Solvent Polarity Parameter Research Articles

Solubility behavior of Rosiglitazone in ten pure solvents: Model correlation, thermodynamic calculations, and molecular simulation

Rosiglitazone is an oral antidiabetic medication primarily used to treat type 2 diabetes. Herein, the single crystal structure of Rosiglitazone (a = 14.0613(7) Å, b = 8.4675(4) Å, c = 29.8841(16) Å, space group Pbca, Z = 8, V = 3558.1(3) Å3) was analyzed for the first time. Through solubility measurements, model correlation, thermodynamic calculations, and molecular simulations, the dissolution of Rosiglitazone in ten pure solvents was comprehensively investigated. The solubility order at 298.15 K is acetone > methyl acetate > ethyl acetate > butyl acetate > acetonitrile > alcoholic solvents (methanol, ethanol, n-propanol, iso-propanol, n-butanol). Rosiglitazone exhibits higher solubility in non-alcoholic solvents, whereas its solubility in alcoholic solvents is similar and relatively low. Subsequently, the correlation between the experimentally measured solubility of Rosiglitazone and the Modified Apelblat model, λh model, NRTL model, and Van’t Hoff model was examined. The Van’t Hoff equation calculations proved that the dissolution of Rosiglitazone was an endothermic process driven by entropy and characterized by non-spontaneity. The calculation of solvent polarity and Hansen solubility parameters (HSP) reveals that the primary factor influencing the solubility of Rosiglitazone is polarity in highly polar solvents, while the dominant factor is molecular volume in low-polarity solvents. Furthermore, the molecular interactions of solute and solvents were investigated by molecular simulation, including the calculation of electrostatic potential, 2D fingerprint plots and solvation free energy, which provided insights into the mechanism of Rosiglitazone dissolution behavior in different solvents.

Estimation of Electric Dipole Moment by Solvatochromism, Computational Method, and Study of the Effect of Solvents by Preferential Solvation of 6 - Methoxy-4-(4-Nitro-Phenoxy Methyl)-Chromen-2-One (6mnpm).

At room temperature, the absorption and fluorescence properties of coumarin 6-Methoxy-4-(4-nitro-phenoxy methyl)-chromen-2-one (6MNPM) are investigated in pure organic solvents and a combination of acetonitrile (ACN) and tetrahydrofuran (THF). The pure solvents' influence on spectral characteristics is examined by applying theories such as Kamlet and Catalan's multiple linear regression techniques, Reichardt's microscopic solvent polarity parameter, and the Lippert-Mataga polarity function. The significant role of solute-solvent interactions in pure solvents, particularly dielectric interaction and hydrogen bonding. However, hydrogen bonding interactions dominate the contribution of dielectric interactions. The electric dipole moments of both the ground as well as excited states had been calculated using the Solvatochromic method. The value of the excited state electric dipole moment and the redshifts of the emission spectra show that the emitting singlet state has an intramolecular charge transfer (ICT) character. From Catalan's linear regression, we found that di-polarity has a much smaller influence than polarizability. By solvation study, we conclude that Tetrahydrofuran solvent is preferred over Acetonitrile.

Solvatochromism, preferential solvation and excited state dipole moments of flufenamic acid in different solvent polarities

The influence of pure solvent and binary solvent mixtures on the optical properties of non-steroidal anti-inflammatory drug (NSAID) molecule, specifically flufenamic acid (FLA), has been studied using absorption and fluorescence spectroscopic techniques. A bathochromic shift is observed in the emission wavelength of FLA with an increase in the solvent polarity of pure solvents, attributed to the highest stability of the excited state. The spectral properties are correlated with Lippert–Mataga, solvent polarity parameter, Kamlet, and Catalan solvent polarity parameters, suggesting that both general and specific solvent effects influence the spectral properties, with general solvent effects dominating over specific solvent effects. Preferential solvation studies have been carried out in tetrahydrofuran (THF) and water solvent mixture, revealing variations in the preference for solvation of FLA as a function of the mole fraction of water. Solvatochromic data are utilized to estimate the excited state dipole moment in pure solvents using different solvatochromic methods, revealing that the excited state dipole moment of FLA is higher than its ground state counterpart. The increase in dipole moment in the excited state compared to the ground state is explained based on intramolecular charge transfer (ICT), with elaboration and discussion on the possible resonance structure corresponding to ICT, inferring the more polar nature of the excited state compared to the ground state. The effect of solute polarizability on the excited state dipole moment and change in dipole moment is also discussed.

Novel Cu(II) and Zn(II) Nanocomplexes Based on 5,6‐Diphenyl‐1,2,4‐Triazine: Preparation, Spectroscopic, TD‐DFT Calculations, Molecular Docking and Solvatochromic Studies

ABSTRACTThe reaction between 2‐hydroxy‐1‐naphthaldehyde and 3‐hydrazino‐5,6‐diphenyl‐1,2,4‐triazine produced a novel hydrazone ligand (DTHMN), which reacted with Cu(II) and Zn(II) metal ion in molar ratio 1:1, giving octahedral Cu(II)‐DTHMN and tetrahedral Zn(II)‐DTHMN nanosized complexes. The structural geometries have been elucidated on the basis of elemental analysis, nuclear magnetic resonance, infrared, electronic, and electron spin resonance spectra, and magnetic and molar conductance measurements as well as x‐ray diffraction and thermal analysis. TEM analysis showed that Zn(II)‐DTHMN complex has nano‐rode morphology shape. On the other hand, Cu(II)‐DTHMN has sphere shape within nanodomain. The DTHMN ligand exhibits ONN chelating sites through N‐triazine ring, azomethine nitrogen, and deprotonated OH group, forming the mononuclear metal complexes. The synthesized compounds showed a distinct solvatochromic behavior in different polar solvents. A bathochromic alteration is observed when moving from less to high polar solvents, indicating strong solute–solvent interactions accompanied by intramolecular charge transfer (ICT). The ground and excited state dipole moments of these compounds were determined experimentally by solvatochromic shift method using Bilot–Kawski, Lippert–Mataga, Bakhshiev, and Kawski–Chamma–Viallet functions and a microscopic Reichardt's solvent polarity parameter (ETN). The dipole moment is increased significantly upon excitation referring to stabilizing the excited species includes n–π* transition by polarity of solvent. The experimental results are generally consistent with those values obtained by B3LYP/GENECP method at 6‐311G(d,p) basis set for C, H, N, and O atoms and SDD (Stuttgart/Dresden) basis set for the metal atoms. The compounds were tested for antimicrobial efficiency against Gram‐positive bacteria, Gram‐negative bacteria, and fungus strain. Finally, molecular docking was used to study the interactions between donors (the current compounds) and receptors FabH–CoA complex (PDB code: 1HNJ).

New approach: Solvent effects of benzaldehyde in aliphatic alcohol solvents with FT-IR spectroscopy and augmented vertex-adjacency matrices

In this study of benzaldehyde (BNZ) in 7 aliphatic alcohol solvents, were undertaken to investigate the solvent/solute interaction with Fouirer Transform Infrared Spectroscopy (FT-IR), BNZ produced carbonyl group stretching vibration frequencies (ν(C=O)1 and ν(C=O)2). In the present paper, ν(C=O)1 and ν(C=O)2 of BNZ are observed and correlated with the solvent acceptor number (AN), dipolarity/polarizability (π*), hydrogen-bond donor acidity (α), hydrogen-bond acceptor basicity (β), solvent polarity parameter [ET(30)], KBM parameter ƒ(ε), boiling point (bp) and the linear solvation energy relationship (LSER) using single and multiple regression analysis. All calculations were performed for ν(C=O)1 and ν(C=O)2 and compared. ν(C=O)1 was believed to correspond to a single hydrogen bonded BNZ-alcohol complex, while ν(C=O)2 was believed to correspond to a multiple hydrogen bonded BNZ-alcohol complex and multiple hydrogen-bonded alcohol molecules. It was seen that LSER equation as multiple regression analysis was better than single regression analysis in explaining solute-solvent interactions due to the higher correlation coefficients obtained. The correlations of a set of the mathematical characteristics of the augmented vertex-adjacency matrices (AV-AM) obtained by the chemical structure of BNZ with solvent parameters and ν(C=O) were investigated. It was determined that the correlation factors (R2 > 0.999) of the multiparameter regression models obtained using the matrix results were higher than the correlation factors (R2 > 0.99) of the LSER equations including solvent parameters.

Exploring solvatochromism: a comprehensive analysis of research data of the solvent -solute interactions of 4-nitro-2-cyano-azo benzene-meta toluidine

This study investigates the solvatochromic behavior of a new D1 disperse dye, focusing on the 4-nitro-2-cyano-azo-Benzene-metaToluidine type. Using UV-visible spectroscopy, we analyze the dye’s performance in single solvents and binary mixtures. Our analysis includes the evaluation of solvent polarity parameters and dye structure parameters, with emphasis on the longest wavelength intramolecular charge transfer absorption band. We identify nonlinear and linear patterns in the electronic transition energies plots with respect to solvent composition. Statistical analysis considers correlation coefficients, root mean squared error, mean absolute percentage error, and other parameters, providing insights into data accuracy and precision. This experimental and statistical study explores the absorption spectrum, wavelength characteristics, absorption energy, and polarity of a novel azo dye across various solvent and solute environments. These findings contribute to a comprehensive understanding of the dye’s photophysical and photochemical properties, potentially enabling applications in optical sensors and advanced materials.Graphical abstract

Synthesis, Spectral Characterization and Photoluminescence of 3-chloro-6-methoxy-2-(methylsulfanyl)quinoxaline in Different Solvents: An Experimental and Theoretical Investigation Using DFT.

In the present work, we synthesized 3-chloro-6-methoxy-2-(methyl sulfanyl) quinoxaline (3MSQ) using a microwave-assisted synthesis method. The physicochemical structural analysis of the synthesized compound utilizing 1H-NMR, 13C-NMR, and FT-IR spectroscopy techniques. The photophysical properties of 3MSQ was examined through absorption and fluorescence spectroscopy. Spectroscopic analyses revealed a bathochromic shift in both absorption and fluorescence spectra, attributed to the π → π* transition. Ground and excited state dipole moments was experimentally determined using the solvatochromic shift method, employing various correlations such as Lippert's, Bakhshiev's, Kawski-Chamma-Viallet's equations, and solvent polarity parameters. Our findings indicate that the excited state dipole moments exceed those of the ground state, suggesting increased polarity in the excited state. Further, the while detailed bond length, bond angles, dihedral angles, Mulliken charge distribution, ground state dipole moments and HOMO-LUMO energy gap estimated through ab initio computations using Gaussian-09W. The value of energy band gap obtained from both the methods are in good agreement. Furthermore, employing DFT computational analysis, we identified reactive centers such as electrophilic and nucleophilic sites using molecular electrostatic potential (MESP) 3D plots. Additionally, CIE chromaticity analysis was performed to understand the photoluminescent properties of 3MSQ. The insights derived from these analyses contribute to a better understanding of the molecule's electronic structure, photophysical properties, and solute-solvent interactions, thus providing valuable information regarding its behaviour and characteristics under diverse conditions. These results contribute to a comprehensive understanding of the molecular structure and properties of 3-chloro-6-methoxy-2-(methyl sulfanyl) quinoxaline (3MSQ).

Photochemical synthesis and solvatochromic fluorescence behavior of imide-fused phenacenes

Chrysenes, picene, fulminene, modified with imide, bromo, and amino functionalities, were synthesized through Mallory photoreaction as the key step, and their electronic spectra were investigated. Fluorescence spectra of chrysene-diimide CHRDI and bromo-substituted phencanene-imides, BrCHRI, BrPICI, BrFULI were dependent on solvent polarity to display appreciable fluorescence color changes. The solvatofluorochromic behavior was analyzed by conventional relationships between Stokes shift and solvent polarity parameters, such as Lippert-Mataga and Bilot-Kawski equations. The results indicated that the solvatofluorochromism was derived from the intramolecular charge transfer (ICT) nature in the excited state. Theoretical studies using time-dependent density-functional theory revealed that the phenacene-imide molecules in the fluorescent state possessed ICT characters between the strongly electron-withdrawing imide moiety and moderately electron-donating phenacene cores. Amino-substituted chrysene-imide NH2CHRI showed fluorescence band in a red region (λFL = 618 nm) in toluene with a very large Stokes shift (Δν∼ = 7630 cm−1) suggesting that the molecule in the fluorescent state was highly polarized. The present results indicate that phenacenes would provide potential platforms for constructing future functional fluorophores through an appropriate functionalization.

Bent naphthodithiophenes: synthesis and characterization of isomeric fluorophores.

Thiophene-containing heteroarenes are one of the most well-known classes of π-conjugated building blocks for photoactive molecules. Isomeric naphthodithiophenes (NDTs) are at the forefront of this research area due to their straightforward synthesis and derivatization. Notably, NDT geometries that are bent - such as naphtho[2,1-b:3,4-b']dithiophene (α-NDT) and naphtho[1,2-b:4,3-b']dithiophene (β-NDT) - are seldom employed as photoactive small molecules. This report investigates how remote substituents impact the photophysical properties of isomeric α- and β-NDTs. The orientation of the thiophene units plays a critical role in the emission: in the α(OHex)R2 series conjugation from the end-caps to the NDT core is apparent, while in the β(Oi-Pent)R2 series minimal change is observed unless strong electron acceptors, such as β(Oi-Pent)(PhCF3)2, are employed. This push-pull acceptor-donor-acceptor (A-D-A) fluorophore exhibits positive fluorosolvatochromism that correlates with increasing solvent polarity parameter, E T(30). In total, these results highlight how remote substituents are able to modulate the emission of isomeric bent NDTs.

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.

Multiparametric Investigations on Solvation Behaviour and Spectral Shifts of Symmetric Aromatic Diselenides: A case study of Diphenyldiselenide

ABSTRACT Decorating symmetric aromatic diselenide motif such as in diphenyldiselenide (DPDSe) with diverse supra-functionalities provides a plethora of bioactivities for pharmacological applications. Solvent studies of bioactive molecules are vital descriptors for their drug development as these can predict the drug–target interaction. This study aims to evaluate the influence of intermolecular interactional forces on the solvation behaviour and spectral shifts of DPDSe. The solvation behaviour of DPDSe was evaluated primarily via solvent polarity and solvent parameters. The observed solvatochromic shifts were analysed with various solvent study models, of which Kamlet–Taft and Catalan models were found to be most suitable for describing intermolecular interactions of DPDSe. The experimental data suggest an overall red shift with increasing solvent polarity. Moreover, data analysis using solvatochromic models predict negative coefficients for solvent dipolarity (π*) and solvent polarisabilities (SP) and (SdP). The studied dipole moment values indicate the more polar nature of DPDSe in the excited state relative to the ground state, further corroborating the observed bathochromic shift with increasing solvent polarity.

Reichardt’s Dye-Based Solvent Polarity and Abraham Solvent Parameters: Examining Correlations and Predictive Modeling

The concept of “solvent polarity” is widely used to explain the effects of using different solvents in various scientific applications. However, a consensus regarding its definition and quantitative measure is still lacking, hindering progress in solvent-based research. This study hopes to add to the conversation by presenting the development of two linear regression models for solvent polarity, based on Reichardt’s ET(30) solvent polarity scale, using Abraham solvent parameters and a transformer-based model for predicting solvent polarity directly from molecular structure. The first linear model incorporates the standard Abraham solvent descriptors s, a, b, and the extended model ionic descriptors j+ and j−, achieving impressive test-set statistics of R2 = 0.940 (coefficient of determination), MAE = 0.037 (mean absolute error), and RMSE = 0.050 (Root-Mean-Square Error). The second model, covering a more extensive chemical space but only using the descriptors s, a, and b, achieves test-set statistics of R2 = 0.842, MAE = 0.085, and RMSE = 0.104. The transformer-based model, applicable to any solvent with an associated SMILES string, achieves test-set statistics of R2 = 0.824, MAE = 0.066, and RMSE = 0.095. Our findings highlight the significance of Abraham solvent parameters, especially the dipolarity/polarizability, hydrogen-bond acidity/basicity, and ionic descriptors, in predicting solvent polarity. These models offer valuable insights for researchers interested in Reichardt’s ET(30) solvent polarity parameter and solvent polarity in general.

Estimation of dipole moments by Solvatochromic shift method, spectroscopic analysis of UV–Visible, HOMO-LUMO, ESP map, Mulliken atomic charges, NBO and NLO properties of benzofuran derivative

Solvatochromic shift method has been used to estimate ground state (μg) and excited state (μe) dipole moments of benzofuran derivative (5NFMOT) at room temperature indifferent solvents. This method involves Lippert, Bakhshiev and Kawski-Chamma-Viallet equations. Reichardt microscopic solvent polarity parameter was used to calculate the change in dipole moment. Effect of solvents on absorption and fluorescence spectra was investigated using Kamlet and Catalan's MLR approach. Computational studies of benzofuran derivative were carried out using Gaussian 16. Geometry optimization was performed using DFT method at 6–311++G (d, p)/B3LYP basis set. UV–Visible spectra have been studied by using TD-DFT method for the same basis set. The μg was obtained from DFT method, whereas μe from TD-DFT method. It has been observed that both from experimentally and theoretically the ground state dipole moment is higher than the excited state dipole moment. HOMO-LUMO surfaces and Mulliken atomic charges have been studied in gas phase and solution. Furthermore, 3D plots of electrostatic potential map are used to identify reactive centers such as electrophilic and nucleophilic sites. NBO analysis is helpful to obtain stability and charge delocalization of the title molecule. Polarizablity, and hyper polarizability values were used to study the NLO properties.

Fluorosolvatochromic Behavior of 2,3‐Naphthalimides Expanded by Double Fusion with Benzothiophene and Benzofuran Units

AbstractAs new polycyclic aromatic hydrocarbons (PAHs) containing an imide group, we designed and synthesized 2,3‐naphthalimide fused with benzothiophene 1 or benzofuran 2. 1 and 2 have a push‐pull structure attributed to the imide group and the electron‐donating heterocyclic moieties, indicated that 1 and 2 play as a fluorosolvatochromic dye. 1 and 2 were synthesized in 3‐steps. The absorption and fluorescence spectra were measured in twelve different solvents. The absorption spectra of 1 and 2 showed a slight solvent dependence. On the other hand, a strong solvent dependence was observed in the fluorescence spectra of 1 and 2, that is, fluorosolvatochromism. The plots of the emission maximum versus the solvent polarity parameter ET(30) for 1 and 2 exhibited a good linear correlation. Multiple linear regression analysis using Catalán scale suggested that the fluorescence behavior of 1 and 2 is influenced by the acidity and dipolarity of the solvents. The changes in the dipole moment between the ground and excited states estimated by the Lippert‐Mataga equation were 7.6 D for 1 and 7.2 D for 2.

Synthesis and spectral investigation of novel 4-aryl-5-(aryldiazenyl)thiazole dyes festooned with fluorene moiety: Experimental and theoretical insight

A series of novel 4-aryl-5-(aryldiazenyl)thiazole dyes 7a-h pendant to fluorene group were synthesized form easily accessible starting materials. The absorption spectra of the synthesized azodyes were recorded in different solvents with variable chemical and physical properties. Structural Elucidation of the synthesized azodyes were carried out by UV–vis, IR and NMR spectroscopies as well as elemental analyses. Different solvent parameters, such as microscopic solvent polarity, Kamlet-Taft and Catalan parameters were employed in order to assess the solute–solvent interactions and the solvatochromic shifts of the absorption maximum of the 4-aryl-5-(aryldiazenyl)thiazole dyes under investigation. The solvent scales constitute the most appropriate method for interpreting the solvatochromic behavior of the synthesized azodyes. Furthermore, the dyes' absorption ability revealed that the substituent effect on UV–vis absorption spectra is strongly influenced by the electronic nature of the substituent on the 1-phenyl ring. It was also observed that the absorption spectra were sensitive to acidic and basic media. The synthesized azo compounds showed spectral changes that revealed that azo tautomers formed at acidic pH while hydrazo tautomers at alkaline pH. To gain a thorough understanding of the stability and geometrical characteristics of the azo-hydrazo tautomers, DFT calculations were also performed on the synthetic dyes.

Determination of L-Glutamine Solubility in 12 Pure Solvent Systems from 283.15 to 323.15 K

The mole fraction solubility of L-glutamine in 12 pure solvents (methanol, n-propanol, sec-butanol, 2-butanone, ethanol, acetonitrile, n-butanol, ethyl acetate, n-pentanol, water, n-hexane, and isobutanol) was determined by the static gravimetric method at a temperature range of 283.15–323.15 K under a pressure of 98.8 kPa. The equilibrium solid phase of L-glutamine in the solvent systems was characterized by powder X-ray diffraction analysis. The solubility in the 12 monosolvents was found to increase with absolute temperature. The maximum and minimum values were in water and ethyl acetate, respectively. The empirical solvent polarity parameters (ET(30)), cohesive energy density, and hydrogen bond donor/acceptor (HBD/HBA) tendencies were employed to analyze the solubility behavior and solvent effects. The solubility data were fitted using the modified Apelblat model and the Yaws model, at the same time, the model parameters and data deviation values were calculated. These two solubility models were evaluated using the Akaike Information Criteria and Akaike weights. The results showed that the modified Apelblat model had better correlation results. The solubility data could be used in the preparation and optimization of L-glutamine crystallization processes.

Effect of the π-bridge structure on the intramolecular charge transfer of push–pull 2-phenylthiophene and 2-(furan-2-yl)pyridine derivatives

Effect of the bridge structure on the photophysical properties of D-π-A of structurally similar 2,5-diphenylthiophene (cpd. I) and 2-(5-phenylfuran-2-yl)pyridine (cpd. 2) derivatives having the same electron donating and electron withdrawing groups were studied in different solvents. Solvent effect on the absorption and fluorescence emission spectra as well as their excited state decay were studied in detail. Introduction of 2,5-diphenylthiophene and 2-(5-phenylfuran-2-yl)pyridine between methoxy and carbonitrile groups lead to a shift of about 20 nm in both the absorption and fluorescence emission maxima of the former. Stokes shift of about 90 nm was observed for both compounds in protic solvents and polar aprotic solvents and decreases as the solvent polarity decreases. The solvatochromism in the fluorescence emission spectra was higher than the observed in absorption spectra, indicating higher dipole moment in the excited state than in the ground state for both compounds. DFT and TD-DFT optimized geometry calculations show that (I) is planar in the excited state while (II) is planar in both the ground and excited states reflecting the importance of the bridge structure on the geometry in the ground and excited states. Theoretical calculations of the dipole moment change from the ground to the excited states were consistent with the values obtained from Lippert-Mataga relationship and higher than values obtained from Reichardt-Ravi relationship. It has been found that the fluorescence lifetime of both compounds was found to decrease as the emission energy increases and being higher for (II) than for (I), and also was found to increase as the solvent’s dielectric constant increases. All photophysical properties were found to correlate well with Reichardt’s solvent polarity parameter, ETN. We have employed Kamlet-Taft, Catalán and Laurence et al. multi-parametric relationships to assign the contribution of the specific and non-specific solute–solvent interactions. Non-specific interactions were found to be mostly dominating in all cases.

TD-DFT calculations, dipole moments, and solvatochromic properties of 2-aminochromone-3-carboxaldehyde and its hydrazone derivatives.

2-Aminochromone-3-carboxaldehyde (ACC) and its hydrazones (ACMHCA and ACMNPHTCA) with semicarbazide hydrochloride and N-phenylthiosemicarbazide were synthesized and characterized by elemental analysis and spectral studies. The solvatochromic behavior of the title compounds in various solvents showed distinct bathochromic shifts on going from nonpolar to polar solvents, suggesting intramolecular-charge-transfer (ICT) solute-solvent interactions. The ground and excited state dipole moments of ACC, ACMHCA, and ACMNPHTCA were determined experimentally by the solvatochromic shift method using the Bilot-Kawski, Lippert-Mataga, Bakhshiev, Kawski-Chamma-Viallet functions, and a microscopic Reichardt's solvent polarity parameter (ENT). All the investigated molecules showed a substantial increase in the dipole moment upon excitation to the emitting state. The experimental results were generally consistent with the values obtained by the TD-DFT, B3LYP/6-311G++(d,p) method. Molecular electrostatic potential (MEP) mapping and natural charge and natural bonding orbital (NBO) analysis were performed and the results were discussed. The 1H NMR chemical shifts of the prepared compounds were simulated by the gage independent atomic orbital (GIAO) method and compared with their experimental chemical shift values. The biological activity data were correlated with the frontier molecular orbitals. The photovoltaic behavior of the title compounds showed there was sufficient electron injection.

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.

Polarity-Dependent Twisted Intramolecular Charge Transfer in Diethylamino Coumarin Revealed by Ultrafast Spectroscopy

Twisting intramolecular charge transfer (TICT) is a common nonradiative relaxation pathway for a molecule with a flexible substituent, effectively reducing the fluorescence quantum yield (FQY) by swift twisting motions. In this work, we investigate coumarin 481 (C481) that contains a diethylamino group in solution by femtosecond transient absorption (fs-TA), femtosecond stimulated Raman spectroscopy (FSRS), and theoretical calculations, aided by coumarin 153 with conformational locking of the alkyl arms as a control sample. In different solvents with decreasing polarity, the transition energy barrier between the fluorescent state and TICT state increases, leading to an increase of the FQY. Correlating the fluorescence decay time constant with solvent polarity and viscosity parameters, the multivariable linear regression analysis indicates that the chromophore’s nonradiative relaxation pathway is affected by both hydrogen (H)-bond donating and accepting capabilities as well as dipolarity of the solvent. Results from the ground- and excited-state FSRS shed important light on structural dynamics of C481 undergoing prompt light-induced intramolecular charge transfer from the diethylamino group toward –C=O and –CF3 groups, while the excited-state C=O stretch marker band tracks initial solvation and vibrational cooling dynamics in aprotic and protic solvents (regardless of polarity) as well as H-bonding dynamics in the fluorescent state for C481 in high-polarity protic solvents like methanol. The uncovered mechanistic insights into the molecular origin for the fluorogenicity of C481 as an environment-polarity sensor substantiate the generality of ultrafast TICT state formation of flexible molecules in solution, and the site-dependent substituent(s) as an effective route to modulate the fluorescence properties for such compact, engineerable, and versatile chemosensors.