Abstract
The electronic spectra of phenol, 2-chlorophenol, 2-aminophenol, and 2-nitrophenol have been studied both experimentally and computationally. The effect of the substituents on the solvatochromic behavior of the phenols were investigated in polar protic (methanol) and aprotic (dimethyl sulfoxide (DMSO)) solvents. The spectra of 2-nitrophenol recorded the highest red shift in methanol. The observed spectral changes were investigated computationally by means of density functional theory (DFT) methods. The gas phase compounds were fully optimized using B3LYP functionals with 6-31++G(d,p) bases set. The effects of the substituents on the electron distribution in the σ-bonds as well as the natural charge on the constituent atoms were analyzed by natural bond orbital (NBO) and natural population analysis (NPA). Second-order perturbation analyses also revealed substantial delocalization of nonbonding electrons on the substituents onto the phenyl ring, thereby increasing its electron density. Full interaction map (FIM) also showed regions of varying propensities for hydrogen and halogen bonding interactions on the phenols.
Highlights
Experimental DetailsAll the phenols and solvents used for this work were purchased from VWR Chemicals, UK, and used without further purification. e phenols were completely soluble in methanol and dimethyl sulfoxide (DMSO)
E electronic spectra of phenol, 2-chlorophenol, 2-aminophenol, and 2-nitrophenol have been studied both experimentally and computationally. e effect of the substituents on the solvatochromic behavior of the phenols were investigated in polar protic and aprotic (dimethyl sulfoxide (DMSO)) solvents. e spectra of 2-nitrophenol recorded the highest red shift in methanol. e observed spectral changes were investigated computationally by means of density functional theory (DFT) methods. e gas phase compounds were fully optimized using B3LYP functionals with 6-31++G(d,p) bases set. e effects of the substituents on the electron distribution in the σ-bonds as well as the natural charge on the constituent atoms were analyzed by natural bond orbital (NBO) and natural population analysis (NPA)
R+ to investigate a series of parasubstituted phenols, Zhang et al [16] found that resonance effect contributed largely to the O-H bond dissociation energy (BDE). is effect was high in electron withdrawing groups as compared to electron-donating analogs
Summary
All the phenols and solvents used for this work were purchased from VWR Chemicals, UK, and used without further purification. e phenols were completely soluble in methanol and DMSO. All the phenols and solvents used for this work were purchased from VWR Chemicals, UK, and used without further purification. E phenols were completely soluble in methanol and DMSO. Stock solutions of 2 mM concentrations were prepared for all the compounds. Ese were further diluted to working concentrations between 0.2 and 1.0 mM. UV absorption spectra were taken on a Spectroquant UV/VIS spectrophotometer Pharo 300 at the Chemistry Laboratory of the Institute of Industrial Research, Council for Scientific and Industrial Research, Ghana, between 250 and 400 nm. Molar absorptivities (ε) were estimated by measuring the absorbance of the diluted solutions at the respective λmax values
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