• Bulletin of the Korean Chemical Society
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• v.28 no.8
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• pp.1256-1260
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• 2007

Two β-diketone derivatives bearing triphenylene (1-naphthalene-2-yl-3-triphenylen-2-yl-propane-1,3-dione (NTPD)) and naphthalene (1,3-di-naphthalene-2-yl-propane-1,3-dione (DNPD)) and their Ln(III) complexes (Ln = Er or Gd) were synthesized and their photophysical properties were investigated. The sensitized emission of Er3+ ion in Er3+-[NTPD]3(terpy) and Er3+-[DNPD]3(terpy) was observed upon excitation at absorption maximum of ligands. Their photophysical studies indicate the sensitization of Er3+ luminescence by energy transfer through the excited triplet state of β-diketone ligand. The energy transfer rate through the excited triplet state of β-diketone ligand to Er3+ ion occurs faster than that of the oxygen quenching rate.

• Bulletin of the Korean Chemical Society
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• v.31 no.5
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• pp.1283-1288
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• 2010

A novel polyaminopolycarboxylate ligand with many coordination sites, N,N,$N^1,N^1,N^2,N^2$-[( 2,4,6-tri(aminomethyl)-pyridine]hexakis(acetic acid) (TPHA), was designed and synthesized and its lanthanide complexes $Na_6Tb_2$(TPHA)$Cl_6{\cdot}14H_2O$, $Na_6Eu_2$(TPHA)$Cl_6{\cdot}8H_2O$, $Na_6Gd_2$(TPHA)$Cl_6{\cdot}11H_2O$ and $Na_6Sm_2$(TPHA)$Cl_6{\cdot}9H_2O$ were successfully prepared. The ligand and the complexes were characterized by elemental analysis, IR, mass, NMR and TG-DTA. The TG-DTA studies indicated that the complexes had a high thermal stability, whose initial decomposition temperature was over $270^{\circ}C$. The luminescence properties of the complexes in solid state were investigated and the results suggested that $Tb^{3+}$ and $Eu^{3+}$ ions could be sensitized efficiently by the ligand, especially the Tb(III) complex displayed a very strong luminescence intensity (> 10000) and only displayed characteristic metal-centered luminescence. Also, the correlative comparison between the structure of ligand and luminescence properties showed how the number of the coordination atoms of ligand can be a prominent factor in the effectiveness of ligand-to-metal energy transfer.

• Bulletin of the Korean Chemical Society
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• v.34 no.11
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• pp.3488-3490
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• 2013

• Bulletin of the Korean Chemical Society
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• v.30 no.7
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• pp.1553-1558
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• 2009

A series of Eu(III) complexes with various neutral ligands (2,2’:6’,2"-terpyridine (T), diglyme (D), 1N-(2-dimethylamino) ethyl)-1N, 2N, 2N-trimethylethane-1,2-diamine (PT), di-(2-picolyl)-amine derivative (HT), and multidentate terpyridine derivative (DT)) were synthesized to investigate the effect of coordination environment on the sensitized luminescence of Eu(III) complexes. The nine coordination sites of the $Eu^{3+}$ ion are occupied by three bidentate carboxylate moieties and one neutral ligand. The highest emission intensity is obtained for $Eu^{3+}$- $[NA]_3$ (PT), due to the difference in energy transfer efficiency and symmetry of the first coordination sphere of $Eu^{3+}$ ion. But, the lowest emission intensity is obtained for $Eu^{3+}$-$[NA]_3$(T). Terpyridine may not play an important role antenna for photosensitizing $Eu^{3+}$ ion. It could be attributed to the weak spectral overlap integral J value between its phosphorescence band and $Eu^{3+}$ion absorption band. Therefore, different coordination environment of $Ln^{3+}$ ion play an important role in providing sensitization of lanthanide ion emission.

• Rapid Communication in Photoscience
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• v.2 no.1
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• pp.34-37
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• 2013

Two novel antenna complexes of $Eu^{III}$ with 1-naphthoic acid (NA) as primary ligand and two aromatic N-donor ligands namely N-hexyl-N-(pyridin-2-yl) pyridin-2-amine (1) and 4-((dipyridin-2-ylamino)methyl)benzoic acid (2) have been synthesized and characterized by various spectroscopic techniques. The room-temperature (298 K) photoluminescence spectrum of $Eu^{III}$ complexes composed of typical line like emissions, assigned to transitions between the first excited state $^5D_0$ to the $^7F_J$ (J = 0-4), resulting in red emission along with the residual emission from the 1-naphthoic acid moiety in the blue region. The determined CIE color coordinate value for the complex 2 is (x = 0.36, y = 0.34), which is in white region.

• Journal of the Korean Chemical Society
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• v.37 no.10
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• pp.895-902
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• 1993

The chemical behavior of trivalent lanthanide ($Pr^{3+}\;and\;Dy^{3+}$) and organo ligands (phen' and terpy') complexes was investigated by the use of UV/vis-spectrophotometric, magnetization and electrochemical method. The magnitude of crystal field splitting energy, the pairing energy and spin state was obtained from the spectra of complexes. These complexes were founded to be diamagnetics, delocalization and low spin complexes. The electrochemical behavior of complexes was observed by the use of cyclic voltammetry in aprotic media. These reduction peaks were irreversible two step reduction processes by electron transfer.

• Macromolecular Research
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• v.11 no.3
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• pp.133-145
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• 2003

We have developed novel lanthanide-cored supramolecular systems with highly efficient light-harvesting dendritic arrays for integrated planar waveguide-typed amplifiers. Er$^{3+}$ ions were encapsulated by the supramolecular ligands, such as porphyrins and macrobicyclics. The supramolecular ligands have been designed and synthesized to provide enough coordination sites for the formation of stable Er(III)-chelated complexes. For getting a higher optical amplification gain, also, the energy levels of the supramolecular ligands were tailored to maintain the effective energy transfer process from supramolecular ligands to erbium(III) ions. Furthermore, to maximize the light-harvesting effect, new aryl ether-functionalized dendrons as photon antennas have been incorporated into lanthanide-cored supramolecular systems. In this paper, molecular design, synthesis and luminescent properties of novel lanthanide-cored integrated supramolecular systems with highly efficient light-harvesting dendritic arrays will be discussed.d.

• Bulletin of the Korean Chemical Society
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• v.15 no.9
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• pp.782-785
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• 1994

The dissociation kinetics of linear polyaminopolycarboxylate complexes of lanthanide ions (L$n^{3+}: Ce^{3+},\;Eu^{3+}\;and\;Yb^{3+}$) has been studied in an aqueous solution of 0.10 M (NaCl$O_4$) at 25.0${\pm}0.1^{\circ}C$ using Cu(II) ions as a scavenger. The dissociation rates of acid-catalyzed pathway decrease in the order Ln(EPDTA$)^- > Ln(DPOT)^- > In(TMDTA)^- > Ln(MPDTA)^- > Ln(EDTA)^- > Ln(PDTA)^- > Ln(DCTA)^-$ according to the present and literature data. An increase in the N-Ln-N chelate ring from 5 to 6 and substitution of two methyl groups, one ethyl and hydroxyl group on a chelate ring carbon of these ligands leads to a decrease in kinetic stabilities of the complexes. The substitution of one methyl group and cyclohexyl ring on a ring carbon, however, results in a significant increase in the kinetic stability of the resulting $Ln^{3+}$ complexes. Individual reaction steps taking place for each system, with different copper, acetate buffer concentration and pH dependence, are also discussed.

• Bulletin of the Korean Chemical Society
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• v.33 no.11
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• pp.3777-3787
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• 2012

Three kinds of 3D isomorphous and isostructural coordination polymers, namely, $\{[Ln_2(PDA)_3(H_2O)_3]{\cdot}0.25H_2O\}_{\infty}$ (Ln = La(1), Sm(2), and Gd(3)) ($PDA^{2-}$ = pyridine-2,6-dicarboxylate anion) have been synthesized under hydrothermal conditions and characterized by elemental analyses, IR spectroscopy, thermal analyses and single crystal X-ray diffraction. In these MOFs, Ln(III) centers adopt eight-coordinated and nine-coordinated with the $N_1O_7$ and $N_2O_7$ donor sets to construct distorted trianglar dodecahedron geometry and tricapped trigonal prism configurations, respectively. Based on the building block of tetranuclear homometallic $Ln_4C_4O_8$ unit (16-membered ring), 1-3 are connected into highly ordered 2D sheets via O-C-O linkers and further constructed into 3D architectures through hydrogen bonds. Crystallographic parameters suggest that the lanthanide contraction effect exist in these coordination polymers. Luminescent properties of the lanthanide-based MOFs (metal-organic frameworks) have been measured at room temperature, which reveal that they presenting ionselective characters toward certain metals, such as $Mg^{2+}$, $Cd^{2+}$ and $Pb^{2+}$ ions.

• Journal of the Korean Chemical Society
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• v.43 no.3
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• pp.257-263
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• 1999

Ln-macrocyclic([20]DOTA) complexes, [Ln([20]DPTA)(NO_{3})(H_{2}O)](NO_{3})_{2} \cdotxH_{2}O{Ln(III)=Pr, Sm, Gd, Dy}, which had been synthesized from 2, 6-diformyl-p-cresol(DFPC), was placed in methanol for 2 days, and $[Ln([20]DPTA)(NO_{3})(CH_{3}OH)]^{2+}$ was formed. The equilibrium constants(L) for the substitution of coordinated $CH_{3}OH$ in the Ln-[20]DOTA complexes by various auxiliary ligands, $L_{a}(=monodentate ligands; pyridine, imidazole, triethylamine, diethylamine, piperidine) were determined spectroscopically at $25^{\circ}C$ and 0.1M. The pKa of auxiliary ligand is in the order of pyridine < imidazole < triethylamine < diethylamine < piperidine, however the K has shown the trend of pyridine < imidzole < diethylamine < piperidine < triethylamine.