Effect of solvents, solvent mixture and silver nanoparticles on photophysical properties of a ketocyanine dye.

The effect of solvents of varying polarity and hydrogen bonding ability, solvent mixture and silver nanoparticles on the photophysical properties of a ketocyanine dye, 2,5-di[(E)-1-(4-diethylaminophenyl) methylidine]-1-cyclopentanone (2,5-DEAPMC), is investigated at room temperature. Solvent effect is analyzed using Lippert-Mataga bulk polarity function, Reichardt's microscopic solvent polarity parameter, and Kamlet's and Catalan's multiple linear regression approaches. The spectral properties better follow Reichardt's microscopic solvent polarity parameter than the Lippert-Mataga bulk polarity function. This indicates that both general and specific solute-solvent interactions are operative. Kamlet's and Catalan's multiple linear regression approaches indicate that polarizability/dipolarity solvent influences are greater than hydrogen bond donor and hydrogen bond acceptor solvent influences. The solvatochromic correlations are used to estimate excited state dipole moment using the experimentally determined ground state dipole moment. The excited state dipole moment of the dye is found to be larger than its corresponding ground state dipole moment and ground and excited state dipole moments are not parallel, but subtend an angle of 77°. The absorption and emission spectra are modulated in the presence silver nanoparticles. The fluorescence of 2,5-DEAPMC is quenched by silver nanoparticles. The possible fluorescence quenching mechanisms are discussed. Copyright © 2016 John Wiley & Sons, Ltd.

Specific interactions of alcohols and non-alcohols with a biologically active boronic acid derivative: a spectroscopic study.

The photophysical properties of 4-fluoro-2-methoxyphenyl boronic acid (4FMPBA) are characterized using absorption and fluorescence techniques in series of non-alcohols and alcohols. The results are analyzed using different solvent polarity functions and Kamlet and Catalan's multiple regression approaches. The excited state dipole moment and change in dipole moment are calculated using both the solvatochromic shift method and Reichardt's microscopic solvent polarity parameter ETN. The ground state dipole moment is evaluated using quantum chemical calculations. It is found that general solute-solvent and hydrogen bond interactions are operative in this system. A red shift of ~ 9 nm in the emission spectra is observed with an increase in the solvent polarity, which depicts π→π(*) transitions, as well as the possibility of an intramolecular charge transfer (ICT) character in the emitting singlet state of 4FMPBA. The relative quantum yield, radiative and non-radiative decay constants are calculated in alkanes and alcohols using the single point method. It is found that the quantum yield of the molecule varies from 16.81% to 50.79% with the change in solvent polarity, indicating the dependence of fluorescence on the solvent environment. Copyright © 2015 John Wiley & Sons, Ltd.

Investigation of role of silver nanoparticles on spectroscopic properties of biologically active coumarin dyes 4PTMBC and 1IPMBC.

The role of silver nanoparticles on spectroscopic properties of biologically active coumarin dyes 4-p-tolyloxymethyl-benzo[h]coumarin (4PTMBC) and 1-(4-iodophenoxymethyl)-benzo[f]coumarin (1IPMBC) has been investigated using absorption and fluorescence spectroscopy. Silver nanoparticles are synthesized by chemical reduction method and the estimated size by Mie theory is 12 nm. The absorption spectral changes of dyes in the presence of silver nanoparticles suggest their possible interaction with silver nanoparticles. The apparent association constants of the interaction are estimated using Benesi-Hildebrand model. Fluorescence quenching has been observed in both the dyes with the addition of silver nanoparticles. The Stern-Volmer plots of fluorescence quenching are found to be nonlinear showing positive deviation. The magnitudes of quenching rate parameter and fluorescence lifetime measurements indicate the presence of both collisional and static quenching mechanisms. The binding constants and the number of binding sites for the static type of quenching have been estimated from the fluorescence data. The role of diffusion, energy transfer and electron transfer processes in fluorescence quenching mechanism has been discussed.

Photophysical characteristics of biologically active 4-aryloxymethyl coumarins 4PTMBC and 1IPMBC.

The absorption and fluorescence characteristics of biologically active coumarin derivatives 4-p-tolyloxymethyl-benzo[h]coumarin (4PTMBC) and 1-(4-iodo phenoxymethyl)-benzo[f]coumarin (1IPMBC) are studied at room temperature in a series of organic solvents and 1,4-dioxane - acetonitrile solvent mixture. The effect of pure solvents on the spectral properties are analyzed using Lippert-Mataga polarity function, Reichardt's microscopic solvent polarity parameter, Kamlet's and Catalan's multiple linear regression approaches. Both general solute - solvent interactions and hydrogen bonding interactions are operative in these systems. However, the contribution of hydrogen bonding interactions is less compared to general solute-solvent interactions. The solvatochromic correlations are used to estimate excited state dipole moment using experimentally determined ground state dipole moment. The bathochromic shift of the emission spectra and the increase in excited state dipole moment indicate the intramolecular charge transfer (ICT) character in the emitting singlet state. The solvation studies in 1,4-dioxane - acetonitrile solvent mixture suggest that these dyes are preferentially solvated by 1,4-dioxane.

Effect of solvents on photophysical properties and quenching of 2-{[3-(1H-benzimidazole-2-yl) phenyl] carbonoimidoyl}phenol.

The effect of solvents of varying polarity on the absorption and fluorescence emission of the Schiff base, 2-{[3-(1H-benzimidazole-2-yl) phenyl]carbonoimidoyl}phenol, was studied using Lippert-Mataga bulk polarity function, Reichardt's microscopic solvent polarity parameter and Kamlet's multiple linear regression approach. The spectral properties follow Reichardt's microscopic solvent polarity parameter better than Lippert-Mataga bulk polarity parameter, indicating the presence of both general solute-solvent interactions and specific interactions. Catalan's multiple linear regression approach indicates the major role of solvent polarizability/dipolarity influence compared with solvent acidity or basicity. The solvatochromic effect was utilized to calculate the dipole moments of ground and excited states of the Schiff base using different methods. Bathochromic shift in the emission spectrum and the increase in dipole moment in the excited state signifies the intramolecular charge transfer character in the emitting singlet state. Fluorescence quenching by aniline was also studied in 1,4-dioxane and n-butanol, and the results were analyzed using sphere of action static quenching and finite sink approximation models.

Effect of solvents on the spectroscopic properties of LD-489 & LD-473: estimation of ground and excited state dipole moments by solvatochromic shift method.

The absorption and fluorescence spectra of 6,7,8,9-tetrahydro-6,8,9-trimethyl-4-(trifluoro methyl)-2H-pyrano[2,3-b][1,8]naphthyridin-2-one (LD-489) and 1,2,3,8-tetrahydro-1,2,3,3,8-pentamethyl-5-(trifluoromethyl)-7H-pyrrolo[3,2-g]quinolin-7-one (LD-473) have been recorded at room temperature in different solvents and 1,4-dioxane-acetonitrile solvent mixtures. The UV-Visible absorption spectra are less sensitive to solvent polarity than the corresponding fluorescence spectra in both the dyes which show pronounced solvatochromic effect. The effects of solvents upon the spectral properties are analyzed using Lippert-Mataga polarity function, Richardts microscopic solvent polarity parameter and Catalán's multiple linear regression approach. Both general solute-solvent interactions and specific interactions are operative in these systems. The solvatochromic correlations are used to estimate excited state dipole moments using experimentally determined ground state dipole moments. The excited state dipole moment for both the dyes are found to be larger than their corresponding ground state dipole moment and is interpreted based on their resonance structures.

Solvent effects on the absorption and fluorescence spectra of some laser dyes: estimation of ground and excited-state dipole moments.

The absorption and fluorescence spectra of three extensively used laser dyes namely 1,1,4,4-tetraphenyl-1,3-butadiene (TPB), 2-(4'-t-butylphenyl)-5-(4''-biphenylyl)-1-oxa-3,4-diazole (BPBD), 1,4-bis[2-(2-methylphenyl)ethenyl]-benzene (Bis-MSB) have been recorded at room temperature (300K) in solvents of different polarities. The effects of the solvents upon the spectral properties are discussed. The ground-state dipole moments (mu(g)) were determined experimentally by Guggenheim and Higasi method separately and were compared with theoretical values obtained using quantum chemical method. The ground-state dipole moments obtained by using Guggenheim method were then used in the estimation of excited-state dipole moments (mu(e)) by using Lippert's, Bakhshiev's and Kawski-Chamma-Viallet's equations. In all the above three equations the variation of the Stokes shift with the solvent dielectric constant and refractive index was made use of. It was observed that dipole moments of excited state were higher than those of the ground state for all the dyes.