• Bulletin of the Korean Chemical Society
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• v.30 no.5
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• pp.1061-1066
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• 2009

Two fluoro-substituted 2-pyrazoline derivatives, 1-phenyl-3-(4-methoxyphenyl)-5-(4-fluorophenyl)-2-pyrazoline (1) and 1-phenyl-3-(4-methoxyphenyl)-5-(2-fluoro-phenyl)-2-pyrazoline (2) have been synthesized and characterized by elemental analysis, IR, UV-Vis and fluorescence spectra. The crystal structure of 1 has been determined by X-ray single crystal diffraction. For the two compounds, density functional theory (DFT) calculations of the structures and natural population atomic charge analysis (NPA) have been performed at B3LYP/6-311G** level of theory. By using TD-DFT method, electron spectra of 1 and 2 have been predicted, which are very approximate with the experimental ones. Comparative studies on 1 and 2 indicate that the location change of fluorine atom in 5-position phenyl ring of 2-pyrazoline does not make significant change of geometries and electronic transition bands, but it leads to evident change of atomic charge distributions and peak intensities of UV and fluorescence spectra.

• Proceedings of the Korean Vacuum Society Conference
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• 2010.02a
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• pp.310-310
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• 2010

Electronic and photovoltaic characteristics of two sensitizers (TA-BTD-CA and TA-BTD-St-CA), composed of a different $\pi$-conjugation in the linker group, have been investigated by theoretical and experimental methods. The electronic structure, transition dipole moment and oscillator strengths of two sensitizers have been scrutinized by using density functional theory (DFT) and time-dependent DFT (TD-DFT) method. The LUMO level and the oscillator strength of TA-BTD-St-CA was higher than that of TA-BTD-CA, which may facilitate the electron injection process as well as increase the absorption coefficient. The relative efficiencies of the electron injection from the excited sensitizer to nanocrystalline TiO2 and SnO2 films have also been investigated by nanosecond transient absorption spectroscopy. The relative electron injection efficiency of TA-BTD-St-CA exhibited similar injection efficiency for two different semiconductors. However, in the case of TA-BTD-CA sensitizer, electron injection into SnO2 was approximately three times larger than that into TiO2. This enhancement of electron injection of TA-BTD-CA for the SnO2 is due to the increment of the driving force caused by positive shift of conduction band of semiconductor, which was also confirmed from the investigation for the photovoltaic characteristics according to the electrolyte additive, such as LiI additive.

• Bulletin of the Korean Chemical Society
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• v.33 no.11
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• pp.3879-3882
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• 2012

• Bulletin of the Korean Chemical Society
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• v.31 no.9
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• pp.2531-2536
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• 2010

Density functional theory (DFT) and time-dependent DFT (TD-DFT) calculations have been employed to investigate the molecular structures and absorption spectra of two dyes containing diphenylaniline and 4-diphenylamino-diphenylaniline as donor moiety (TPA1 and TPA3). The geometries indicate that the strong conjugation is formed in the dyes. The electronic structures suggest that the intramolecular charge transfer from the donor to the acceptor occurs, and the electron-donating capability of 4-diphenylamino-diphenylaniline is stronger than that of diphenylaniline. The computed highest occupied molecular orbital (HOMO) energy levels are -5.31 and -4.90 eV, while the lowest unoccupied molecular orbital (LUMO) energies are -2.29 and -2.26 eV for TPA1 and TPA3, respectively, revealing that the interfacial charge transfer between the dyes and the semiconductor electrode are electron injection processes from the photon-excited dyes to the semiconductor conduction band. Furthermore, all the experimental absorption bands of TPA1 and TPA3 have been assigned according to the TDDFT calculations.

• 한국신재생에너지학회:학술대회논문집
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• 2010.06a
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• pp.88.1-88.1
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• 2010

Organic dyes, because of their many advantages, such as high molar extinction coefficients, convenience of customized molecular design for desired photophysical and photochemical properties, inexpensiveness with no transition metals contained, and environment-friendliness, are suitable as photosensitizers for the Dye-sensitized Solar Cell (DSSC). The efficiency of DSSC based on metal-free organic dyes is known to be much lower than that of Ru dyes generally, but a high solar energy-to-electricity conversion efficiency of up to 8% in full sunlight has been achieved by Ito et al. using an indoline dye. This result suggests that smartly designed and synthesized metal-free organic dyes are also highly competitive candidates for photosensitizers of DSSCs with their advantages mentioned above. Recently, the performance of DSSC based on metal-free organic dyes has been remarkably improved by several groups. We had reported the novel organic dye with double electron acceptor chromophore, which was a new strategy to design an efficient photosensitizer for DSSC. To verify the strategy, we synthesized organic dyes whose geometries, electronic structures and optical properties were derived from preceding density functional theory (DFT) and time-dependent density functional theory (TD-DFT) calculations. In this paper, we successfully synthesized the chromophore containing multi-acceptor push-pull system from triphenylamine with thiophene moieties as a bridge unit. Organic dyes with a single electron acceptor and double acceptor system were also synthesized for comparison purposes. The photovoltaic performances of these dyes were compared, and the recombination dark current curves and the incident photon-to-current (IPCE) efficiencies were also measured in order to characterize the effects of the multi-anchoring groups on the open-circuit voltage and the short-circuit current. In order to match specifications required for practical applications to be implemented outdoors, light soaking and thermal stability tests of these DSSCs, performed under $100mWcm^{-2}$ and $60^{\circ}C$ for 1000h.

• Bulletin of the Korean Chemical Society
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• v.27 no.7
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• pp.1048-1052
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• 2006

Ab initio calculations of the structure, atomic charges and natural bond orbital (NBO) have been performed at HF/6-311G** and B3LYP/6-311G** levels for the title compound of dibenzothiazyl-disulfide. The calculated results show that the two nitrogen atoms have the biggest negative charges and they are the potential sites to react with the metallic ions, which make the title compound become a di-dentate ligand. Vibrational frequencies of the title compound have been obtained and compared with the experimental value and the comparison indicates that B3LYP/6-311G** level is better than HF/6-311G** level to predict the vibrational frequencies for the system studied here. For the title compound, electronic absorption spectra calculated by time?ependent density functional theory (TD-DFT) are more accurate than Hartree-Focksingle-excitation CI (CI-Singles) method. NBO analyses show that the electronic transitions are mainly derived from the contribution of bands $\pi\rightarrow\pi^{*}$. Thermodynamic calculated results show that the formation of the title compound from 2-mercaptobenzothiazole is a spontaneous process at room temperature with the change of free Gibbs being negative value.

• Bulletin of the Korean Chemical Society
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• v.31 no.8
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• pp.2151-2157
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• 2010

Spectroscopic and quantum mechanical studies of the Et3PAuCl complex were performed to characterize the effect of aurophilicity on the optical properties. When excited with UV light at low temperature, the crystalline complex produced a deep luminescence in both the blue (high-energy) and red (low-energy) regions of the spectrum. The intensity of the low-energy luminescence was markedly reduced in the powdered state and quenched in the solution state. Time-dependent density functional theory (TD-DFT) calculations on electronic structures of both the ground and excited states of aggregates $[Et_3PAuCl]_n$ (n = 1 - 3) indicated that the low-energy luminescence was attributable to Au-centered transitions, which are significantly affected by aurophilic interactions. By contrast, the high-energy luminescence appeared to be independent of the state of the complex and was strongly associated with the charge transfer from Cl to Au.

• Bulletin of the Korean Chemical Society
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• v.28 no.9
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• pp.1539-1544
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• 2007

1-Phenyl-3-p-fluorophenyl-5-p-chlorophenyl-2-pyrazoline has been synthesized and characterized by elemental analysis, IR, UV-Vis and X-ray single crystal diffraction. Density functional calculations show that B3LYP/6-311G** method can reproduce the structural parameters. The electronic absorption spectra have been predicted based on the optimized structure by using 6-311G** and 6-311++G** basis sets and compared with the experimental values. The results indicate that TD-DFT method can only predict the electronic absorption spectra of the system studied here approximately. On the basis of vibrational analyses, the thermodynamic properties of the title compound at different temperatures have been calculated, revealing the correlations between ,C0p,m,S0m,H0m and temperature.

• Bulletin of the Korean Chemical Society
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• v.35 no.2
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• pp.587-596
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• 2014

A new ${\pi}$-stacked donor-acceptor (D-A) system, [Ru(1-([2,2'-bipyridine]-6-yl-methyl)-3-(2-cyclohexa-2',5'-diene-1,4-dionyl)-1H-imidazole)(2,2':6',2"-terpyridine)]$[PF_6]_2$ (ImQ_T), has been synthesized and characterized. Similar to its precedent, [Ru(6-(2-cyclohexa-2',5'-diene-1,4-dione)-2,2':6',2"-terpyridine)(2,2':6',2"-terpyridine)]$[PF_6]_2$ (TQ_T), this system has a cofacial alignment of terpyridine (tpy) ligand and quinonyl (Q) group, which facilitates an electron transfer through ${\pi}$-stacked manifold. Despite the presence of lowest-energy charge transfer transition from the Ru-based-HOMO-to-Q-based-LUMO (MQCT) predicted by theoretical calculations by using time-dependent density functional theory (TD-DFT), the experimental steady-state absorption spectrum does not exhibit such a band. The selective excitation to the Ru-based occupied orbitals-to-tpy-based virtual orbital MLCT state was thus possible, from which charge separation (CS) reaction occurred. The photo-induced CS and thermal charge recombination (CR) reactions were probed by using ultrafast visible-pump/mid-IR-probe (TrIR) spectroscopic method. Analysis of decay kinetics of Q and $Q^-$ state CO stretching modes as well as aromatic C=C stretching mode of tpy ligand gave time constants of <1 ps for CS, 1-3 ps for CR, and 10-20 ps for vibrational cooling processes. The electron transfer pathway was revealed to be Ru-tpy-Q rather than Ru-bpy-imidazol-Q.

• Journal of the Korean Chemical Society
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• v.51 no.4
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• pp.318-323
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• 2007

Electronic photofragmentation spectrum of protonated tyrosine-alanine dipeptide ions(YAH+) was obtained in the wavenumber region of 34500~36700 cm-1 using a quadrupole ion trap time-of-flight mass spectrometer (QIT-TOFMS). YAH+ ions were produced by electrospray ionization, stored in the ion trap and then irradiated by ultraviolet laser pulses which induced photofragmentation of the ions. The electronic photofragmentation spectrum was obtained by monitoring the photodissociation yields of YAH+ ions as a function of the laser wavelength. The spectrum exhibited two broad peaks which were assigned as S1 and S2 by theoretical calculations using a time-dependent density functional method. The broad widths of the peaks in the spectrum were explained by the overlaps of the peaks originated from various conformers of YAH+ ions which were present in the gas phase at room temperature and also by the contributions of the hot bands.