• Bulletin of the Korean Chemical Society
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• 제21권12호
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• pp.1202-1206
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• 2000

Transmission of substituent effects through 5-membered heteroaromatic rings is investigated theoretically at the RHF/6-31+G and B3LYP/6-31+G levels using the equilibria for the $OH^- addition to five-membered heteroaromatic aldehydes (5MHA). The transmission efficiency (S) in 5MHA(A) increases in the order NH>O>S>PH but the order exactly reverses in 5MHA($T^-$). This is originated by the delocalizability of the ${\pi}$ lonepair on Y, $$n_\pi$(Y)$. A better correlation is obtained with ${\sigma}_p^-$ in the Hammett plots with positive slope, $p_z$ > 0, indicating that the substituent (Z) effects are not transmitted by a direct conjugation. The magnitude of $p_z$ for Y=NH is the largest among the heteroaromatic systems, which is consistent with the largest transmission efficiency change $({\Delta}S)$. The equilibria for the addition processes are favorable in the gas phase $({\Delta}G^o<0)$, which reverses to unfavorable in aqueous solution $({\Delta}G^o>0)$ due to the relatively large salvation energy of $OH^-$ in the initial state in aqueous solution. The orders of ${\Delta}G^o$ and $p_z$ in the gas phase are almost maintained in solution.

• Bulletin of the Korean Chemical Society
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• 제32권spc8호
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• pp.2906-2910
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• 2011

A fluorescent nucleoside analogue, $^AC$, featuring two non-complementary nucleobases linked through an ethynyl group, was synthesized. The extended ${\pi}$-conjugation imparts $^AC$ with red-shifted absorbance (relative to adenine and cytosine) and pale-blue fluorescence. It spontaneously forms nanoparticles, which exhibit considerably enhanced fluorescence, without the help of any additional stabilizing agent. The DMSO/water ratio was an important factor influencing the construction of the NPs. X-ray crystallography confirmed the structure of $^AC$; dynamic light scattering and scanning electron microscopy confirmed the existence of the nanoparticles.

• Rapid Communication in Photoscience
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• 제3권3호
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• pp.42-47
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• 2014

Development of molecular and supramolecular systems showing efficient photoinduced energy or electron transfer are of current research interest due to their applications in various chemical and biological processes. Various polypyridine metal complexes including Ru(II), Ru(III), Os(II), Pt(II), Fe(II), Re(I), Ir(III) and so on as a metal center introduce for expanding some more understanding of molecular-scale photoelectronics. Their complexes are concisely classified by the types of relay ligands as follows; (a) metal-direct ligand-metal system; dinuclear or trinuclear systems, (b) metal-nonconjugated ligand-metal system and metal-nonconjugated ligand system having flexible/rigid ligand, (c) metal-conjugated ligand-metal system, and (d) conjugated ligand-metal-conjugated ligand system and metal-self assembly ligand-metal system. It is pointed out that the role played by the relay ligands is important in constructing the metal complexes.

• 한국전기전자재료학회논문지
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• 제14권2호
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• pp.133-138
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• 2001

We studied the optical properties of poly(3-hexylthiophene) for applying to the emitting material of organic electro luminescent device. The infrared spectrum and NMR of synthesized polymer gave good evidence for the conjugation of 3-hexylthiophene monomer unit. We confirmed that poly(3-hexylthiophene) contains the HT(head-to-tail)-HT(head-to-Tail) linkage larger than 65% based on NMR analysis. FTIR and raman spectroscopy show that poly(3-hexylthiophene) has two main vibration levels which have an energy about 0.18eV and 0.36eV. Electronic absorption spectra shifted to the shorter wavelength with increasing temperature, which is related to a conformational transition of the polymer. Photoluminescence spectrum generated at low temperature(10K) is separated at 669nm, 733nm and 812nm that it's because of phonon energy generated from the lattice vibration.

• Bulletin of the Korean Chemical Society
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• 제33권4호
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• pp.1225-1230
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• 2012

A new unsymmetrical zinc phthalocyanine has been designed and synthesized based on the 'push-pull' and extended ${\pi}$-conjugation concept for the dye-sensitized solar cells. Three tert-butoxy groups, which act as electron releasing ('push'), enhance the solubility of phthalocyanine in common organic solvents and reduce the aggregation. Hydroxy substituted 9,10-anthraquinones act as electron acceptors ('pull') for the study of photoinduced electron transfer processes as well as grafting onto nanocrystalline $TiO_2$. The new unsymmetrical zinc phthalocyanine was fully characterized by FTIR, UV-vis, $^1H$ NMR, cyclic voltammetry and differential pulse voltammetry. The new sensitizer was tested in dye-sensitized solar cells, and gave a better performance.

• 폴리머
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• 제25권3호
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• pp.399-405
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• 2001

Poly[3-octylthiophene-co-3-(4-fluorophenyl)thiophene]를 2:1, 1:1, 1:2의 몰 비로 공중합한 뒤 유기 발광 소자를 제작하였다. 이렇게 공중합한 고분자의 광ㆍ전기적인 특성을 PL, EL 스펙트럼과 I-V, V-L 곡선을 이용하여 조사하였고, 전자 흡수 스펙트럼과 순환 전압 전류 곡선을 이용하여 band diagram을 얻었다. P(OT/FPT)(1:1)의 경우 LUMO 값이 -3.35eV로 가장 낮았다. EL과 PL 스펙트럼에서는 fluorophenyl 기의 함량이 증가함에 따라 발광 파장이 장파장으로 이동하였으나, P(OT/FPT)(1:2)의 경우에는 단파장으로 이동하였다 이것은 fluoro-phenyl 기의 함량이 증가하여 고분자 사슬이 뒤틀리게 되어 ${\pi}$-conjugation이 깨어져 공액 길이가 짧아지는 효과를 나타냈기 때문이다. P(OT/FPT)(1:1)는 34cd/$m^2$으로 가장 우수한 휘도를 갖는 짙은 적색 발광을 하였다. 또한 발광 효율에서도 P(OT/FPT)(1:1)가 가장 우수한 것으로 나타났다. P(OT/FPT)(1:2)의 경우 필름 표면이 고르지 못하여 국부적으로 누설 전류가 흐르기 때문에 발광 효율이 낮아지는 것으로 믿어진다.

• Bulletin of the Korean Chemical Society
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• 제33권6호
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• pp.1861-1866
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• 2012

The new semiconducting copolymers with 4,4-dialkyl-$4H$-cyclopenta[2,1-$b$:3,4-$b^{\prime}$]dithiophene and 2,2-dimethyl-$2H$-benzimidazole units were synthesized. The fused aromatic rings, such as cyclopentadithiophene (CPDT) unit, can make the polymer backbone more rigid and coplanar, which induces long conjugation length, narrow band gap, and strong intermolecular ${\pi}-{\pi}$ interaction. The stacking ability was controlled through attaching of linear or branched alkyl side chains. The spectra of PEHCPDTMBI and PHCPDTMBI in the solid films show absorption bands with maximum peaks at 401, 759 and 407, 768 nm, and the absorption onsets at 925 and 954 nm, corresponding to band gaps of 1.34 and 1.30 eV, respectively. The devices comprising PHCPDTMBI with $TiO_X$ showed a $V_{OC}$ of 0.39 V, a $J_{SC}$ of 1.14 $mA/cm^2$, and a $FF$ of 0.34, giving a power conversion efficiency of 0.15%. The PHCPDTMBI with linear alkyl chain on CPDT shows good solubility in organic solvent with higher PCE value than that of PEHCPDTMBI.

• 한국신재생에너지학회:학술대회논문집
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• 한국신재생에너지학회 2011년도 춘계학술대회 초록집
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• pp.120.2-120.2
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• 2011

The improvement of solar energy-to-electricity conversion efficiency has continued to be an important research area of dye-sensitized solar cells (DSSCs). The mechanism of DSSCs is based on the injection of electrons from the photoexcited dye into the conduction band of nanocrystalline TiO2 or ZnO. Thus, the electronic structures, such as HOMO, LUMO, and HOMO-LUMO band gaps of dye moleculed in DSSC are deeply related to the electron transfer by photoexcitation and redox potential. 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 DSSC. We believe that practically useful organic dye photosensitizers can be produced by exploiting electron donor/acceptor system with proper length of ${\pi}$-conjugation in a chromophore to control the absorption wavelength and enhance the photovoltaic performance. In this research, We designed and synthesized organic dyes also investigated the photoelectrochemical properties of a series of ionic dyes in DSSCs.

• Bulletin of the Korean Chemical Society
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• 제31권8호
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• pp.2175-2179
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• 2010

Quantum mechanical properties of unsymmetrical and unfunctionalized trans-stilbene derivatives 1-3, which had been prepared by solid-phase parallel syntheses, were characterized using mPW1PW91/6-311G(d,p) (hybrid HF-DF) calculations. The total electronic energies, normal vibrational modes, Gibbs free energies, and HOMOs and LUMOs of sixteen different structures from three different groups were analyzed. The energy differences between the HOMOs and LUMOs of the various unsymmetrical trans-stilbenes are in accord with the maximum absorption peaks of the experimental UV spectra of 1-3. The calculated normal vibrational modes of 21 were comparable with its experimental IR spectrum. The $\pi$-conjugation in the para-connected biphenyl group of 2 is better than the one in the metaconnected biphenyl group on the shorter side of 3.

• Bulletin of the Korean Chemical Society
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• 제25권5호
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• pp.704-710
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• 2004

A poly(1-hexyl-3,4-dimethyl-2,5-pyrrolylene) (PHDP) was prepared and its luminescence in tetrahydrofuran (THF) was studied. When PHDP is excited by UV light, it produces very strong blue luminescence. The quantum yield of PHDP (Q = 36.9%) is much greater than that of the monomer, 1-hexyl-3,4-dimethylpyrrole (HDP) with Q = 0.61%. The principal luminescence of PHDP has a single decay component with ca. 1 ns, whereas the decay of HDP is complicated. The molecular structure and conformational behavior of HDP and the oligomers up to trimer have been also determined by ab initio Hartree-Fock (HF/6-31$G^{**}$), density functional theory (DFT-B3LYP/6-31$G^{**}$), and semiempirical (ZINDO) methods. According to the results of calculations, it is proposed that the enhanced quantum yield of the polymer PHDP results mostly from the ${\pi}$-conjugation between neighboring pyrrole rings.