• Bulletin of the Korean Chemical Society
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• v.18 no.1
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• pp.66-70
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• 1997

The polymerization of 4, 4-bis(acetoxymethyl)-1, 6-heptadiyne (BAH) was carried out by MoCl5 and WCl6 with various organometallic cocatalysts. MoCl5-based catalysts were more effective than WCl6-based ones for the cyclopolymerization of BAH. Poly(BAH) was characterized to have polymer backbone with conjugated double bond and cyclic structure by IR, UV-visible, and 1H-and 13C NMR spectroscopies. The polymer was stable up to 310 ℃ and 5 % weight loss show up at 350 ℃. The resulting dark violet polymer exhibited good solubility in common organic solvents and could be cast on a glass plate to give film with good mechanical properties. It was found that oxygen permeability (PO2) and permselectivity (PO2/PN2) of the resulting polymer were 15.2 barrer and 2.84, respectively.

• Bulletin of the Korean Chemical Society
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• v.2 no.3
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• pp.105-112
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• 1981

Various $3{\alpha}$, $5{\alpha}$-cyclocholestan-6${\beta}-yl$ ethers were synthesized from solvolysis reactions of cholesteryl tosylate. ${3\alpha}$, $5{\alpha}$-Cyclocholestan-6${\beta}-yl$ sulfides were the sole products when cholesteryl tosylate was solvolyzed in thiol solvents. Diol solvolysis products were derivatized to aromatic esters, and nuclear magnetic resonance spectroscopic method was used to show that aromatic rings can approach C-18 methyl group and the side chain.

• Bulletin of the Korean Chemical Society
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• v.3 no.1
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• pp.5-9
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• 1982

Reactions of cobalt(II) chloride with 2,2'-dipyridylamine (dpa) in alcoholic solutions afford the complex of octahedral $Co(dpa)_2Cl_2{\cdot}CH_3OH$. The octahedral complex is converted to tetrahedral $Co(dpa)Cl_2$ in certain solvents or at the elevated temperature, and the tetrahedral complex is changed to the octahedral one with added dpa. The electronic spectra of the complexes in DMF, measured with various concentrations of 2,2'-dipyridylamine, establish the equilibrium; $td-Co(dpa)Cl_2+dpa_\rightleftarrows^Koh-Co(dpa)_2Cl_2$. The equilibrium constants determined by the analysis of the visible spectra are 6.4, 3.6 and 2.0 $M^{-1}$, respectively, at 25.5, 38.0 and $49.0^{\circ}C,\;with\;{\Delta}H^{\circ}\;and\;{\Delta}S^{\circ}$being -9.5 kcal/mole and -28 eu.

• Bulletin of the Korean Chemical Society
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• v.12 no.6
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• pp.705-708
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• 1991

Novel polysilamethylenosilanes (PSMS) were prepared by Wurtz type co-condensation of various mixtures of 2,4,4,6-tetrachloro-2,6-dimethyl-2,4,6-trisilahept ane (TSH) and dimethyldichlorosilane (D). When TSH was incorporated more than 25 mole%, PSMS polymers were soluble in common organic solvents probably due to the polycarbosilane linkage brought from TSH. The molecular weights of the polymer were measured by gel permeation chromatography and showed higher molecular weight with high TSH content. The thermal gravimetric residues increased as TSH contents increased. These properties suggested that PSMS polymers could be useful as ceramic precursors for silicon carbide.

• Bulletin of the Korean Chemical Society
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• v.18 no.7
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• pp.730-733
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• 1997

Monofluoroiron(Ⅲ) tetraphenylporphyrin, Fe(TPP)F, and difluoroiron(Ⅲ) tetraphenylporphyrin, [Fe(TPP)F2]- were generated in a various non-aqueous solvents by the reaction between Fe(TPP)Cl and tetrabutylammonium fluoride TBAF 3H2O. Formation of the these complexes was detected by the appearance of the ν(F-Fe) (ν, stretching vibration) at 506 cm-1 for Fe(TPP)F and the ν(F-Fe-F) at 448 cm-1 for [Fe(TPP)F2]-, simultaneously, with 441.6 nm excitation by Resonance Raman (RR) spectroscopy. These assignments were confirmed by observed frequency shifts due to 56Fe/54Fe and TPP/TPP-d8/TPP-N15 isotopic substitutions. Difluoroiron complex is an iron(Ⅲ) high-spin complex with the oxidation sensitive band at 1347 cm-1 for ν4 and core size/spin state sensitive band at 1541 cm-1 for ν2.

• Bulletin of the Korean Chemical Society
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• v.19 no.7
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• pp.738-742
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• 1998

A new polyamide was prepared from 4,4'-(hexafluoroisopropylidene)di-aniline and 4-[NN-bis(2-carboxyethyl)] amino-4'-nitrostilbene. This polymer was cast into thin films by spin coating cyclohexanone solution. After being poled, the electro-optic coefficients of electrode poled polymer films were measured by the reflection measurement technique using an incident laser beam of 1.3 Jim. The film poled at the field strength of 1.2 V/μm exhibited the electro-optic coefficient (r33) of 5.9 pm/V. The relaxation behavior of the poled polymer film was compared with other reported polymers bearing the same NLO chromophores. Due to stiff and highly polar nature of the backbone and also due to formation of interchain hydrogen bonds, this polymer reveals a slower relaxation characteristics. The polymer is amorphous and soluble in various organic solvents.

• Bulletin of the Korean Chemical Society
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• v.16 no.10
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• pp.972-976
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• 1995

A trace amount of 4-biphenylcarboxylate having a pre-twisted biphenyl moiety was attached to a poly(methyl methacrylate) side chain and the fluorescence properties of the chromophore were investigated in various solvents such as ethyl acetate and butyl chloride. At room temperature, the polymer exhibited a distinct red shift of the short wavelength emission (325 nm) and an enhanced emission intensity around 430 nm upon excitation at the absorption red edge. The temperature dependence of the intensity ratio (R) of the 325 nm emission to the 430 nm emission was observed when exciting at the red edge over the temperature range between -20 and 60 ℃. However, the temperature dependence was not observed when exciting at the shorter wavelength. The Arrhenius plot of the R value shows the activation energy of 6.0 kJ/mol which is in good agreement with the energy required for the twist of the biphenyl moiety. Together with the results of red edge excitation effects it was concluded that the pre-twisted geometry of the biphenyl moiety is preserved by the restriction of the polymer chain to facilitate the formation of the twisted intramolecular charge transfer (TICT) state upon excitation.

• Bulletin of the Korean Chemical Society
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• v.15 no.5
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• pp.374-378
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• 1994

Square planar nickel(II) complexes with various 1-alkyl derivatives of the 14-membered pentaaza macrocycle 8-methyl-8-nitro-1,3,6,10,13-pentaazacyclotetradecane can be readily prepared by two-step metal template condensation reactions of ethylenediamine, nitroethane, formaldehyde, and appropriate primary alkylamines. In coordinating solvents the nickel (II) complexes form octahedral species containing two axially coordinated solvent molecules and thus show square planar-octahedral equilibrium. The properties of the pentaaza macrocyclic complexes are considerably different from those of the complexes of analogous hexaaza and tetraaza macrocyclic complexes. Synthesis, characterization, and spectroscopic and chemical properties of the new complexes are described.

• Bulletin of the Korean Chemical Society
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• v.16 no.6
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• pp.518-523
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• 1995

New square planar nickel(Ⅱ) complexes with various 1-alkyl (4a-4c) and 1-hydroxyalkyl (4d-4f) derivatives of the 14-membered pentaaza macrocycle 8-ethyl-8-nitro-1,3,6,10,13-pentaazacyclotetradecane have been synthesized by two-step metal template condensation reactions of ethylenediamine, nitroethane, formaldehyde, and appropriate primary amines. The nitro group and/or hydroxyl group of 4a-4f are not directly involved in the coordination. The nickel(Ⅱ) complexes exist in coordinating solvents such as MeCN, Me2SO, and H2O as equilibrium mixtures of the square planar [Ni(L)]2+(L=4a-4f) and octahedral species [Ni(L)S2]2+(S=solvent molecule). Although the ligand field strength and redox potentials of the complexes are not affected by the nature of the substituents, the formation of octahedral species for 4d-4f in MeCN is strongly restricted by the hydroxyl group. Synthesis, characterization, and solution behaviors of the nickel(Ⅱ) complexes are described.

• Bulletin of the Korean Chemical Society
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• v.13 no.6
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• pp.625-627
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• 1992

This article deals with the synthesis and characterization of poly [N-(propargyloxy)phthalimide][poly (POPI)]. The polymerization of POPI was carried out by various transition metal catalysts. $MoCl_5$-based catalysts were found to be more effective than $WCl_6$-based catalysts. However, the polymer yield was relatively low (maximum 35%). The polymerization of POPI by $PdCl_2$ gave poly (POPI) in fair yields in DMF and pyridine. The resulting poly (POPI)s were mostly insoluble in organic solvents. The infrared spectrum of poly (POPI) showed no peak at 2135 $cm^{-1}$ due to acetylenic $C{\equiv}C$ stretching frequency. Instead, the carbon-carbon double bond stretching frequency was observed at 1600-1650 $cm^{-1}$. The TGA thermogram showed that the present poly (POPI) is thermally stable up to $160^{\circ}C.$.