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Theoretical design, synthesis and studies on the solvatochromic behaviour of low band gap phenylenevinylene based copolymers
摘要： A new series of low band gap phenylenevinylene based copolymers was designed by employing density functional theory in the periodic boundary condition using HSE06 exchange correlation functional using 6-31G basis set and synthesized via the Gilch polymerization. The theoretical band gap of the copolymers MD-CA-PPV, MD-FL-PPV, MD-PT-PPV and MD-AN-PPV were found to be 1.98, 2.07, 2.31 and 1.99 eV respectively using the DFT/HSE06/6-31G calculation and the optical band gap of 1.96, 2.03, 2.01 and 1.98 eV respectively, according to the onset edge of lower energy peak of the polymers in solution. The experimental results supported the theoretical prediction. Solvatochromic behaviour of the synthesized copolymers was studied thoroughly in toluene/acetonitrile mixtures of varying polarity at room temperature. The absorption spectrum of the PPV polymers was sensitive to solvent effects which showed bathochromic and hypsochromic shifts with increasing solvent polarity indicating that the transitions involved were π-π* and n-π*. The ground and excited state dipole moments were calculated using solvatochromic correlations. Onsager radius determined from ab initio calculation was used in the determination of dipole moments. The change in the dipole moment (Δμ) was calculated both from solvatochromic shift method and on the basis of microscopic empirical solvent polarity parameter (ET(30)) and values are compared. It was observed that the excited state dipole moment (μe) was larger than its ground state (μg) counterpart. This indicated that a substantial redistribution of the π-electron densities occurred in the more polar excited state for the selected phenylenevinylene polymers. The third-order nonlinear optical (NLO) properties of the copolymers, evaluated by Z-scan method with nanosecond laser beam at 532 nm, are reported. The nonlinear absorption coefficient of the copolymers were calculated to be 0.17×10-10, 2.06 × 10-10, 0.63 × 10-10 and 2.83 × 10-10 esu, respectively for MD-CA-PPV, MD-FL-PPV, MD-PT-PPV and MD-AN-PPV which certified that the polymers showed semiconductor properties.
关键词： Nonlinear optical properties,Solvatochromic properties,Gilch polymerisation,Density functional theory,Poly(p-phenylenevinylene) derivatives
更新于2025-09-19 17:15:36
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MCM-SO3H catalyzed synthesis of environment-sensitive fluorophores incorporating pyrene moiety: Optimization, fluorescence emission and theoretical studies
摘要： Six new highly fluorescent 5-(aryl)-1-phenyl-3-(pyren-1yl)-2-pyrazolines were synthesized by reaction of various (E)-3-aryl-1-(pyren-1-yl)prop-2-en-1-ones with phenyl hydrazine in the presence of sulfonated mesoporous silica (MCM-SO3H) as efficient and eco-friendly acidic catalyst. The chemical structures of all synthesized compounds were illustrated on the basis of spectral data (IR, 1H NMR and 13C NMR). This was followed by photophysical properties-based absorption and emission studies of the target compounds in solutions of different solvent polarities. The microenvironment-sensitive fluorescent pyrazolines labeled with pyrene exhibited valuable fluorescence properties with emission in the range of 600–700 nm with a marked response to change in the environmental polarities. A significant and pronounced red shift was observed in the emission spectrum of 5-(aryl)-1-phenyl-3-(pyren-1yl)-2-pyrazolines Δλ ～ 50 nm compared to the absorption spectrum Δλ ～ 10 nm upon increasing the solvent polarity. This indicated the presence of higher dipole moment in the excited state than in the ground state and the transition involved are π-π* transition through the charge transfer phenomena. The fundamental understanding of solvatochromic properties were analyzed through Lippert-Mataga and Reichardts correlations in order to estimate the change in dipole moments (Δμ) which suggested the emissive state of designed fluorescent 2-pyrazoline derivatives is of strong ICT character.
关键词： Pyrene,Solvatochromic properties,Eco-friendly,2-Pyrazolines,Fluorophores,MCM-SO3H
更新于2025-09-10 09:29:36