• Bulletin of the Korean Chemical Society
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• 제30권7호
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• pp.1452-1458
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• 2009

The change in the electronic absorption and emission energy of 7-aminocoumarin derivatives in binary solvent mixtures has been studied. The electronic transition energy along with the Stokes' shift is correlated with the orientation polarizability of the solvent as well as the empirical solvent polarity parameters $E_T$ (30). It is observed that the emission peak shift traces the change of $E_T$ (30) value very closely in binary solvent mixtures. The emission transition more strongly depends on the solvent polarity than the absorption, which indicates the dipole moment gets larger on excitation. From the dependence of the Stokes’ shift of 7-aminocoumarins with the solvent polarity parameters and the ground state dipole moment obtained by the semi-empirical calculations, the excited state dipole moment was estimated. The fluorescence lifetime change of 7-aminocoumarins in binary solvent mixtures was measured and the results are explained in terms of molecular conformation and solvent polarity. The study indicates the empirical solvent polarity $E_T$ (30) is a good measure of microscopic solvent polarity and it probes in general the non-specific solvent interactions.

• Journal of Photoscience
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• 제6권2호
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• pp.61-65
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• 1999

The fluorescence properties and photoisomerization behavior of 1-(9-anthryl)-2-(n-quinolinyl)ethene (n-AQE, n=2-4) have been investigated in various solvents. t-3-AQE is strongly fluorescent, but does not accomplish photoisomerization, similar to parent hydrocarbon compound, t-1-(9-anthryl)-2-phenylethene (t-9-APE) or t-1-(9-anthryl)-2-(1-naphthyl)ethene (t-1-ANE). Fluorescence and photoisomerization oft-2-AQE and t-4-AQE are strongly affected by solvent polarity. Dependence of fluorescence quantum yield on the solvent polarity is moderate for t-2-AQE and large for t-4-AQE. In nonpolar solvent (in n-hexane), they exhibit relatively strong fluorescence, but do not isomerize to cis isomer on irradiation, even if inefficient isomerization is observed for t-4-AQE. However, as solvent polarity increases, their fluorescences become weak with efficient photoisomerization to corresponding cis isomer. Intramolecular charge-transfer excited state is presumed to contribute to photoisomerization. The S$_1$ decay parameters were found to be solvent-dependent due to the charge-transfer character of lowest S$_1$ state. In polar solvents, the activation barrier to twisting is reduced enhancing the isomerization of r-2-AQE and t-4-AQE in the singlet manifold.

• Bulletin of the Korean Chemical Society
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• 제13권6호
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• pp.636-642
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• 1992

Preferential solvation (PS) phenomena of solutes based on solvent polarity, $E_T$ and AN, were studied by UV/vis. and NMR spectra in MeOH binary mixtures. According to the extent of solvent-solvent interaction, different solvation phenomena were found. PS concept was applied to explain the reactivity of tert-butyl halides solvolysis. The findings of solvation phenomena have been related to the rate of solvolysis and PS suggested as a reason for the solvent dependence of the rates of reaction. Moreover, we found that the results of principal components analysis using six parameters are in good accordance with the results of PS phenomena in mixed methanol systems.

• Bulletin of the Korean Chemical Society
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• 제20권11호
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• pp.1263-1268
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• 1999

The fluorescence properties and photoisomerization behavior of 1-(9-anthryl)-2-(2-quinolinyl)ethene (2-AQE) have been investigated in various solvents. Instead of phenyl ring in 1-(9-anthryl)-2-phenylethene, the intro-duction of quinoline ring reduces not only the fluorescence yield but also the photoisomerization yield, due to competition of efficient radiationless deactivation and an increase in the torsional barrier for twisting in the singlet manifold. The S1 decay parameters were found to be solvent-dependent due to the charge-transfer character of lowest S1 state. Polar solvents reduce the activation barrier to twisting, thus slight enhancing the isomerization of t-2-AQE in the singlet manifold. As solvent polarity is increased, Φf of c-2-AQE is greatly reduced, but Φc →ｔ is practically independent of solvent polarity. Dual fluorescence in t-2-AQE was observed and two fluorescing species could be assigned t-2-AQE and c-2-AQE, where the ratio between two species was dependent on the solvent polarity. Interestingly, in the concentration above 1×10 -4 M, the shapes of the fluorescence excitation spectra of t- and c-2-AQE are significantly altered without spectral changes of their fluorescence and absorption, probably due to the formation of excimer.

• Bulletin of the Korean Chemical Society
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• 제19권5호
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• pp.561-564
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• 1998

Solvent effects on the reactions of DANSYL and BANSYL chlorides with substituted pyridines have been investigated using two parameters of Taft's solvatochromic correlation and four parameters of Kirkwood-Onsager, Parker, Marcus, Hildebrand equation. The acetonitrile molecules accelerate charge separation of the reactants and stabilize the transition state. The coefficient of the solvent parameters provide a good information to predict and to analyze the reaction mechanism. The nucleophilic substitution reaction of DANSYL and BANSYL chlorides with substituted pyridines are ruled by the contribution of the change in dipole moment term and polarity-polarizability term.

• 대한화학회지
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• 제37권12호
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• pp.1025-1034
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• 1993

정상 액체 크로마토그래피에 사용되는 2-propanol / hexane 혼합용매계와 ethyl acetate / hexane 혼합용매계에 대하여 전 용매조성에 대한 극성도 지수 ${\pi}^*$, $\alpha$ , $\beta$값을 측정하였다. 이 중 hexane/ethyl acetate계는 전 조성에 대하여 $\alpha$ 가 0으로 정의되므로 ${\pi}^*$와 $\beta$값만을 측정하였다. 기존의 문헌치 ${\pi}^*$, $\alpha$ , $\beta$와 일관성이 있는 극성도 지수를 구하기 위하여 본 연구의 실측치와 문헌치간에 좋은 직선상관성을 가정하여 보정하였으며 최종 보정된 혼합용매 극성도 지수의 용매 조성에 따른 변화는 각 용매성분의 화학적 성질에서 예측할 수 있는 경향에 부합하는 결과를 보였다. 이들 두 용매계에 대하여 관찰된 일반적인 경향은 다음과 같다. 극성도 대 조성배의 그래프에서 ${\pi}^*$값은 더 극성인 용매의 조성비가 증가할수록 증가하는 경향을 보이고, $\alpha$ 와 $\beta$ 값은 더 극성인 용매의 조성비가 0일 때 최소값을 갖고 조성비의 증가에 따라 극대치를 이룬 다음 다시 감소하는 특이한 경향을 보였다.

• 대한화학회지
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• 제28권4호
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• pp.210-216
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• 1984

MeOH-MeCN 혼합용매의 Taft용매 파라미터인 ${\pi}^{\ast}$(용매의 polarity-polarizability), ${\alpha}$(용매의 수소결합 주게 산도) 그리고 ${\beta}$(용매의 수소결합 받게 염기도)를 여러 지시약을 사용하여 분광용매화 비교법으로 구하였다. 또한 Swain의 용매 파라미터인 A(음이온을 용매화 시키는 척도)와 B(양이온을 용매화 시키는 척도)를 반응속도 자료를 이용하여 최소 자승법으로 구하였다. 용매 상수 ${\beta}$는 용매의 염기도에 의존하며 혼합용매의 MeOH 함량이 증가할 수록 $(MeOH)_n$의 기여에 의해 증가하는 것을 알 수 있었다. ${\pi}^*$는 용매의 쌍극자 모멘트에 의존하며 혼합용매의 MeCN 함량이 증가할 수록 ${\pi}^{\ast}$값도 커지며 ${\alpha}$는 MeOH의 수소결합주게 효과에 의해 혼합용매의 MeOH함량이 증가할 수록 크게 증가하는 것을 나타냈다. 앞서 보고된 반응들에 용매 파라미터를 적용하여 반응상수를 구하였으며 Taft의 반응상수 a, s와 Swain의 반응상수 a, b사이에는 용매 척도의 차이 때문에 서로 연관성이 없었다. 그러나 그들의 비인 a/s와 a/b는 서로 좋은 직선관계를 보여 주었으며 이들 반응상수 비를 이용하여 반응 메카니즘이나 치환기 변화 및 이탈기 변화에 미치는 용매효과를 논의 하였다.

• Bulletin of the Korean Chemical Society
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• 제27권12호
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• pp.2011-2018
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• 2006

We have investigated the solvent effects on $\Delta log\;K_s $(the difference of stability constant of binding) and the different free energies of binding of $Nd^{3+}$ and $Eu^{3+}$ ions to 18-crown-6, i.e., the selectivity of $Nd^{3+}$ and $Eu^{3+}$ ions to 18-crown-6 using a Monte Carlo simulation of statistical perturbation theory (SPT) in diverse solvents. The stability constant ($\Delta log\;K_s $) of binding of $Nd^{3+}$ and $Eu^{3+}$ ions to 18-crown-6, in $CH_3OH$ was calculated in this study as -1.06 agrees well with the different experimental results of -0.44~-0.6, respectively. We have reported here the quantitative solvent-polarity relationships (QSPR) studied on the solvent effects the relative free energies of binding of $Nd^{3+}$ and $Eu^{3+}$ ions to 18-crown-6. From the calculated coefficients of QSPR, we have noted that solvent polarity (ET) and Kamlet -Tafts solvatochromic parameters (b ) dominate the differences in relative solvation Gibbs free energies of $Nd^{3+}$ and $Eu^{3+}$ ions but basicity (Bj) dominates the negative values in differences in the stability constant ($\Delta log\;K_s $) as well as the relative free energies of binding of $Nd^{3+}$ and $Eu^{3+}$ ions to 18-crown-6 and acidity (Aj) dominates the positive values in differences in the stability constant ($\Delta log\;K_s $) as well as the relative free energies of binding of $Nd^{3+}$ and $Eu^{3+}$ ions to 18-crown-6.

• Archives of Pharmacal Research
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• 제20권3호
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• pp.269-274
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• 1997

Solubilities of oleanolic acid and ursolic acid in aqueous surfactant solutions, liquid polyethylene glycols (PEG), and solvents of various polarity were measured. The results showed that the solutes were slightly or moderately solubilized in the surfactant solutions and the liquid PEGS. It was also revealed that the solutes were slightly soluble in the solvent of either extreme polarity or nonpolarity, but moderately soluble in solvents of intermediate polarity of which solubility parameters are around 10. The solubility parameters of these solutes were calculated from the group contribution to be 10.2 for both of them. Of the solvents tested, tetramethylurea was exceptionally effective in solubilizing the solutes. The solutes were also moderately soluble in the aqueous cosolvents containing tetramethylurea. This suggests that the mixed systems of tetramethylurea could be employed for the solubilization in the formulation of these compounds as an aqueous system.

• Bulletin of the Korean Chemical Society
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• 제16권7호
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• pp.574-577
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• 1995

Solvatochromic effect and hydrogen bonding interaction of NPNOH, NPNO- and NPNOR were investigated. Electronic transition energies of the dyes were plotted against empirical solvent polarity parameters, Taft's π* and Reichardt's ET(30). Good correlations were observed when the excitation energies were plotted against the energy calculated by multiple linear regression method which was developed by Taft. There is an intrinsic difference between betaine for ET(30) polarity scale and the azoderivative, which is derived from the specific hydrogen bond incurred with probe molecules and solvents. The hydrogen bonding plays a very important role for stabilization of an excited state molecule by solvents especially when a solute possesses a negative charge as with NPNO-.