• 제목/요약/키워드: $\pi$-bonding

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Direct printing of organic single crystal nanowire arrays by using Liquid-bridge-mediated nanotransfer molding

  • Oh, Hyun-S.;Baek, Jang-Mi;Sung, Myung-M.
    • 한국진공학회:학술대회논문집
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    • 한국진공학회 2011년도 제40회 동계학술대회 초록집
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    • pp.473-473
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    • 2011
  • In recent years, organic thin film transistors OTFTs based on conductive-conjugated molecules have received significant attention. We report a fabrication of organic single crystal nanowires that made on Si substrates by liquid bridge-mediated nanotransfer molding (LB-nTM) with polyurethane acrylate (PUA) mold. LB-nTM is based on the direct transfer of various materials from a stamp to a substrate via a liquid bridge between them. In liquid bridge-transfer process, the liquid layer serves as an adhesion layer to provide good conformal contact and form covalent bonding between the organic single crystal nanowire and the Si substrate. Pentacene is the most promising organic semiconductors. However pentacene has insolubility in organic solvents so pentacene OTFTs can be achieved with vacuum evaporation system. However 6, 13-bis (triisopropylsilylethynyl) (TIPS) pentacene has high solubility in organic solvent that reported by Anthony et al. Furthermore, the substituted rings in TIPS-pentacene interrupt the herringbone packing, which leads to cofacial ${\pi}-{\pi}$ stacking. The patterned TIPS-Pentacene single crystal nanowires have been investigated by Atomic force microscopy (AFM), Transmission Electron Microscopy (TEM), X-Ray Diffraction (XRD), Scanning Electron Microscopy (SEM) and electrical properties.

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Engineered biochar from pine wood: Characterization and potential application for removal of sulfamethoxazole in water

  • Jang, Hyun Min;Yoo, Seunghyun;Park, Sunkyu;Kan, Eunsung
    • Environmental Engineering Research
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    • 제24권4호
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    • pp.608-617
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    • 2019
  • The adsorption of sulfamethoxazole (SMX) onto a NaOH-activated pine wood-derived biochar was investigated via batch experiments and models. Surprisingly, the maximum adsorption capacity of activated biochar for SMX (397.29 mg/g) was superior than those of pristine biochars from various feedstock, but comparable to those of commercially available activated carbons. Elovich kinetic and Freundlich isotherm models revealed the best fitted ones for the adsorption of SMX onto the activated biochar indicating chemisorptive interaction occurred on surface of the activated biochar. In addition, the intraparticle diffusion limitation was thought to be the major barrier for the adsorption of SMX on the activated biochar. The main mechanisms for the activated biochar would include hydrophobic, π-π interactions and hydrogen bonding. This was consistent with the changes in physicochemical properties of the activated biochar (e.g., increase in sp2 and surface area, but decrease in the ratios of O/C and H/C).

Efficiency Factors of Singlet Oxygen Generation from Core-Modified Expanded Porphyric : Tetrathiarubyrin in Ethanol

  • 하정현;정국영;김민선;이양훈;신구;김용록
    • Bulletin of the Korean Chemical Society
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    • 제22권1호
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    • pp.63-67
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    • 2001
  • The photophysical properties and the singlet oxygen generation efficiency of tetrathiarubyrin have been investigated to elucidate the possibility of its use as a photodynamic therapy (PDT) photosensitizer by steady-state and time-resolved spectroscopic methods. The observed photophysical properties were affected by various molecular aspects, such as extended ${\pi}conjugation$, structural distortion, and internal heavy atom. The steady-state electronic absorption spectrum was red-shifted due to the extended $\pi-conjugation$, and the spin orbital coupling was enhanced by the structural distortion and the internal heavy atom effect. As a result of the enhanced spin orbital coupling, the triplet quantum yield increased to 0.90 $\pm$ 0.10 and the triplet state lifetime was shortened to 7.0 $\pm$ 1.2 ${\mu}s$. Since the triplet state decays at a relatively faster rate, the efficiency of the oxygen quenching of the triplet state decreases. The singlet oxygen quantum yield was estimated to be 0.52 $\pm$ 0.02, which is somewhat lower than expected. On the other hand, the efficiency of singlet oxygen generation during the oxygen quenching of triplet state, $f{\Delta}^T$, is near unity. Such high efficiency of singlet oxygen generation can be explained by the following two possible factors: The hydrogen bonding of ethanol which impedes the deactivation pathway of the charge transfer complex with oxygen to the ground state, the less probability of the aggregation formation.

Coordination of an Amino Alcohol Schiff Base Ligand Toward Cd(II)

  • Mardani, Zahra;Hakimi, Mohammad;Moeini, Keyvan;Mohr, Fabian
    • 대한화학회지
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    • 제63권1호
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    • pp.29-36
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    • 2019
  • A potentially tetradentate Schiff base ligand, 2-((2-((pyridin-2-ylmethylene)amino)ethyl)amino)ethan-1-ol (PMAE), and its cadmium(II) complex, [$Cd(PMAE)I_2$] (1), were prepared and characterized by elemental analysis, FT-IR, Raman, $^1H$ and $^{13}C$ NMR spectroscopies and single-crystal X-ray diffraction. In the crystal structure of 1, the cadmium atom has a slightly distorted square-pyramidal geometry and a $CdN_3I_2$ environment in which the PMAE acts as an $N_3$-donor. In the crystal packing of the complex, the alcohol and amine groups of the coordinated ligands participate in hydrogen bonding with iodide ions and form $R^2{_2}(14)$ and $R^2{_2}(8)$ hydrogen bond motifs, respectively. In addition to the hydrogen bonds, the crystal network is stabilized by ${\pi}-{\pi}$ stacking interactions between pyridine rings. The thermodynamic stability of the isolated ligand and its cadmium complex along with their charge distribution patterns were studied by DFT and NBO analysis.

Synthesis and Structural Characterization of Main Group 15 Organometallics R3M and R(Ph)2P(=N-Ar)(M = P, Sb, Bi; R = phenanthrenyl; Ar = 2,6-iPr2-C6H3)

  • Lee, Eun-Ji;Hong, Jin-Seok;Kim, Tae-Jeong;Kang, Young-Jin;Han, Eun-Me;Lee, Jae-Jung;Song, Ki-Hyung;Kim, Dong-Uk
    • Bulletin of the Korean Chemical Society
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    • 제26권12호
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    • pp.1946-1952
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    • 2005
  • New group 15 organometallic compounds, M$(phenanthrenyl)_3$ (M = P (1), Sb (2), Bi (3)) have been prepared from the reactions of 9-phenanthrenyllithium with $MCl_3$. A reaction of 9-(diphenylphosphino)phenanthrene with 2,6-diisopropylphenyl azide led to the formation of (phenanthrenyl)${(Ph)}_2P$=N-(2,6-$^iPr_2C_6H_3$) (4). The crystal structures of 2 and 4 have been determined by single-crystal X-ray diffractions, both of which crystallize with two independent molecules in the asymmetric unit. Compound 2 shows a trigonal pyramidal geometry around the Sb atom with three phenanthrenyl groups being located in a screw-like fashion with an approximately $C_3$ symmetry. A significant amount of CH- -$\pi$ interaction exists between two independent molecules of 4. The phosphorus center possesses a distorted tetrahedral environment with P-N bond lengths of 1.557(3)$\AA$ (P(1) N) and 1.532(3)$\AA$ (P(2)-N), respectively, which are short enough to support a double bond character. One of the most intriguing structural features of 4 is an unusually diminished bond angle of C-N-P, attributable to the hydrogen bonding of N(1)-H(5A) [ca. 2.49$\AA$ between two adjacent molecules in crystal packing. The compounds 1-3 show purple emission both in solution and as films at room temperature with emission maxima ($\lambda_{max}$) at 349, 366, and 386 nm, respectively, attributable to the ligand centered $\pi$ $\rightarrow$ $\pi^\ast$ transition in phenanthrene contributed by the lone pair electrons of the Gp 15 elements. Yet the nature of luminescence observed with 4 differs in that it originates from $\pi$ (diisopropylbenzene)-$\pi^\ast$ (phenanthrene) transitions with the $\rho\pi$contribution from the nitrogen atom. The emission maximum of 4 is red-shifted ranging 350-450 nm due to the internal charge transfer from the phenanthrenyl ring to the N-arylamine group as deduced from the ab initio calculations.

항암성물질의 개발을 위한 cis-Diamminedichloroplatinum (cis-DDP) 류와 DNA base인 1-Methylcytosine의 Interaction에 관한 분자궤도함수론적 연구 (The MO Study about Interaction of cis-Diamminedichloroplatinum (cis-DDP) Complexes with DNA base, 1-Methylcytosine, for Development of Anti-Tumor Drugs)

  • 김의락;김상해
    • 대한화학회지
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    • 제34권4호
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    • pp.331-339
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    • 1990
  • cis-diamminedichloroplatinum (II)에서 아민리간드가 변화할 때, 항암성과 백금원자의 전자구조 사이의 관계를 연구하였고, 또 이러한 착물과 DNA base인 1-methylcytosine의 상호작용에 대한 메카니즘을 알기 위해서 백금(II)착물들을 분자궤도함수론적으로 연구하였다. 그 결과, 백금착물에서 중심금속의 atomic charge가 항암성에 영향을 미치고 있음을 알았다. 또한 백금착물과 1-methylcytosine의 결합은 리간드에서 금속원자로 전하이동을 하였고, 이 때 Pt(II)의 6p-orbital이 중요한 하고 있음을 발견한다. Pt-N3결합성은 $\alpha$$\pi$ 성분을 포함하고 있으며, 실험한 값과 비교할 때 비교할 때 항암성이 큰 백금착물일수록 Pt-N3 결합이 강하게 형성하고 있었다.

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Synthesis, Crystal structure, and Magnetic Properties of Dinuclear Iron(III) Complexes with Methoxo Bridges

  • Shin, Jong-Won;Han, Jeong-Hyeong;Rowthu, Sankara Rao;Kim, Bong-Gon;Min, Kil-Sik
    • Bulletin of the Korean Chemical Society
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    • 제31권12호
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    • pp.3617-3622
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    • 2010
  • The reaction of stoichiometric amount of $FeCl_2{\cdot}4H_2O$, (2-pyridylmethyl, 3-pyridylmethyl)amine (2,3-pyma) and sodium azide/sodium thiocyanate in methanol under aerobic conditions affords the dinuclear Fe(III) complexes, [(2,3-pyma) $(N_3)_2Fe({\mu}-OCH_3)_2Fe(N_3)_2$(2,3-pyma)]${\cdot}CH_3OH$ (1) and [(2,3-pyma)$(NCS)_2Fe({\mu}-OCH_3)_2Fe(NCS)_2$(2,3-pyma)] (2) in good yield. Two bis-methoxy-bridged diiron(III) complexes are isolated and characterized. The coordination geometries around iron(III) ions in 1 and 2 are the same tetragonally distorted octahedron. The iron(III) ions are coordinated by two nitrogens of a 2,3-pyma, two nitrogens of two azide/thiocyanate ions, and two oxygens of two methoxy groups. Both compounds are isomorphous. The structures of 1 and 2 display the C-$H{\cdots}\pi$ and/or $\pi-\pi$ stacking interactions as well as hydrogen bonding interactions, respectively. Compounds 1 and 2 show significant antiferromagnetic couplings through the bridged methoxy groups between the iron(III) ions in the temperature range from 5 to 300 K ($H=-2JS_1{\cdot}S_2$, J=-19.1 and $-13.9\;cm^{-1}$ for 1 and 2).

RELATION BETWEEN MICROSTRUCTURE AND SOFT MAGNETIC PROPERTIES OF Fe-TM-C-N (TM:Hf, Zr AND Nb) NANOCRYSTALLINE FILMS

  • Ryu, H.J.;Choi, J.O.;Han, S.H.;Kim, H.J.;Lee, J.J.;Kang, I.K.
    • 한국자기학회지
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    • 제5권5호
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    • pp.519-523
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    • 1995
  • The Fe-TM-C-N nanocrystalline films (TM : Hf, Zr and Nb) are investigated to examine the relation between microstructure and soft magnetic properties. In these films, as the atomic radius of TM element increases, $P_{N2}$ which was added to get good soft magnetic properties was decreased and the maximum value of the permeability shifted to the high Fe range in the composition diagram. The best soft magnetic properties achieved in these films are : Hc of 0.15 Oe, $\mu_{eff}$ of 7800 (1MHz) and $4{\pi}M_{s}$ of 17.5 kG in Fe-Hf-C-N film ; Hc of 0.06 Oe, $\mu_{eff}$ of 2750 (1MHz) and $4{\pi}M_{s}$ of 16.8 kG in Fe-Zr-C-N film and Hc of 0.31 Oe; $\mu_{eff}$ of 2100 (1MHz) and $4{\pi}M_{s}$ of 15.5 kG in Fe-Nb-C-N film. It was considered that the stronger the bonding force between TM and C(N), the finer TM(C,N) phase is precipitated and therefore, the finer $\alpha$-Fe grains are formed. The effective permeability of the Fe-Zr-C-N films and Fe-Nb-C-N films remains nearly constant up to 10 MHz.

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새로운 항균제(抗菌劑)로서 1-(phenoxymethyl)benzotriazole 유도체(誘導體)의 합성(合成)과 정량적(定量的) 구조활성관계(構造活性關係)(QSAR) 분석(分析) (Synthesis and quantitative structure-activity relationships(QSAR) analysis of 1-(phenoxymethyl) benzotriazole derivatives as new fungicide)

  • 성낙도;임치환;최우영;고동성;권기성
    • Applied Biological Chemistry
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    • 제33권3호
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    • pp.231-238
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    • 1990
  • 14종의 새로 합성된 1-(phenxymethyl)benzotriazole(I)(Y=0)과 1-(thiophenoxymethyl)benzotriazole (II)(Y=S) 및 1-(azidomethy) benzotriazole(III) 유도체의 구조와 in vitro에서 Pyricularia oryzae, Fusarium axysporum f.sp.sesami, Valsa ceratosperma 및 Botrytis cinerea에 대한 균사 생장을 50% 저해하는 활성($pI_{50}$)사이의 구조-항균활성 상관관계들을 QSAR방법으로 연구하였다. (I)의 항균활성은 (II)와 (III)보다 우세하였으며 phenoxy group(I)의 치환기 효과는 수소 결합성 (HB)과 포물선 관계의 electronic effect($\sigma$), steric effect($B_1$)그리고 hydrophobic effect($\pi$)로 설명된다. P. oryzae와 F. axysporum f.sp.sesami의 항균 활성에 대한 치환기의 적정값은 $B_1$=1.40A, (H)와 $\sigma=0.07{\sim}0.15$, (H)이고 V. ceratosperma와 B. cinerea에 대하여는 각 각 $\sigma=0.23{\sim}0.28$, (C1)과 $\pi=0.70$, (C1)이었으며 가장 호과적인 화합물인 ( I a)와 ( I d)의 구조-활성관계가 검토되었다.

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Electronic Spectroscopy and Ligand Field Analysis of $\Lambda$-fac-Tris(L-alaninato)chromium(III)

  • Choi, Jong-Ha
    • Journal of Photoscience
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    • 제3권1호
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    • pp.43-47
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    • 1996
  • The 77 K emission and excitation, and room-temperature UV-visible spectra of $\Lambda$-fac[Cr(L-ala)$_3$] (ala = alanine anion) have been measured. The ten electronic transitions due to spinallowed and spin-forbidden are assigned. With the observed electronic transition energies, ligand field optimizations have been performed to determine the bonding properties of L-alanine anion toward chromium(III). The angular overlap model (AOM) parameters obtained indicate that it is electron-donating ligand which has values of e$_{\sigma}O$, e$_{\pi}O$, and e$_{\sigma}N$ slightly lower than those of glycine anion (gly). It seem that the decrease of the ligand field properties is due to steric effect of extra methyl group and inductive effect of adjacent carbonyl group.

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