• Bulletin of the Korean Chemical Society
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• 제17권6호
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• pp.564-567
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• 1996

• Bulletin of the Korean Chemical Society
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• 제26권12호
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• pp.1969-1974
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• 2005

Composite systems of $Eu(phen)_2Cl_3{(H_2O)}_2$, Eu(DN-bpy)$(phen)Cl_3{(H_2O)}_2$ and Eu(DB-bpy)$(phen)Cl_3{(H_2O)}_2$ (DNbpy: $4,4^\prime$-Dinonyl-$2,2^\prime$-dipyridyl; DB-bpy: $4,4^\prime$-Di-tert-butyl-$2,2^\prime$-dipyridyl) with crown ethers of Benzo-15-crown-5 (B15C5), Benzo-18-crown-6 (B18C6), 18-crown-6 (18C6), Dibenzo-18-crown-6 (DB18C6) and Dibenzo-24-crown-8 (DB24C8) were fabricated successfully and characterized by using photoluminescent spectroscopy and luminescent lifetime measurements. All composites formed show high luminescence mainly in red region. It was found that the heterocyclic ligands such as phen, DN-bpy and DB-bpy as well as the crown ethers have great influences on the photoluminescent properties of $Eu^{3+}$ ion. The environment around $Eu^{3+}$ ion in the composite systems changes greatly,presumably the variation of the first coordination sphere. The $Eu^{3+}$ ion occupies higher symmetrical environment and in more than one kind of symmetrical site in the composite systems studied in this work.

• Bulletin of the Korean Chemical Society
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• 제19권2호
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• pp.207-211
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• 1998

Potentiometric characteristics of DOS plasticized PVC-based membranes containing upper-rim calix[4]crown neutral carrier to various metal cations and protonated alkylamines have been examined. Although the calix[4]crown-based membrane electrodes exhibited substantial emf responses to alkali and alkaline earth metal cations, their high detection limits (- log[Cs+]=4.5) and sub-Nernstian response slopes (48 mV/pCs+) to the most selective cation, cesium, indicate that the metal cation complexing ability of calix[4]crown is much weaker than that of macrocyclic crown ethers. However, the calix[4]crown-based membrane electrodes exhibited near-Nernstian response slopes (56 mV/decade for hexylNH3+) with low detection limits (log[hexylNH3+]= - 6.7) to most alkylammonium ions compared to those of blank (DOS plasticized PVC membrane with no ionophore) or crown ether-based membranes. While the selectivity patterns of blank and crown ether-based membranes are determined primarily by the lipophilicity of alkylammonium ions, the membranes doped with calix[4]crown ionophore could effectively discriminate the steric shapes of nonpolar alkyl groups of alkylammonium ions.

• Bulletin of the Korean Chemical Society
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• 제24권5호
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• pp.674-676
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• 2003

• 대한약학회:학술대회논문집
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• 대한약학회 2001년도 Proceedings of International Convention of the Pharmaceutical Society of Korea
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• pp.280.2-280.2
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• 2001

• Bulletin of the Korean Chemical Society
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• 제11권4호
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• pp.276-281
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• 1990

The equivalent conductance of univalent cation (potassium, silver, thallium and ammonium) perchlorates in methanol containing 18-membered crown ethers, 18-crown-6 (18C6) and 1,10-dithia-18-crown-6 (DT18C6) were measured at different temperatures. The equivalent conductances of ammonium perchlorate were increased by increasing content of DT18C6 exceptionally, due to more favorable solvations than complexations. From the equivalent conductance changes, the formation constants for 1:1 compmlexes have been determined, and the values of enthalpy and entropy changes have been calculated. The complexations of 18C6 and DT18C6 with the univalent cations under investigation are all exothermic and the ${\Delta}$S values are all negative and no considerable differences around 50 J/ (k mol). The selectivity order of 18C6 is $K^+ > Tl^+ > Ag^+ > NH_4^+$, while that of DT18C6 is $Ag^+ > Tl^+ > NH_4^+ > K^+$. By sulfur substitutions in 18C6 result in significant decrease in stability, but the stability of $Ag^+$-DT18C6 complex are $10^4$ times larger than those of $K^+$. This increase of stabilities for $Ag^+$-DT18C6 complex are primary due to the result of favorable exothermic heat of reaction between the polarizable soft cation and soft sulfur centers. In NMR experiment, the stepwise additions of cation perchlorates into crown ether solutions induced two major spectral changes. First, the resonance all shift down field and the cation induced shifts were linear up to 1:1 cation/crown ratio, above which no further changes were observed. On the basis of these results, it could be concluded that 1:1 complex is formed. Second, the magnitudes of cation induced shifts were different each other in same ligand. By addition of silver ion to the solution of DT18C6, the largest shift of proton peak near the sulfur atom was observed. These effects are also arisen from the results of covalent bonding between "soft-soft" interactions.

• 대한화학회지
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• 제58권2호
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• pp.193-197
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• 2014

Dibenzo-18-crown-6, dibenzo-21-crown-7 and dihydroxy dibenzo-18-crown-6 were synthesized by Bayer-Villiger oxidation strategy. Dibenzo-18-crown-6 and dibenzo-21-crown-7 could be synthesized through a three-step protocol starting from salicylaldehyde. Salicylaldehyde was reacted with bis-(2-chloroethyl)ether using $K_2CO_3$ in acetonitrile to link the two phenolic groups with the oxyethylene bridge followed by conversion of the formyl group to the hydroxy group via a Baeyer-Villiger reaction and finally linking the two phenolic group with appropriate oxyethylene bridge. The two target crown ethers were obtained in overall yield, 24% and 30%, respectively. This method has a great potential for synthesis of symmetrical as well as unsymmetrical dibenzo crowns with varying oxyethylene bridges. Baeyer-Villiger oxidation could be used to prepare dihydroxy derivative of dibenzo-18-crown-6 through acetylation of dibenzo-18-crown-6 followed by Baeyer-Villiger oxidation. The Baeyer-Villiger oxidation could be substantially accelerated using trifluoroacetic acid.

• 한국응용과학기술학회지
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• 제22권1호
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• pp.50-55
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• 2005

A comparison of alkali metal cation and alkaline earth cation solvent extraction was made for three additional monoionizable crown ethers and one diionizable crown ether. sym-(n-Octyldibenzo)-16-crown-5-oxyacetic acid $\underline{1}$ exhibited high efficiency and selecvity in solvent extraction of alkali metal cations with respect to that observed with alkaline earth cations. Sizes of $Na^+$ and $Ca^{2+}$ appropriately match with the cavity size of monoethyl sym-bis[4(5)-tert-butylbenzo]-16-crown-5-oxymethylphosphonic acid $\underline{3}$. As the result, $Na^+$ and $Ca^{2+}$ are the best extracted. sym-(n-Octyldibenzo)-16-crown-5-oxymethyldiphosphonic acid $\underline{4}$was found to be somewhat selective for $Na^+$ over $Li^+$ and other alkaline earth metal cations. In the complexation of alklaine earth cations by crown ether diphosphonic acid $\underline{4}$, $Ca^{2+}$ and $Sr^{2+}$ are the appropriate sizes, but lager $Ba^{2+}$ may be due to favorable formation of a sandwich type complex between the crown ether cavity and the dianion of the deprotonated crown ether phoaphonic acid moiety.

• Bulletin of the Korean Chemical Society
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• 제35권9호
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• pp.2723-2725
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• 2014

Recently we have reported a novel class of anion receptors which are based on 2n-crown-n topology. Trioxane derivatives are capable of anion sensing through pure aliphatic C-H hydrogen bonding. In this work, we highlight another interesting property, i.e., they can also recognize cations as normal crown ethers (3n-crown-n topology). Since the same functional moiety can recognize anions and cations, these coronands are predicted to be amphi-ionophores. However, we could not detect cations even in the gas phase. Considering trioxane is analogous to [$1_6$]starand, this was rather counter-intuitive. The calculation results show that these coronands can detect alkali metals with very low affinity. The low affinity toward cations should be responsible for this failure of experimental detection. With careful theoretical study, we found that this low affinity toward cations could be explained by the unfavorable charge-dipolar moiety orientations as proposed by Cui et al. As in the case of [$1_6$]starand, this is an example that underscores the importance of charge-dipolar moiety orientation in supramolecular interactions.

• Bulletin of the Korean Chemical Society
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• 제33권10호
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• pp.3497-3500
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• 2012