ABSTRACT
A series of novel Schiff's bases have been synthesized from 3-(1,3-benzothiazol-2-yl)-2-hydroxynaphthalene-1-carbaldehyde. The presence of hydroxyl group ortho to the benzothiazolyl group as well as the imine linkage lead to the occurrence of excited state intramolecular proton transfer process. The computational strategy was used to study the ESIPT process of the synthesized Schiff's bases, which revealed surprisingly that the keto form predominantly exists in the ground state contradicting the ESIPT process. Density functional theory and time dependent density functional theory have been used to investigate the structural parameters and photophysical properties in different solvents of one of the Schiff's bases. The experimental results correlate well with the computed results. All Schiff's bases show good thermal stability.
Subject(s)
Aldehydes/chemistry , Naphthalenes/chemistry , Optical Phenomena , Schiff Bases/chemistry , Absorption, Physicochemical , Electrons , Models, Molecular , Molecular Conformation , Protons , Quantum Theory , Solvents/chemistry , Spectrometry, Fluorescence , Spectrophotometry, Ultraviolet , Spectroscopy, Fourier Transform Infrared , Temperature , ThermogravimetryABSTRACT
Excited state intramolecular proton transfer inspired 3-(1,3-benzothiazol-2-yl)-2-hydroxynaphthalene-1-carbaldehyde, showing solid state fluorescence has been synthesized. Existence of excited state intramolecular proton transfer process between carbonyl group and phenolic OH group has been theoretically predicted using computational method. Density functional theory and time dependent density functional theory computations have been used to investigate structural parameters and understand the photophysical properties of the synthesized carbaldehyde. The photophysical properties of carbaldehyde were evaluated using UV-Visible and fluorescence spectroscopy and are found to be very sensitive to the microenvironment such as solvent polarity and pH. The experimental absorption-emission a results are correlated with the computed values. The increase in the dipole moment of A2-Keto(*) than A2-Enol(*) suggested the presence of keto form in the excited state and which is responsible for the single fluorescence emission with a large Stokes shift in all solvents.
Subject(s)
Computer Simulation , Models, Chemical , Naphthalenes/chemistry , Hydrogen-Ion Concentration , Molecular Structure , Spectrometry, FluorescenceABSTRACT
Two novel ESIPT molecules, 2-[4-(1,3-benzothiazol-2-yl)naphtho[1,2-d][1,3]oxazol-2-yl]phenol 9a and 4-[4-(1,3-benzothiazol-2-yl)naphtho[1,2-d][1,3]oxazol-2-yl]benzene-1,3-diol 9b were synthesized by condensing 1-amino-3-(1,3-benzothiazol-2-yl)naphthalen-2-ol with 2-hydroxybenzoic acid and 2,4-dihydroxybenzoic acid respectively. The novel compounds were characterized by FT-IR, (1)H NMR, Mass spectral and elemental analysis. Effect of polarity on photo physical properties, absorption and emission were studied. Compounds showed single absorption and dual emission due to ESIPT phenomenon. The structural changes due to ESIPT phenomenon in terms of bond angle, bond distances and geometry were investigated by using Gaussian 03 software. These two novel ESIPT molecules are thermally stable up to 200 °C.
