• 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.28 no.8
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• pp.1249-1255
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• 2007

We have investigated the photophysical properties of dansyl-N-methylaminobenzoic acid (DABAH) as a ligand and its lanthanide (Ln3+)-cored complexes (Ln3+-(DABA)3(terpy)) in order to determine the main energy transfer pathway for sensitized near infrared emission of Ln3+ ions (Ln3+ = Nd3+ and Er3+) in Ln3+- (DABA)3(terpy). The fluorescence spectrum of DABAH shows a large Stokes shift with increasing solvent polarity. This large Stokes shift might be due to the formation of a twisted intramolecular charge transfer (TICT) state, as demonstrated by the large dipole moment in the excited state. It is in good agreement with the result that the phosphorescence even in the Gd3+-cored complex based on the DABAH ligand was not observed, maybe due to the highly forbidden character of the S1 → T1 transition in the DABAH ligand. A short decay component (ca. 1 ns) was observed in Er3+-(DABA)3(terpy) whereas the fluorescence lifetimes of DABAH and its Gd3+-(DABA)3(terpy) are observed about ~10 ns. The short component could be originated from the energy transfer process between the ligand and the Ln3+ ion. Based on the fluorescence of DABAH its Ln3+- (DABA)3(terpy), the sensitization of Ln3+ luminescence in the Ln3+-(DABA)3(terpy) takes place by the energy transfer via the TICT state of DABAH in the excited singlet state rather than via the excited triplet state.

• 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.

• Bulletin of the Korean Chemical Society
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• v.26 no.7
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• pp.1057-1064
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• 2005

Photoluminescence (PL) spectra of Eu(III) and Tb(III) complexes with mixed oxydiacetate (ODA) and 1,10-phenanthroline (phen) ligands and with homoleptic ODA reveal characteristic line-splitting at 10 K, depending on the site-symmetry of the lanthanide ion in the complex. The energy-level schemes of the $^7F_J$ states and the emitting levels for Eu(III) and Tb(III) ions have been proposed by simulating the line splitting in the framework of crystal-field Hamiltonian. The sets of refined crystal-field parameters for the experimentally determined sitesymmetry satisfactorily reproduce the experimental energy-level schemes. In addition, the PL quantum yield and the decay time were determined at room temperature. The PL quantum yields of [$Eu(ODA){\cdot}(phen){\cdot}4H_2O]^+$ and [Tb$(ODA){\cdot}(phen){\cdot}4H_2O]^+$ in the crystalline state (Q = 17.7 and Q = 56.6%, respectively) are much greater than those of [Eu($ODA)_3]^{3-}and\;[Tb(ODA)_3]^{3-}$(Q = 1.1 and Q = 1.3, respectively), due to the energy transfer from phen to the lanthanide ion. In the aqueous state, the relaxation of the phen moiety due to the solvent results in the reduction of the quantum yield and the shortening of the lifetime.

• Bulletin of the Korean Chemical Society
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• v.25 no.6
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• pp.852-858
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• 2004

Crystal structures of lanthanide complexes with NTA (NTA = nitrilotriacetate) are reported. The complexes of $[Ln(NTA)_2{\cdot}H_2O]^{3-}$ (Ln = Sm, Eu, Gd, Tb and Ho) crystallize in the orthorhombic space group Pccn. In the structures, the trivalent lanthanide ions are completely encapsulated via coordination to the two nitrogen atoms and the six carboxylate oxygen atoms of the two NTA ligands, and one water oxygen atoms. The complexes form a slightly distorted capped-square-antiprism polyhedron. Of the complexes, $[Eu(NTA)_2{\codt}H_2O]^{3-}$,\;[Tb(NTA)_2{\cdot}H_2O]^{3-}\;and\;[Dy(NTA)_2{\cdot}H_2O]^{3-}$ excited at the 325 He-Cd line produce very characteristic luminescence features, arising mostly from the f ${\to}$ f transitions. The absolute quantum yields of these complexes are determined at room temperature. Surprisingly, the $[Dy(NTA)_2{\cdot}H_2O]^{3-}$ complex is more luminescent than the $[Eu(NTA)_2{\cdot}H_2O]^{3-}\;and\;[Tb(NTA)_2{\cdot}H_2O]^{3-}$ complexes.

• Bulletin of the Korean Chemical Society
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• v.20 no.3
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• pp.297-300
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• 1999

The protonation constants of the macrocyclic ligands, 1,4-dioxa-7,10,13,16-tetraaza-cyclooctadecane-N,N',N",N"'-tetra(acetic acid) [N-ac4[18]aneN402] and 1,4-dioxa-7,10,13,16-tetraazacyclooctadecane-1,4-dioxa-7,10,13,16-N,N',N",N"'-tetra(methylacetic acid) [N-meac4[18]aneN4O2] have been determined by using potentiometric method. The protonation constants of the N-ac4[18]aneN4O2 were 9.31 for logK1H, 8.94 for logK2H, 7.82 for logK3H, 4.48 for logK4H and 2.94 for logK5H. And the protonation constants of the N-meac4[18]aneN4O2 were 9.34 for logK1H, 9.13 for logK2H, 8.05 for logK3H, 5.86 for logK4H, and 3.55 for logK5H. The stability constants of complexes on the divalent transition ions (Co2+, Ni2+, Cu2+, and Zn2+) and tiivalent metal ions (Ce3+, Eu3+, Gd3+, and Yb3+) with ligands N-ac4[18]-aneN4O2 and N-meac4[18]aneN4O2 have been obtained from the potentiometric data with the aid of the BEST program. The three higher values of the protonation constants for synthesized macrocyclic ligands correspond to the protonation of nitrogen atoms, and the fourth and fifth values correspond to the protonation of the carboxylate groups for the N-ac4[18]aneN4O2 and N-meac4[18]aneN4O2. The meatal ion affinities of the two tetra-azamacrocyclic ligands with four pendant acetate donor groups or methylacetate donor groups are compared. The effects of the metal ions on the stabilities are discussed, and the trends in stability constants resulting from changing the macrocyclic ring with pendant donor groups and acidity of the metal ions.

• Proceedings of the Korean Vacuum Society Conference
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• 2016.02a
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• pp.292-292
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• 2016

Transition metal dichalcogenides (TMDs) with a two-dimensional layered structure have been considered highly promising materials for next-generation flexible, wearable, stretchable and transparent devices due to their unique physical, electrical and optical properties. Recent studies on TMD devices have focused on developing a suitable doping technique because precise control of the threshold voltage ($V_{TH}$) and the number of tightly-bound trions are required to achieve high performance electronic and optoelectronic devices, respectively. In particular, it is critical to develop an ultra-low level doping technique for the proper design and optimization of TMD-based devices because high level doping (about $10^{12}cm^{-2}$) causes TMD to act as a near-metallic layer. However, it is difficult to apply an ion implantation technique to TMD materials due to crystal damage that occurs during the implantation process. Although safe doping techniques have recently been developed, most of the previous TMD doping techniques presented very high doping levels of ${\sim}10^{12}cm^{-2}$. Recently, low-level n- and p-doping of TMD materials was achieved using cesium carbonate ($Cs_2CO_3$), octadecyltrichlorosilane (OTS), and M-DNA, but further studies are needed to reduce the doping level down to an intrinsic level. Here, we propose a novel DNA-based doping method on $MoS_2$ and $WSe_2$ films, which enables ultra-low n- and p-doping control and allows for proper adjustments in device performance. This is achieved by selecting and/or combining different types of divalent metal and trivalent lanthanide (Ln) ions on DNA nanostructures. The available n-doping range (${\Delta}n$) on the $MoS_2$ by Ln-DNA (DNA functionalized by trivalent Ln ions) is between $6{\times}10^9cm^{-2}$ and $2.6{\times}10^{10}cm^{-2}$, which is even lower than that provided by pristine DNA (${\sim}6.4{\times}10^{10}cm^{-2}$). The p-doping change (${\Delta}p$) on $WSe_2$ by Ln-DNA is adjusted between $-1.0{\times}10^{10}cm^{-2}$ and $-2.4{\times}10^{10}cm^{-2}$. In the case of Co-DNA (DNA functionalized by both divalent metal and trivalent Ln ions) doping where $Eu^{3+}$ or $Gd^{3+}$ ions were incorporated, a light p-doping phenomenon is observed on $MoS_2$ and $WSe_2$ (respectively, negative ${\Delta}n$ below $-9{\times}10^9cm^{-2}$ and positive ${\Delta}p$ above $1.4{\times}10^{10}cm^{-2}$) because the added $Cu^{2+}$ ions probably reduce the strength of negative charges in Ln-DNA. However, a light n-doping phenomenon (positive ${\Delta}n$ above $10^{10}cm^{-2}$ and negative ${\Delta}p$ below $-1.1{\times}10^{10}cm^{-2}$) occurs in the TMD devices doped by Co-DNA with $Tb^{3+}$ or $Er^{3+}$ ions. A significant (factor of ~5) increase in field-effect mobility is also observed on the $MoS_2$ and $WSe_2$ devices, which are, respectively, doped by $Tb^{3+}$-based Co-DNA (n-doping) and $Gd^{3+}$-based Co-DNA (p-doping), due to the reduction of effective electron and hole barrier heights after the doping. In terms of optoelectronic device performance (photoresponsivity and detectivity), the $Tb^{3+}$ or $Er^{3+}$-Co-DNA (n-doping) and the $Eu^{3+}$ or $Gd^{3+}$-Co-DNA (p-doping) improve the $MoS_2$ and $WSe_2$ photodetectors, respectively.

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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• 2002.11a
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• pp.581-584
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• 2002

A new method for the preparation of lanthanide ions activated strontium aluminates phosphor by combustion method has been proposed. Combustion method consist of the redox reactions between the respective metal nitrates and urea in a preheated funace at $500^{\circ}C$. The luminescence behavior of the phosphor was studied and compared with corresponding phosphor prepared by conventional method. Effect of $Mg^{2+}$ ion concentration in strontium aluminate phosphor was investigated and the maximum luminescence of about $100cd/m^2$ was obtained. This method gave better brightness and small size to the phosphor than made by conventional method.

• Bulletin of the Korean Chemical Society
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• v.4 no.5
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• pp.231-234
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• 1983

The stability constant for the complex of $UO_2^{2+}$ with a macrocyclic aminoether ligand, 1,7,10,16-tetraoxa-4,13-diazacyclooctadecane, has determined in aqueous solution. The conductivity and pH metric measurements suggest that the ligand forms a stable 1:1 complex with $UO_2^{2+}$ ion, and the complex is an ionic form, $UO_2L^{2+}$, in aqueous solution. The fact that the ligand does not form a complex with lanthanides, such as $Ce^{3+}$, $Sm^{3+}$, and $Nd^{3+}$ ions, in aqueous solution suggests a possibility of separation of the lanthanide elements from uranium matrix using the macrocyclic aminoether ligand.

• Journal of the Korean Ceramic Society
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• v.54 no.2
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• pp.96-101
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• 2017

In this article, pure $m-LaVO_4:Eu^{3+}$ and $t-LaVO_4:Eu^{3+}$ nanocrystals were prepared by an EG-assisted hydrothermal method with regular shapes. A series of controlled experiments showed that the pH value of a mixed solution, the volume ratio of $EG/H_2O$ and the dosage of the doped $Eu^{3+}$ all had an important effect on the sizes and shapes of the final products. Furthermore, the constitutional unit of the products changed from 0D to 2D with an increase in the EG dosage. The PL results showed that $t-LaVO_4$ doped with $Eu^{3+}$ ions had better luminescence properties than $m-LaVO_4$ due to its special structure. All of these results not only expand our understanding of the luminescence properties of lanthanide orthovanadates, but they also elucidate the principles of the crystal growth.