taft solvatochromic model indicates that non-specific interactions are dominant in controlling the photophysical properties. Catalán's solvent dipolarity/polarizability parameter is found to play a significant role in solvatochromic behaviour which is also designated by the Laurence model.

Surface functionality and electrochemical investigations of a graphitic electrode as a candidate for alkaline energy conversion and storage devices.

Graphite is a typical electrocatalyst support in alkaline energy conversion and storage devices such as fuel cells, supercapacitores and lithium ion batteries. The electrochemical behaviour of a graphite electrode in 0.5 M NaOH was studied to elucidate its surface structure/electrochemical activity relationship. Graphite voltammograms are characterized by an anodic shoulder AI and a cathodic peak CI in addition to the oxygen reduction reaction plateaus, PI and PII. AI and CI were attributed to oxidation and reduction of some graphite surface function groups, respectively. Rotating ring disk electrode (RRDE) study revealed two different oxygen types assigned as inner and outer oxygen. The inner oxygen was reduced via the more efficient 4-electron pathway. The outer oxygen reduction proceeded with a lower efficient 2-electron pathway. The calculated percentages of the 4-electron pathway were ranged from 70% to 90%. A full mechanism for the graphite surface function groups changes over the studied potential window was suggested through the combination between the voltammetric, FT-IR and Raman results.