• Bulletin of the Korean Chemical Society
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• 제19권9호
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• pp.980-985
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• 1998

The excited-state intramolecular proton transfer (ESIPT) emission has been observed for 0.01 mM p-aminosalicylic acid (AS) in nonpolar aprotic solvents as demonstrated by the large Stokes' shifted fluorescence emission around 440 nm in addition to the normal emission at 330 nm. However in aprotic polar solvent such as acetonitrile, the large Stokes' shifted emission band becomes broadened, indicating existence of another emission band originated from intramolecular charge transfer (ICT). It is noteworthy that in protic solvents such as methanol and ethanol the normal and ICT emissions are quenched as the AS concentration decreases, followed by the appearance of new emission at 380 nm. These results are interpreted in terms of ESIPT coupled charge transfer in AS. Being consistent with these steady-state spectroscopic results, the picosecond time-resolved fluorescence study unravelled the decay dynamics of the ESIPT and ICT state ca. 300 ps and ca. 150 ps, respectively with ca. 40 ps for the relaxation time to form the ICT state.

• Bulletin of the Korean Chemical Society
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• 제6권1호
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• pp.23-29
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• 1985

The charge-transfer complexing properties of 1-methyl nicotinamide (MNA), an acceptor, and adenine, a donor, were investigated in water and SDS micellar solutions in relation to the intramolecular interaction in nicotinamide adenine dinucleotide ($NAD^+$). The spectral and thermodynamic parameters of MNA-indole and methyl viologen-adenine complex formations were determined, and the data were utilized to evaluate the charge-transfer abilities of MNA and adenine. The electron affinity of nicotinamide was estimated to be 0.28 eV from charge-transfer energy $of{\sim}300$ nm for MNA-indole. The large enhancement of MNA-indole complexation in SDS solutions by entropy effect was attributed to hydrophobic nature of indole. The complex between adenine and methyl viologen showed an absorption band peaked near 360 nm. The ionization potential of adenine was evaluated to be 8.28 eV from this. The much smaller enhancement of charge-transfer interaction involving adenine than that of indole in SDS solutions was attributed to weaker hydrophobic nature of the donor. The charge-transfer energy of 4.41 eV (280 nm) was estimated for nicotinamide-adenine complex. The spectral behaviors of $NAD^+$ were accounted to the presence of intramolecular interaction in $NAD^+$, which is only slightly enhanced in SDS solutions. The replacement of nicotinamide-adenine interaction in $NAD^+$ by intermolecular nicotinamide-indole interaction in enzyme bound $NAD^+$, and guiding role of adenine moiety in $NAD^+$ were discussed.

• Bulletin of the Korean Chemical Society
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• 제28권8호
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• pp.1249-1255
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• 2007

We have investigated the photophysical properties of dansyl-N-methylaminobenzoic acid (DABAH) as a ligand and its lanthanide (Ln3+)-cored complexes (Ln3+-(DABA)3(terpy)) in order to determine the main energy transfer pathway for sensitized near infrared emission of Ln3+ ions (Ln3+ = Nd3+ and Er3+) in Ln3+- (DABA)3(terpy). The fluorescence spectrum of DABAH shows a large Stokes shift with increasing solvent polarity. This large Stokes shift might be due to the formation of a twisted intramolecular charge transfer (TICT) state, as demonstrated by the large dipole moment in the excited state. It is in good agreement with the result that the phosphorescence even in the Gd3+-cored complex based on the DABAH ligand was not observed, maybe due to the highly forbidden character of the S1 → T1 transition in the DABAH ligand. A short decay component (ca. 1 ns) was observed in Er3+-(DABA)3(terpy) whereas the fluorescence lifetimes of DABAH and its Gd3+-(DABA)3(terpy) are observed about ~10 ns. The short component could be originated from the energy transfer process between the ligand and the Ln3+ ion. Based on the fluorescence of DABAH its Ln3+- (DABA)3(terpy), the sensitization of Ln3+ luminescence in the Ln3+-(DABA)3(terpy) takes place by the energy transfer via the TICT state of DABAH in the excited singlet state rather than via the excited triplet state.

• Bulletin of the Korean Chemical Society
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• 제25권6호
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• pp.907-909
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• 2004

• 한국광과학회:학술대회논문집
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• 한국광과학회 1995년도 학술대회지
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• pp.11-11
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• 1995

• Bulletin of the Korean Chemical Society
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• 제14권6호
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• pp.704-708
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• 1993

The intramolecular charge transfer (ICT) phenomena of the photoexcited 2-biphenylcarboxylic acid (2BPCA) and 4-biphenylcarboxylic acid (4BPCA) have been investigated in some surfactant micellar solutions. The ICT emission of 4BPCA and 2BPCA in aqueous solution at sufficiently low pH (1-3) has been observed to be markedly quenched and blue-shifted upon addition of a cationic surfactant, cetyltrimethylammonium chloride (CTAC) in contrast to little change in anionic sodium dodecyl sulfate (SDS) and neutral Brij 35. An anionic emission band has been observed to be enhanced at expense of the ICT emission as a function of the concentration of CTAC. These results with the micellar effects on the fluorescence decay kinetics of 4BPCA suggest that formation of the ICT state of the excited acids is inhibited by CTAC-induced proton transfer as well as the decrease in the polarity and/or hydrogen-bonding ability of the micellar microenvironment entrapping the acids.

• Bulletin of the Korean Chemical Society
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• 제32권3호
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• pp.981-987
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• 2011

The anomalous spectroscopic properties of quercetin-3-O-rhamnoside (QCRM) and quercetin-3-O-rutinoside (QCRT) in AOT reverse micelle were studied. The excited state intramolecular proton transfer (ESIPT) occurs through the strong hydrogen bond between the -OH at position 5 and the carbonyl oxygen. Because the ESIPT can only happens in the $S_1$ state and the Franck-Condon factor involved in the $S_2\;{\rightarrow}\;S_1$ internal conversion is small, the $S_2\;{\rightarrow}\;S_o$ emission alone appears. Because the molecular planarity is improved at the interior of the micelle, the excited state intramolecular charge transfer in the $S_1$ state is extended, and the excited state is more tolerable for any quenching effects in the micelle. Therefore, an $S_1\;{\rightarrow}\;S_o$ emission was newly discovered under this micelle microenvironment. For the $S_2\;{\rightarrow}\;S_o$ emission, the quantum yields increase but the quantum yield of the $S_1\;{\rightarrow}\;S_o$ emission approximately decreases as the water concentration in the micelle increases.

• Current Photovoltaic Research
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• 제5권2호
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• pp.43-46
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• 2017

Large absorption band shift has been observed for the azo-dye (disperse red-13, DR-13) attached on the surface of silica spheres. Urethane linkage has been utilized to form covalent bond between azo-dye (-OH) and 3-isocyanatopropyltriethoxysilane (ICPTES, -N=C=O). The synthesized ICPTES-DR-13 (ICPDR) molecules were attached to the silica spheres by the hydrolysis and condensation reaction. Although the absorption peak of DR-13 in methanol is at 510 nm, the absorption peak of the ICPDR-silica spheres shifts to 788 nm. The large absorption peak shift is due to the formation of intramolecular charge-transfer band with large aggregated ICPDR.

• Bulletin of the Korean Chemical Society
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• 제35권1호
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• pp.135-140
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• 2014

A bent-shape triazolyl derivative was synthesized via click chemistry, and its photophysical property was investigated in various solvents. In contrast to the invisible ultraviolet emission of other solutions, the chloroform solution exhibited a blue light emission at 460 nm. Furthermore, the blue fluorescence intensified as the UV exposure time at 365 nm increased. On the basis of $^1H$-NMR, pH paper, and acid-addition studies, we confirmed that chloroform was decomposed into HCl with the aid of the triazolyl derivative. The density functional theory calculations suggested that the eye-detectable blue fluorescence was attributed to an intramolecular charge transfer process of the protonated triazolyl derivative in the chloroform solution.

• Bulletin of the Korean Chemical Society
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• 제13권6호
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• pp.613-620
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• 1992

The solvent-dependent photophysical properties of 2-biphenylcarboxylic acid (2BPCA) and 4-biphenylcarboxylic acid(4BPCA), which have a pre-twisted conformation in the ground state, have been investigated. The fluorescence spectra of 4BPCA show vibrational structure with a non-mirror image to the absorption spectra in nonpolar solvent while those of 2BPCA show no structure even in nonpolar solvents. As the solvent polarity increases, the fluorescence spectra become diffuse and broad with a strong red shift resulting in the large Stokes shift. The large fluorescence Stokes shift of BPCA's in polar solvent is also partially due to an intramolecular charge transfer (ICT) interaction in the excited state, as demonstrated by the large dipole moment in the excited state (7.6-10.6 D). The fluorescence decay behaviors of BPCA's (decay-times and their pre-exponential factors) also depend on solvent polarity in agreement with the solvent-dependent properties of the steady-state fluorecence. The data have been discussed in terms of change in the excited-state potential energy surface with respect to change of the dihedral angle of biphenyl moiety.