• Title/Summary/Keyword: benzene-bridged

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Study on the Hydrophobicity and Mechanical Properties of Silica-Based Aerogel by Introducing Organic Benzene (벤젠 유기물 도입에 따른 실리카 기반 에어로겔의 소수성 및 기계적 특성 연구)

  • Qi, Wang;Lee, Jihun;Dhavale, Rushikesh P.;Choi, Haryeong;Kim, Taehee;Park, Hyung-Ho
    • Journal of the Microelectronics and Packaging Society
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    • v.27 no.4
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    • pp.135-141
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    • 2020
  • The silica aerogels with benzene-bridged were designed to have uniform network structure, ordered pore structure, improved mechanical properties and excellent textural properties. Adding organic to enhance the mechanical properties of silica aerogels is a common method, but textural properties of aerogels with organic are reduced due to the organic-inorganic phase separation. In this paper, we use a simple and low-cost method to increase mechanical properties while maintaining textural properties of SiO2 aerogels. Two types of benzene-bridged precursors were prepared to study the effect of the number of hydroxyl band on the textural and mechanical properties. The porous silica aerogel was prepared by a simple, cost effective and pollution-free sol-gel method. This method does not require additional silylating reagents. The benzene-bridged silica aerogel samples prepared had excellent textural properties, high specific surface area (1,326 ㎡/g), porous structure and hydrophobicity (>140°). The mechanical strength of 2T4 is more than 5 times that of pure silica aerogel.

Polymeric Membrane Cesium-Selective Electrodes Based on Quadruply-bridged Calix[6]arenes

  • Choe, Eun Mi;O, Hye Jin;Go, Seung Hwa;Choe, Yong Guk;Nam, Gye Chun;Jeon, Seung Won
    • Bulletin of the Korean Chemical Society
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    • v.22 no.12
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    • pp.1345-1349
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    • 2001
  • New quadruply-bridged calix[6]arenes (I-V) have been studied as cesium selective ionophores in poly(vinyl chloride) (PVC) membrane electrodes. PVC membranes were prepared with dioctyl sebacate (DOS) or 2-nitrophenyl octyl ether (o-NPOE) as the sol vent mediator and potassium tetrakis(p-chlorophenyl)borate as the lipophilic salt additive. These ionophores produced electrodes with near-Nernstian slope. The selectivity coefficients for cesium ion with respect to alkali, alkaline earth and ammonium ions have been determined. The lowest detection limit (logaCs+ = -6.3) and the higher selectivity coefficient (logkpotCs+,Rb+ = -2.1 by SSM, -2.3 by FIM for calix[6]arene I) for Cs+ have been obtained for membranes containing quadruply-bridged calix[6]arenes (I, Ⅱ, Ⅲ), which have no para t-butyl substituents on the bridging benzene ring.

Sonochemical Synthesis of Closed [5,6]-bridged Aziridino[70]fullerene Derivative and Self-assembled Multilayer Films

  • Yoon, Shin-Sook;Hwang, Sung-Ho;Hong, Sung-Kyu;Lee, Jeong-Ho;Ko, Weon-Bae
    • Carbon letters
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    • v.10 no.4
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    • pp.325-328
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    • 2009
  • This cycloaddition of [70]fullerene with methyl azidoacetate in benzene under ultrasonic irradiated condition afforded the closed [5,6]-bridged aziridino[70]fullerene derivative, which was unusual product of cycloaddition to the 5,6-junction of fullerene. Its structure was determined by FAB-MS, UV-vis, $^1H-$ and $^{13}C$-NMR spectral data. The closed [5,6]-bridged aziridino[70]fullerene-functionalized gold nanoparticle films were self-assembled using the layer-by-layer method on the reactive of glass slides functionalized with 3-mercaptopropyl trimethoxysilane. The functionalized glass slides were alternately soaked in the solution containing closed the [5,6]-bridged aziridino[70]fullerene and 4-aminothiophenoxide/hexanethiolate-protected gold nanoparticles. The closed [5,6]-bridged aziridino[70]fullerene-functionalized gold nanoparticle films have grown up to 5 layers depending on the immersion time. The self-assembled nanoparticle multilayer films were characterized using UV-vis spectroscopy showed that the surface plasmon band of gold at 527 nm gradually became more evident as successive layers were added to the films.

A Study on the Reactivity of Dioxygen Bridged Palladium Complexes Having Amine Ligands (아민을 리간드로 갖는 산소가교 팔라듐 착화합물의 반응성에 관한 연구)

  • Chung, Pyung-Jin
    • Applied Chemistry for Engineering
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    • v.3 no.3
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    • pp.471-481
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    • 1992
  • This study is related to the reactivity of dioxygen bridged palladium complexes having amine ligands. New dloxygen bridged palladium complexes were prepared using superoxide ion(${O_2}^-$) as an oxygen source. The reactions of dioxygen palladium complexes prepared in the study were examined in order to clarify the nature of the coordinated dioxygen. Treatments of a solution of the dioxygen bridged palladium complexes in benzene by water, methanol, acetic acid gave hydrogen peroxide($H_2O_2$) and hydroxy, methoxy, acetoxy-bridged palladium complexes, respectively. The dioxygen bridged palladium complexes reacted with substitution phenols of salicylaldehyde, 8-hydroxyquinoline and active mothylenes of acetylacetone, dimethyl malonate to afford mononuclear complexes of palladium and hydrogen peroxide. Furthermore, she dioxygen bridged palladium complexes changed to acetonyl bridged palladium complex and hydrogen peroxide reacting with acetone. The results suggest that dioxygen is coordinated as peroxo (${O_2}^{2-}$) in the complexes and behaves as a strong base.

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The Study on the Reactivity of Dioxygen Bridged Palladium Complexes Having ${\pi}$-Allyl Ligands (${\pi}$-알릴리간드를 갖는 산소가교 팔라듐착화합물의 반응성에 관한 연구)

  • Pyeong Jin Chung
    • Journal of the Korean Chemical Society
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    • v.30 no.6
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    • pp.516-520
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    • 1986
  • This study is related to reactivity of dioxygen bridged palladium complexes having ${\pi}$-allyl ligands. In this case, new dioxygen bridged palladium complexes were prepared using superoxide ion$(O_2^-)$ as an oxygen source. Reactions of the dioxygen palladium complexes prepared in the study were examined in order to clarify the nature of the coordinated dioxygen. Treatments of a solution of the dioxygen bridged palladium complexes in benzene by water, methanol and acetic acid gave hydrogen peroxide $(H_2O_2)$ as hydroxy-, methoxy-, and acetoxybridged palladium complexes, respectively. The dioxygen bridged palladium complexes reacted also with substitution phenols of salicylaldehyde, 8-hydroxyquinoline and active methylenes of acetylacetone, dimethyl malonate to afford mononuclear complexes of palladium and hydrogen peroxide. The results suggest that dioxygen is coordinated as peroxo $(O_2^{2-})$ in the complexes and behaves as a strong base.

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DFT Study for p-tert-Butylcalix[4]arene Crown Ether Bridged at the Lower Rim with Pyridyl Unit Complexed with Potassium Ion

  • Choe, Jong-In
    • Bulletin of the Korean Chemical Society
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    • v.28 no.12
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    • pp.2310-2314
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    • 2007
  • Stable molecular conformations were calculated for the p-tert-butylcalix[4]arene crown ether bridged at the lower rim with pyridyl unit (1) in the various conformers and their potassium-ion complexes. The structures of three distinct conformations have been optimized using DFT B3LYP/6-31G(d,p) method. Relative stability of free host 1 is in following order: cone (most stable) > partial-cone > 1,3-alternate conformer. For two different kinds of complexation mode, the potassium cation in the crown-ether moiety (cr) has much better complexation efficiency than in the benzene-rings (bz) pocket for all three kinds of conformation of host molecule 1. The relative stability of complex (1+K+) in the cr-binding mode is in following order: partial-cone (most stable) ~ cone > 1,3-alternate conformer.

$^{13}C-^{1}H$ Coupling Constant as a Criterion for the Presence of $\pi$ Bridging in Substituted 9-Benzonorbornenyl Cation

  • Gweon-Young Ryu;Jung-Hyu Shin
    • Bulletin of the Korean Chemical Society
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    • v.14 no.5
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    • pp.546-548
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    • 1993
  • The discrete structure of substituted 9-benzonorbornenyl cation 3a and 3c was studied using the empirical ${\Delta}$J equation which was developed by Kelly and coworker$^5$. The ${\Delta}$J values of substituted 9-benzonorbornenyl cations were obtained from p-methyl-6,7-dimethyl benzonorbornen-9-yl (3a) and 9-methyl-6,7-dimethyl benzonorbonen-9-yl (3c) cations under stable ion conditions, and were compared with those of the corresponding ketone analog; these cations were generated by dissolving the corresponding carbinols in superacid at -120$^{\circ}$C and the nmr spectra taken at -60$^{\circ}$C~-90$^{\circ}$C. The ${\Delta}$J values are 8.7 Hz for the bridgehead carbons in cation 3c and 3.1 Hz for cation 3b. The ${\Delta}$J values at C5,8 in fused benzene ring are 14.3 Hz for cation 3c and 8.7 Hz for cation 3a. The excellent correlation of the ${\Delta}$J values with 1$^9F$ chemical shifts of p-fluorophenyl-6,7-dimethylbenzonorbornenyl cation (3d) indicate that ${\Delta}$J value is a reliable probe to charge density at adjacent cationic carbon. These NMR parameters strongly support that the symmetrically ${\pi}$-bridged nonclassical structure (type 2) of substituted 9-benzonorbornenyl cations in stable ion conditions.

Preparation and Characterization of Dinuclear Metal Complexes, $[(PPh_3)_2(CO)M({\mu}-E)M(CO)(PPh_3)_2](SO_3CF_3)_2$ (M = Rh, Ir; E = 1,4-Dicyanobenzene and 1,4-Dicyano-2-butene)

  • Moonsik Kim;JaeKyun Chin;Jaejung Ko
    • Bulletin of the Korean Chemical Society
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    • v.13 no.5
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    • pp.556-559
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    • 1992
  • Hydrocarbon solution of $(PPh_3)_2(CO)MOSO_2CF_3$ (M= Rh, Ir) reacts rapidly with 1,4-dicyanobenzene or 1,4-dicyano-2-butene to yield dinuclear metal complexes $[(PPh_3)_2(CO)M({\mu}-dicyanobenzene)M(CO)(PPh_3)_2](SO_3CF_3)_2$ (I: M = Rh; II: M = Ir) or $[(PPh_3)_2(CO)M({\mu}-dicyano-2-benzene)M(CO)(PPh_3)_2](SO_3CF_3)_2$ (III: M = Rh; IV: M = Ir), respectively. Compounds I, II, III, and IV were characterized by $^1H$-NMR, $^{31}P$-NMR, and infrared spectrum. Dichloromethane solution of II and IV reacts with $H_2\;and\;I_2$ to yield oxidative addition complexes $[(PPh_3)_2(CO)IrX_2({\mu}-E)X_2Ir(CO)(PPh_3)_2](SO_3CF_3)_2$ (V; E = 1,4-dicyanobenzene, $X_2$ = $H_2$; VI : E = 1,4-dicyano-2-butene, $X_2$ = $H_2$; VII; E = 1,4-dicyanobenzene, $X_2$ = $I_2$). All metal complexes are bridged by the cyanide groups. Compounds Ⅴ, Ⅵ, and Ⅶ are characterized by conventional methods.