• Bulletin of the Korean Chemical Society
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• 제32권9호
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• pp.3290-3294
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• 2011

The properties of monomeric and dimeric salen-aluminum complexes, [salen(3,5-$^tBu)_2$Al(OR)], R = $OC_6H_4-p-C_6H_6$ (H1) and R = [salen(3,5-$^tBu$)AlOPh]C$(CH_3)_2$ (H2) (salen = N,N'-bis-(salicylidene)-ethylenediamine) as host layer materials in red phosphorescent organic light-emitting diodes (PhOLEDs) were investigated. H1 and H2 exhibit high thermal stability with decomposition temperature of 330 and $370^{\circ}C$. DSC analyses showed that the complexes form amorphous glasses upon cooling of melt samples with glass transition temperatures of 112 and $172^{\circ}C$. The HOMO (ca. -5.2~-5.3 eV) and LUMO (ca. -2.3~-2.4 eV) levels with a triplet energy of ca. 1.92 eV suggest that H1 and H2 are suitable for a host material for red emitters. The PhOLED devices based on H1 and H2 doped with a red emitter, $Ir(btp)_2$(acac) (btp = bis(2-(2'-benzothienyl)-pyridinato-N,$C^3$; acac = acetylacetonate) were fabricated by vacuum-deposition and solution process, respectively. The device based on vacuum-deposited H1 host displays high device performances in terms of brightness, luminous and quantum efficiencies comparable to those of the device based on a CBP (4,4'-bis(Ncarbazolyl) biphenyl) host while the solution-processed device with H2 host shows poor performance.

• Bulletin of the Korean Chemical Society
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• 제35권12호
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• pp.3590-3594
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• 2014

Blue phosphorescent $(dfpypy)_2Ir(mppy)$, where dfpypy = 2',6'-difluoro-2,3'-bipyridine and mppy = 5-methyl-2-phenylpyridine, has been synthesized by newly developed effective method and its solid state structure and photoluminescent properties are investigated. The glass-transition and decomposition temperature of the compound appear at $160^{\circ}C$ and $360^{\circ}C$, respectively. In a crystal packing structure, there are two kinds of intermolecular interactions such as hydrogen bonding ($C-H{\cdots}F$) and edge-to-face $C-H{\cdots}{\pi}(py)$ interaction. This compound emits bright blue phosphorescence with ${\lambda}_{max}=472nm$ and quantum efficiencies of 0.23 and 0.32 in fluid and the solid state. The emission band of the compound is red-shifted by 40 nm relative to homoleptic congener, $Ir(dfpypy)_3$. The ancillary ligand in $(dfpypy)_2Ir(mppy)$ has been found to significantly destabilize HOMO energy, compared to $Ir(dfpypy)_3$, $(dfpypy)_2Ir(acac)$ and $(dfpypy)_2Ir(dpm)$, without significantly changing LUMO energy.

• Bulletin of the Korean Chemical Society
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• 제31권9호
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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.

• Bulletin of the Korean Chemical Society
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• 제35권10호
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• pp.3052-3058
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• 2014

In this article, we have designed and synthesized a novel donor-${\pi}$-acceptor (D-${\pi}$-A) type porphyrin-based sensitizer (denoted UI-5), in which a carboxyl anchoring group and a 9,9-dimethyl fluorene were introduced at the meso-positions of porphyrin ring via phenylethynyl and ethynyl bridging units, respectively. Long alkoxy chains in ortho-positions of the phenyls were supposed to reduce the degree of dye aggregation, which tends to affect electron injection yield in a photovoltaic cell. The cyclic voltammetry was employed to determine the band gap of UI-5 to be 1.41 eV based on the HOMO and LUMO energy levels, which were estimated by the onset oxidation and reduction potentials. The incident monochromatic photon-to-current conversion efficiency of the UI-5 DSSC assembled with double-layer (20 nm-sized $TiO_2$/400 nm-sized $TiO_2$) film electrodes appeared lower upon overall ranges of the excitation wavelengths, but exhibited a higher value over the NIR ranges (${\lambda}$ = 650-700 nm) compared to the common reference sensitizer N719. The UI-5-sensitized cell yielded a relatively poor device performance with an overall conversion efficiency of 0.74% with a short circuit photocurrent density of $3.05mA/cm^2$, an open circuit voltage of 0.54 mV and a fill factor of 0.44 under the standard global air mass (AM 1.5) solar conditions. However, our report about the synthesis and the photovoltaic characteristics of a porphyrin-based sensitizer in a D-${\pi}$-A structure demonstrated a significant complex relationship between the sensitizer structure and the cell performance.

• Bulletin of the Korean Chemical Society
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• 제35권2호
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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 Electrochemical Science and Technology
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• 제8권1호
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• pp.43-52
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• 2017

In this paper, for the first time, the electroanalytical study of Triethylenediamine, TEDA was done on a typically graphene modified carbon paste electrode (Gr/CPE) in pH=10.5 of phosphate buffer solutions (PBS). The surface morphology of the bare and modified electrodes was characterized by scanning electron microscopy (SEM), electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV). The electro-oxidation of TEDA was investigated at the surface of modified electrode. The results revealed that the oxidation peak current of TEDA at the surface of Gr/CPE is 2.70 times than that shown at bare-CPE. A linear calibration plot was observed in the range of 1.0 to 202.0 ppm. In this way, the detection limit was found to be 0.18 ppm. The method was then successfully applied to determination of TEDA in aqueous samples obtained from two kinds of activated carbon from the masks of war. On the other hand, density functional theory (DFT) method at B3LYP/6-311++G** level of theory and a conductor-like Polarizable Continuum Model (CPCM) was used to calculate the $pK_a$ values of TEDA. The energies of lowest unoccupied molecular orbital ($E_{LUMO}$) and highest occupied molecular orbital ($E_{HOMO}$), gap energy (${\Delta}E$) and some thermodynamic parameters such as Gibbs free energy of TEDA and its conjugate acid ($HT^+$) were calculated. The results of calculated $pK_a$ were found to be in good agreement with the experimental values.

• Bulletin of the Korean Chemical Society
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• 제32권7호
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• pp.2279-2285
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• 2011

The geometries, electronic structures and absorption spectra of the two organic triphenylamine-based dyes TA-St-CA and TA-DM-CA, containing identical electron donors and acceptors but the different conjugated bridges, were studied by density functional theory (DFT) at the B3LYP and PBE1PBE levels, respectively. The influence of para-orientating methoxyl units on the electronic structures and light absorption properties of the dyes and the consequent photovoltaic performance of the dye-sensitized solar cells (DSSCs) were investigated in detail. The results indicate that the introduction of the para-orientating methoxyl units into the conjugated bridge induces the increased absorption wavelength as well as the more negative EHOMO corresponding to the bigger driving force $(E_{I^-/I^-_3}-E_{HOMO})$ for dye reduction, which together improve the photovoltaic performance of TA-DM-CA, although there is a decline of the open circuit voltage caused by the more negative $E_{LUMO}$.

• 한국재료학회지
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• 제28권1호
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• pp.68-74
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• 2018

Cobalt-incorporated zeolitic imidazolate framework ZIF-8 was synthesized by a simple one-pot synthesis method at room temperature. Powder X-ray diffraction patterns and energy dispersive X-ray spectrum confirmed the formation of the bimetallic Co/Zn-ZIF structure. UV-Vis diffuse reflectance spectra revealed that the bimetallic ZIF had a lower HOMO-LUMO gap compared with ZIF-8 due to the charge transfer process from organic ligands to cobalt centers. A hydrolytic stability test showed that Co/Zn-ZIF is very robust in aqueous solution - the most important criterion for any material to be applied in photodegradation. The photocatalytic efficiency of the synthesized samples was investigated over the Indigo Carmine (IC) dye degradation under solar simulated irradiation. Cobalt incorporated ZIF-8 exhibited high efficiency over a wide range of pH and initial concentration. The degradation followed through three distinct stages: a slow initial stage, followed by an accelerated stage and completed with a decelerated stage. Moreover, the photocatalytic performance of the synthesized samples was highly improved in alkaline environment rather than in acidic or neutral environments, which may have been because in high pH medium, the increased concentration of hydroxyl ion facilitated the formation of hydroxyl radicals, a reactive species responsible for the breaking of the Indigo Carmine structure. Thus, Co/Zn-ZIF is a promising and green material for solving the environmental pollution caused by textile industries.

• Advances in nano research
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• 제12권1호
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• pp.25-35
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• 2022

Within the framework of the density functional theory combined with the method of non-equilibrium Green's functions (DFT + NEGF), the features of electron transport in fullerene nanojunctions, which are «core-shell» nanoobjects made of a combination of fullerenes of different diameters C₂₀, C₈₀, C₁₈₀, placed between gold electrodes (in a nanogap), are studied. Their transmission spectra, the density of state, current-voltage characteristics and differential conductivity are determined. It was shown that in the energy range of -0.45-0.45 eV in the transmission spectrum of the "Au-C₁₈₀-Au" nanojunction appears a HOMO-LUMO gap with a width of 0.9 eV; when small-sized fullerenes C₂₀, C₈₀ are intercalation into the cavity C₁₈₀ the gap disappears, and a series of resonant structures are observed on their spectra. It has been established that distinct Coulomb steps appear on the current-voltage characteristics of the "Au-C₁₈₀-Au" nanojunction, but on the current-voltage characteristics "Au-C₈₀@C₁₈₀-Au", "Au-(C₂₀@C₈₀)@C₁₈₀-Au" these step structures are blurred due to a decrease in Coulomb energy. An increase in the number of Coulomb features on the dI/dV spectra of core-shell fullerene nanojunctions was revealed in comparison with nanojunctions based on fullerene C₆₀, which makes it possible to create high-speed single-electron devices on their basis. Models of single-electron transistors (SET) based on fullerene nanojunctions "Au-C₁₈₀-Au", "Au-C₈₀@C₁₈₀-Au" and "Au-(C₂₀@C₈₀)@C₁₈₀-Au" are considered. Their charge stability diagrams are analyzed and it is shown that SET based on C₈₀@C₁₈₀-, (C₂₀@C₈₀)@C₁₈₀- nanojunctions is output from the Coulomb blockade mode with the lowest drain-to-source voltage.

• 공업화학
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• 제22권1호
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• pp.15-20
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• 2011

2,3-Dimethyl-5,8-dithiophen-2-yl-quinoxaline을 기본 골격으로 한 poly[2,3-dimethyl-5,8-dithiophene-2-yl-quinoxaline-alt-9,9-dihexyl-9H-fluorene] (PFTQT)과 poly[2,3-dimethyl-5,8-dithiophene-2-yl-quinoxaline-alt-10-hexyl-10H-phenothiazine] (PPTTQT)을 Suzuki coupling법을 이용하여 중합 하였다. 합성된 고분자들은 chloroform, chlorobenzene, o-dichlorobenzene, tetrahydrofuran (THF), toluene과 같은 유기용매에 대한 용해도가 우수하였고, PFTQT의 최대흡수파장과 밴드 갭은 각각 440 nm와 2.30 eV이고, PPTTQT의 경우는 각각 445 nm와 2.23 eV이었다. PFTQT의 HOMO 및 LUMO 에너지준위는 -6.05와 -3.75 eV이고, PPTTQT의 경우는 각각 -5.89와 -3.66 eV이었다. 합성된 고분자들과 전자 받개 물질인 (6)-1-(3-(methoxycarbonyl)-{5}-1-phenyl[5,6]-fullerene (PCBM)을 1 : 2의 중량비로 블렌딩하여 제작한 태양전지의 효율은 AM (air mass) 1.5 G, 1 sun 조건($100mA/cm^2$)에서 PFTQT는 0.24%, PPTTQT의 경우는 0.16%로 측정되었다. 그리고 소자의 단락전류 밀도($J_{sc}$), FF (fill factor)와 개방전압($V_{oc}$)은 PFTQT의 경우 각각 $0.97mA/cm^2$, 29%, 0.86 V이며, PPTTQT의 경우 각각 $0.80mA/cm^2$, 28%, 0.71 V이었다.