Salicylidene Aniline Research Articles

Theoretical insights from computational analyses: solvent-polarity-associated excited state behaviours for the novel NP-BSD chemosensor

Given the potential luminous advantages of salicylideneaniline (SA) derivatives, in this work, the phenyl π-extension-bis(salicylidene)-1,5-diaminonaphthalene (NP-BSD) fluorophore is explored on its photo-induced reactional behaviours in solvents theoretically. Given solvent surroundings with different polarities, we studied the hydrogen-bonding interactions in different solvents and their influences on excited state proton transfer (ESPT) reaction by photoexcitation for NP-BSD fluorophore. First, photo-induced geometrical variations related to dual hydrogen bonds (O1-H2···N3 and O4-H5···N6) and infrared (IR) vibrational changes and qualitative chemical bond strength reveal excited-state hydrogen bonding enhancement. Probing into the photo-induced excitation process, the charge redistribution derived from vertical excitation confirms the tendency of ESIPT reaction for NP-BSD fluorophore. By constructing potential energy surfaces (PESs) in three aprotic polar solvents, the excited-state intramolecular double proton transfer (ESIDPT) mechanism of NP-BSD could be verified that could be regulated by solvent polarity. We clarify and present the solvent-polarity-associated ESIDPT behaviours for NP-BSD fluorophore.

Theoretical study of the substituent effects on the ESIPT mechanism of salicylideneaniline and the TICT photochemistry reactions.

The study of salicylideneaniline (SA) and its derivatives is critical due to their special photophysical properties and environmental sensitivity. In this work, the density time-dependent functional theory (TDDFT) and complete-active-space self-consistent-field (CASSCF) methods were carried out to calculate the substituent effect on excited-state properties and dynamics of SA derivatives. We found the para-substitution triggers the excited-state intramolecular proton transfer (ESIPT) reaction, exhibiting the dual-fluorescent phenomena. However, the meta- and ortho-substitutions impel the non-radiative transition process along the minimum energy conical intersection (MECI), forming the twisted intramolecular charge transfer (TICT) state to prevent ESIPT. This investigation of substituent effects on the photochemical processes and photophysical properties will provide the benchmarks for the design of fluorescent materials.

Prediction of Photochromism of Salicylideneaniline Crystals Using a Data Mining Approach.

Salicylideneanilines (SAs) are photochromic compounds that undergo enol-keto photoisomerization in the solid state. Research over the past 60 years has revealed empirically that SAs with steric and planar conformations tend to be photochromic and nonphotochromic, respectively. However, increasing counterexamples in the recent literature raise questions about the nature of the relationship between structure and photochromism in SA crystals and whether the photochromism of SA crystals is predictable. This study is the first to construct a data set on SA crystals and conduct a comprehensive analysis to investigate the relationship between molecular and crystal structures and photochromism. A data mining approach revealed that the dihedral angle is the most dominant structural parameter for photochromism, followed by the Hirshfeld surface volume. SAs with neutral bulky hydrocarbon groups, such as the tert-butyl group, tend to be photochromic because such SAs have steric conformation and a loosely packed structure. In contrast, SAs with fluorine, pyridine, and pyrazine are less likely to be photochromic due to their planar conformation and densely packed structures. The photochromism of the SA crystals in our data set was predicted with high accuracy (>85%) using machine learning. The results of this study provide a useful reference for designing SA crystals with desired photochromic properties.

Salicylideneaniline/Dithienylethene Hybrid Molecular Switches: Design, Synthesis, and Photochromism.

A hybrid molecular switch comprising salicylideneaniline (SA) and dithienylethene (DTE) moieties around a single benzene ring is reported. Due to an interplay between solvent-assisted enol-keto tautomerization in the former moiety and photochromic electrocyclization in the latter, this dithienylbenzene derivative was found to be photoresponsive at room temperature with a thermally stable closed form. The main photoproduct featuring ring-closed DTE and keto-enamine SA structures could be isolated and converted back to the starting material by irradiation with visible light. The optical properties of the potential structures involved in the overall process were characterized by using density functional theory (DFT) calculations in good agreement with the measured data. The reversibility of the conversion could be tuned by the presence of donor and acceptor substituents, while the introduction of the imine in the form of a benzothiazole moiety enabled photochemistry even in nonprotic solvents.

Ultrafast internal conversion and photochromism in gas-phase salicylideneaniline.

Salicylideneaniline (SA) is an archetypal system for excited-state intramolecular proton transfer (ESIPT) in non-planar systems. Multiple channels for relaxation involving both the keto and enol forms have been proposed after excitation to S1 with near-UV light. Here, we present transient absorption measurements of hot gas-phase SA, jet-cooled SA, and SA in Ar clusters using cavity-enhanced transient absorption spectroscopy (CE-TAS). Assignment of the spectra is aided by simulated TAS spectra, computed by applying time-dependent complete active space configuration interaction (TD-CASCI) to structures drawn from nonadiabatic molecular dynamics simulations. We find prompt ESIPT in all conditions followed by the rapid generation of the trans keto metastable photochrome state and fluorescent keto state in parallel. Increasing the internal energy increases the photochrome yield and decreases the fluorescent yield and fluorescent state lifetime observed in TAS. In Ar clusters, internal conversion of SA is severely hindered, but the photochrome yield is unchanged. Taken together, these results are consistent with the photochrome being produced via the vibrationally excited keto population after ESIPT.

Synthesis, Characterization, Theoretical and Experimental Anticancer Evaluation of Novel Cocrystals of 5-Fluorouracil and Schiff Bases against SW480 Colorectal Carcinoma.

The chemotherapeutic agent known as 5-fluorouracil (5-FU) is an artificial fluoropyrimidine antimetabolite that has been widely used for its antineoplastic properties. Cocrystals of 5-fluorouracil (5-FU) with five different Schiff bases (benzylidene-urea (BU), benzylidene-aniline (BA), salicylidene-aniline (SA), salicylidene-phenylhydrazine (SPH), and para-hydroxy benzylideneaniline (HBA)) are reported in this study. The newly synthesized cocrystals were analyzed by FTIR and PXRD. In this study, we investigated the antitumor efficacy of 5-FU derivatives in SW480 colon cancer cells via MTT assay at varying dose concentrations. Molecular docking was performed to predict the binding mechanism of TS with various 5-FU complexes. FTIR revealed the presence of respective functional groups in the prepared cocrystals. The frequencies (v) of N-H (3220.24 cm-1) and carbonyl groups (1662.38 cm-1) in the spectrum of 5-FU shifted considerably in all derivative cocrystal new interactions. There was a noticeable transformation in the PXRD peak of 5-FU at 2θ = 28.37° in all derivatives. The novelty of the present study lies in the fact that 5-FU-BA showed an anticancer potential IC50 (6.4731) far higher than that of 5-FU (12.116), almost comparable to that of the reference drug doxorubicin (3.3159), against SW480 cancel cell lines, followed by 5-Fu-HBA (10.2174). The inhibition rates of 5-FU-BA and 5-FU-HBA were highest among the derivatives (99.85% and 99.37%, respectively) in comparison with doxorubicin (97.103%). The results revealed that the synthesized 5-FU cocrystals have promising antitumor efficacy compared with previously reported 5-FU and 5-FU. The activities of the cocrystals were rationalized by a molecular modeling approach to envisage binding modes with the target cancer protein.

Spectroscopic Tracking of Salicylideneaniline Photocolored Crystals: An Attempt to Quantify Polymorph-Dependent Features toward Precise Structure-Function Correlation Analysis.

Three polymorphs of salicylideneaniline (SA) were prepared, and their photochromic behavior was examined using a recently developed single-crystal microscopic UV-vis spectroscopy approach. This system enabled us to acquire absorption data during the bleaching process as a function of temperature and visible light intensity. First, we demonstrated that, in contrast to the generally accepted assumption, the bleaching curves were notably influenced by the degree of photosaturation at the initial stage. By modifying our kinetic model to include the term representing the initial degree of photosaturation, we successfully obtained the kinetic parameters intrinsic to each crystal structure. Second, we further analyzed the kinetic parameters to show that the bleaching process was accelerated by visible light irradiation to a significantly higher degree than by thermal relaxation. The two bleaching-prompting effects were quantitatively compared between two photochromic polymorphs, α1 and α2; the long life of the photoproduct in α2 was attributed to efficient self-shielding from visible light irradiation enabled by its structural features. These results prompted us to reexamine the simple dualistic photochemical and thermal classification of photochromic systems and will provide a foundation for the precise structure-function analysis of crystalline materials, including SAs.

Thermal-Induced Twisting and Photoinduced Planarization of Salicylideneaniline in Alcohols.

Thermofluorochromism and photochromism of salicylideneaniline (SA) in alcohol were investigated using steady-state and time-resolved fluorescence and absorption spectroscopy. The planar trans-enol form of SA in alcohols is converted into the twisted trans-enol form on heating. This conversion results change in the emission maximum from the 530 to the 440 nm region with an increase in fluorescence intensity, which confirms the absence of intramolecular hydrogen bonding between imine nitrogen and phenolic hydrogen in the twisted trans-enol form. The activation barrier for thermal-induced formation of the twisted trans-enol form in methanol was determined experimentally and was found to be 20.15 ± 2.22 kcal/mol. The rotation of the phenolic C7-C8 and C7-N1 bond followed by breaking of the intramolecular hydrogen bond and formation of an intermolecular hydrogen bond with alcohol solvent molecules results in the thermally stable twisted trans-enol form in alcohol solvents. The biexponential nature of the fluorescence decay of the twisted trans-enol form of SA confirms that the emission originates from multiple (π-π* and n-π*) excited states. On photolysis under UV light, the twisted trans-enol form is converted back into the planar trans-enol form. The time-resolved absorption and excitation-resolved fluorescence spectrum of SA in methanol confirm the existence of the twisted cis-keto form as a transient photochromic intermediate in the light-induced planarization of SA in alcohols. In alcohols, an interplay between the intra- and intermolecular hydrogen-bonding controls excited-state reaction dynamics and conformational relaxation of SA, which are responsible for the photochromism of salicylideneaniline.

A Spectroscopic Study of Tautomeric Equilibrium of Salicylideneaniline in ZSM-5 Zeolites.

Salicylideneaniline (SA) sorbed in cation-exchanged M-ZSM-5 (M = H+, Li+, Na+, K+, Rb+, Cs+ and Zn2+) zeolites was studied by spectroscopic techniques assisted by quantum-chemical calculations. The nature of extra-framework cations present in the zeolite void was found to affect the spectral signature of the sorbed SA molecule that points to the shift of tautomeric equilibrium between the enol and keto forms. Small size cations, such as H+ and Li+, stabilize a cis-keto SA tautomer along with a enol one in the zeolite structure. The calculations indicate that the sorbed cis-keto tautomer may have the dipole large enough to be considered as a zwitterion. New features appearing in the spectra with the increase of the cation size were attributed to the presence of trans-keto SA tautomer, which up to now has been observed only in time-resolved spectroscopic experiments. A strong interaction of the molecule with cations in Zn-ZSM-5 zeolite results in the chelation of enol SA with the divalent Zn2+ ions. The results of the study suggest that the tautomeric equilibrium of molecules belonging to the Schiff base family can be tuned by the confinement in the nanoporous materials via a choice of topology of zeolite framework and the nature of extra-framework cations.

Electronic transport induced by edge modification of graphene electrodes in single molecular device

The aim was to study the electronic transport of molecular devices constructed by salicylidene aniline molecule and graphene electrodes using the density functional theory and non-equilibrium Green’s function. The calculated results demonstrate a switching behavior in two photoisomerizations. In addition, the modification of –OH on the edge of graphene nanoribbons induces the variety of the frontier molecular orbitals and the increase of current, but the decrease of switching ratio. The modification of F on the edge of graphene nanoribbons improves the switching ratio. We explain the negative differential resistance effect found in the device by transmission spectra and the evolution of local density of states at the bias. The results indicate that different modifications on the edge of graphene nanoribbons influence the electronic transport. This method can improve the application of the device in future molecular circuits.

Effect of Nonplanarity on Excited-State Proton Transfer and Internal Conversion in Salicylideneaniline.

Salicylideneaniline (SA) is a prototype for excited-state intramolecular proton transfer (ESIPT) reactions in nonplanar molecules. It is generally understood that the dominant photochemical pathway in this molecule is ESIPT followed by nonradiative decay due to twisting about its phenolic bond. However, the presence of a secondary internal conversion pathway resulting from frustrated proton transfer remains a matter of contention. We perform a detailed nonadiabatic dynamics simulation of SA and definitively identify the existence of both reaction pathways, thereby showing the presence of a secondary photochemical pathway and providing insight into the nature of ESIPT dynamics in molecules with nonplanar ground-state geometries.

The crystallographic, spectroscopic and theoretical studies on (E)-2-(((4-chlorophenyl)imino)methyl)-5-(diethylamino)phenol and (E)-2-(((3-chlorophenyl)imino)methyl)-5-(diethylamino)phenol molecules

Two new salicylideneaniline (SA) derivative compounds (E)-2-(((4-chlorophenyl)imino)methyl)-5-(diethylamino)phenol, compound (I), and (E)-2-(((3-chlorophenyl)imino)methyl)-5-(diethylamino)phenol, compound (II), have been synthesized and characterized by single crystal X-ray diffraction, IR spectroscopy, 1H NMR, 13C NMR and theoretical methods. Both of the compounds which are Schiff base derivatives are isomer of each other. While the compound (I) crystallizes in centrosymmetric monoclinic space group P 21/c, the compound (II) crystallizes in orthorhombic space group P 212121. The theoretical parameters of the molecules have been calculated by using Hartree-Fock (HF) and density functional theory (DFT/B3LYP) with 6-31G (d,p) basis set. These theoretical parameters have been compared with the experimental parameters obtained by XRD. The experimental geometries of the compounds have been superimposed with the theoretical geometries calculated by HF and DFT methods. Furthermore, the theoretical IR calculations, molecular electrostatic potential maps (MEP) and frontier molecular orbitals have been created for the compounds.

Solvent Dependent Dynamics of Salicylidene Aniline in Binary Mixtures of Supercritical CO2 with 1-Propanol or Cyclohexane.

The role of different solvent environments in determining the behavior of molecules in solution is a fundamental aspect of chemical reactivity. We present an approach for exploring the influence of solvent properties on condensed-phase dynamics using ultrafast transient absorption spectroscopy in supercritical CO2. Using supercritical CO2 permits adjustment of the density, by varying the temperature and pressure, whereas varying the concentration or identity of a second solvent, the cosolvent, in a binary mixture allows for adjustments of the degree of interaction between the solute and the solvent. Salicylidene aniline, a prototypical excited-state intramolecular proton-transfer system, is the subject of this study. In this system, the decay rate of the transient absorption signal decreases as the fraction of the cosolvent (for both 1-propanol and cyclohexane) increases. The decay rate also decreases with an increase in the viscosity of the mixture, but the effect is much larger for the 1-propanol cosolvent than for cyclohexane. These observations illustrate that the decay rate of the photoexcited salicylidene aniline depends on more than just the solvent viscosity, suggesting that properties such as polarity also play a role in the dynamics.

Conformational aspects of the photochromic reactivity of two N-salicylidene aniline derivatives in a polymer matrix

Abstract Reversible changes induced by a polystyrene matrix on the photochemistry of two derivatives of N -salicylidene aniline were investigated by steady–state and time resolved spectroscopy. The photosensitivity of N -salicylidene- p -cyanoaniline (SA-CN) and N -salicylidene- p -carboxyaniline (SA-COOH) upon insertion in the matrix was tested by irradiation with UV light. The inactive photochromism of N -salicylidene- p -cyanoaniline has been activated via a conformational change from planar to a non-planar geometry, accompanied by fluorescence quenching. The geometry of SA-COOH molecules in polystyrene matrix remained as flat as in crystals, and its photochemistry was unchanged as well, the pure compound being both photochromic and fluorescent. With the help of flash photolysis and time-resolved fluorescence the transient species in the ns–ms timescale were identified. The transient absorption spectra revealed some differences in the short-lived species between the two compounds, suggesting a rich photochemistry for SA-COOH and transient species with much longer lifetime for SA-CN.

Two-Dimensional Organic Single Crystals with Scale Regulated, Phase-Switchable, Polymorphism-Dependent, and Amplified Spontaneous Emission Properties.

The successful preparation of two-dimensional (2D) single crystals can promote the development of organic optoelectronic devices with excellent performance. A Schiff base compound salicylidene(4-dimethylamino)aniline with aggregation induced emission (AIE) property was employed as the building block to fabricate 2D thin single crystal plates with scales from around 50 μm to 1.5 cm. Yellow and red emissive polymorphs were concomitantly obtained during crystallization. The single-crystal-to-single-crystal (SC-to-SC) transformation from yellow polymorph to red one was demonstrated. Furthermore, both polymorphs exhibited amplified spontaneous emission (ASE) properties. Interestingly, the red polymorph displayed size-dependent ASE characteristics. The larger red polymorph showed near-infrared ASE with maximum at 706 nm, whereas the smaller one presented red ASE with maximum at 610 nm. These results suggest that the different scale single crystalline thin films with perfect optoelectronic properties may be fabricated by using the organic molecules with 2D assembly feature.

Modeling emission features of salicylidene aniline molecular crystals: A QM/QM' approach.

A new computational protocol relying on the use of electrostatic embedding, derived from QM/QM' ONIOM calculations, to simulate the effect of the crystalline environment on the emission spectra of molecular crystals is here applied to the β-form of salicylidene aniline (SA). The first singlet excited states (S1 ) of the SA cis-keto and trans-keto conformers, surrounded by a cluster of other molecules representing the crystalline structure, were optimized by using a QM/QM' ONIOM approach with and without electronic embedding. The model system consisting of the central salicylidene aniline molecule was treated at the DFT level by using either the B3LYP, PBE0, or the CAM-B3LYP functional, whereas the real system was treated at the HF level. The CAM-B3LYP/HF level of theory provides emission energies in good agreement with experiment with differences of -20/-32 nm (cis-keto form) and -8/-14 nm (trans-keto form), respectively, whereas notably larger differences are obtained using global hybrids. Though such differences on the optical properties arise from the density functional choice, the contribution of the electronic embedding is rather independent of the functional used. This plays in favor of a more general applicability of the present protocol to other crystalline molecular systems.

Substituent effects on the absorption and vibrational spectra of some 2-hydroxy Schiff bases: DFT/TDDFT, natural bond orbital and experimental study

The electronic structure of salicylideneaniline (SA) and some of its derivatives are investigated both experimentally and theoretically. The equilibrium geometric structures of the studied compounds are determined at the B3LYP/6-311++G** level of theory. A set of 12 substituted SA derivatives is considered in the present work. The choice of these substituents aims to create a push-pull system on the SA basic structure which would shade light onto its photo physics. The electronic absorption spectra of SA are recorded in the UV-VIS region, in both polar and nonpolar solvents. Assignments of the observed electronic transitions are facilitated via time-dependent density functional theory (TDDFT) computations at the same level of theory. Electronic configurations contributing to each excited state are identified and the relevant MOs are characterized. The extent of delocalization and intramolecular charge transfer are estimated and discussed in terms of natural bond orbitals (NBO) analysis and second order perturbation interactions between donor and acceptor MOs. Solvent effects on the electronic absorption spectra are discussed in terms of the difference in polarizabilities of the ground and excited states. FTIR spectra of SA and its derivatives are measured in KBr platelets. Detailed vibrational assignments are given based on the calculated potential energy distributions. “IR marker bands” that characterize the SA framework are identified. The effect of substituents, the nature of the characteristic “marker bands”, and intensity quenching of some bands are discussed.

Cloud point extraction studies on recovery of nickel(II) from highly saline sulfate medium using salicylideneaniline mono-Schiff base chelating extractant

A novel cloud point extraction process (CPEP) has been developed for recovery of nickel(II) from saline sulfate medium via the use of the lipophilic chelating extractant, salicylideneaniline (SAN), and the nonionic surfactant, Triton X-100. Surfactant solutions are employed in conjunction with SAN to form nickel complexes, which are subsequently entrapped in the micelles of the surfactant-rich phase, upon increase the temperature above the cloud point temperature. The effects of the main experimental parameters such as pH, extractant concentration, non-ionic surfactant concentration and temperature on the cloud point extraction process of nickel(II) with SAN were studied and optimized. The use of the SAN/TritonX-100 system led to very good extraction efficiency and concentrating ability for Ni(II) pollutant. Indeed, nearly 90% extraction efficiency with a minimal volume fraction of surfactant-rich phase (ϕs=0.1), and a high concentration factor (CF≈35) was achieved at pH 8.8, in one step. The analysis of the extraction data revealed that the cloud point process of nickel proceeds via a cation exchange mechanism. The stoichiometry of the complex extracted into the surfactant-rich phase was ascertained by the slope analysis method to have a composition of 1:2 [Ni:SAN]. Under the similar conditions, a higher extraction constant was determined for CPE compared with classical solvent extraction, illustrating the feasibility and utility of CPE for Ni(II) recovery. The optimum conditions of the extraction-recovery have been established as the following: (1) 5.1×10−3mol/L ligand; (2) 5wt.% surfactant; (3) pH of 8.8 and (4) temperature of 65°C.

Photoswitching of the dielectric property of salicylideneaniline

Temperature dependent dielectric constant changes for salicylideneaniline (SA) were observed before and after light irradiation. The dielectric constant for a non-illuminated sample is higher than that for an illuminated one. It was considered that this fascinating observation might reflect dynamic chromophoric structural changes within the tautomers of SA.

Electric field control of proton-transfer molecular switching: molecular dynamics study on salicylidene aniline.

In this letter, we propose a novel, ultrafast, efficient molecular switch whose switching mechanism involves the electric field-driven intramolecular proton transfer. By means of ab initio quantum chemical calculations and on-the-fly dynamics simulations, we examine the switching performance of an isolated salicylidene aniline molecule and analyze the perspectives of its possible use as an electric field-controlled molecular electronics unit.