• Bulletin of the Korean Chemical Society
• /
• v.26 no.8
• /
• pp.1197-1202
• /
• 2005

The Ln(III) complexes with picrate ligand, $[Sm(Pic)_2(H_2O)_6]Pic{\cdot}6H_2O$, 1, and $[Ho(Pic)(H_2O)_7](Pic)_2{\cdot}3H_2O$, 2, have been synthesized and their crystal structures are analyzed by X-ray diffraction methods. Complex 1, crystallizes in the monoclinic $P2_1/n$ space group and complex 2 in the triclinic P-1 space group. In complex 1, two picrate ligands coordinate to the Sm(III) ion, one of them in the bidentate fashion. There are one picrate anion and six water molecules in the crystal lattice. The nine-coordinated Sm(III) ion forms a slightly distorted tricapped trigonal prism. In complex 2, only one picrate ligand coordinates to the metal ion as a monodentate. There are two picrate anions and three water molecules in the crystal lattice. The eight-coordinated Ho(III) ion forms a distorted bicapped trigonal prism. Based on the results of the TG-DTG and DSC thermal analysis, it was analyzed that the lanthanide picrate complexes 1 and 2 are thermally decomposed in three distinctive stages, the dehydration, the picrate decomposition, and the formation of the metal oxide.

• Rapid Communication in Photoscience
• /
• v.1 no.1
• /
• pp.1-9
• /
• 2012

Luminescent lanthanide complexes have been overviewed for advanced photonics applications. Lanthanide(III) ions ($Ln^{3+}$) were encapsulated by the luminescent ligands such as metalloporphyrins, naphthalenes, anthracene, push-pull diketone derivatives and boron dipyrromethene(bodipy). The energy levels of the luminescent ligands were tailored to maintain the effective energy transfer process from luminescent ligands to $Ln^{3+}$ ions for getting a higher optical amplification gain. Also, key parameters for emission enhancement and efficient energy transfer pathways for the sensitization of $Ln^{3+}$ ions by luminescent ligands were investigated. Furthermore, to enhance the optophysical properties of novel luminescent $Ln^{3+}$ complexes, aryl ether-functionalized dendrons as photon antennas have been incorporated into luminescent $Ln^{3+}$ complexes, yielding novel $Ln^{3+}$-cored dendrimer complex such as metalloporphyrins, naphthalenes, and anthracenes bearing the Fr$\acute{e}$chet aryl-ether dendrons, namely, ($Er^{3+}-[Gn-Pt-Por]_3$ (terpy), $Er^{3+}-[Gn-Naph]_3$(terpy) and $Er^{3+}-[Gn-An]_3$(terpy)). These complexs showed much stronger near-IR emission bands at 1530 nm, originated from the 4f-4f electronic transition of the first excited state ($^4I_{13/2}$) to the ground state ($^4I_{15/2}$) of the partially filled 4f shell. A significant decrease in the fluorescence of metalloporphyrins, naphthalenes and anthracene ligand were accompanied by a strong increase in the near IR emission of the $Ln^{3+}$ ions. The near IR emission intensities of $Ln^{3+}$ ions in the lanthanide(III)-encapsulated dendrimer complexes were dramatically enhanced with increasing the generation number (n) of dendrons, due to the site-isolation and the light-harvesting(LH) effects. Furthermore, it was first attempted to distinguish between the site-isolation and the light-harvesting effects in the present complexes. In this review, synthesis and photophysical studies of inert and stable luminescent $Ln^{3+}$ complexes will be dealt for the advanced photonics applications. Also, the review will include the exploratory investigation of the key parameters for emission enhancement and the effective energy transfer pathways from luminescent ligands to $Ln^{3+}$ ions with $Ln^{3+}$-chelated prototype complexes.

• Journal of the Korean Chemical Society
• /
• v.38 no.1
• /
• pp.50-54
• /
• 1994

Spectrophotometric determination of some light lanthanide ions by flow injection method is described. Chromeazurol S forms water soluble complex with lanthanide ions in the presence of DTAB. The absorption maximum of the complexes are from 650 nm to 655 nm and the molar absorptivities were ca. $1.8{\times}10^5\;L mol^{-1}cm^{-1}$ on Tris buffer (pH 10.5). The calibration curves for Nd(III), Eu(III) and Sm(III) obtained by FIA are over the range of 0.1 to 0.6 ppm and the correlation coefficient were ca. 0.9993. The detection limits (S/N) were from 10 ppb for Nd(III) and Eu(III) to 20 ppb for Sm(III). The relative standard deviations was ${\pm}$.2% for 0.4 ppm sample. The samples throughput was ca. $50\;cm^{-1}$.

• Journal of the Korean Chemical Society
• /
• v.55 no.4
• /
• pp.612-619
• /
• 2011

Lanthanide(III) complexes of 1,2-diphenyl-4-butyl-3,5-pyrazolidinedione(phenylbutazone, PB) have been synthesized and characterized by elemental analyses, molar conductance measurements, IR, UV-Vis. and NMR spectra. The spectral data reveal that the PB acts as a bidentate and mono-ionic ligand coordinating through both the carbonyl oxygens of the pyrazolidinedione ring. The molar conductance data suggest that the complexes are non-electrolytes. The thermal behaviour of the complexes was studied by TG and DTG in air atmosphere and the results provide information about dehydration, thermal stability and thermal decomposition. The final products are found to be the corresponding metal oxides. The thermodynamic parameters and kinetic parameters were evaluated for the dehydration and decomposition stages. The negative entropy values of the decomposition stages indicate that the activated complexes have a more ordered structure than the reactants and that the reactions are slower than normal. Based on these studies, the complexes have been formulated as $[Ln(PB)_3]{\cdot}5H_2O$(Ln=La and Ce) and $[Ln(PB)_3(H_2O)_2]{\cdot}2H_2O$(Ln=Pr, Nd and Sm).

• Bulletin of the Korean Chemical Society
• /
• v.30 no.10
• /
• pp.2213-2216
• /
• 2009

A novel carbazole functionalized bis-$\beta$-diketone type organic ligand, 1,1′-(2,6-bispyridyl)bis-3-(9-ethylcarbazole- 3-yl)-1,3-propanedione ($H_2L$) and its corresponding lanthanide complexes $Eu_2(L)_3\;and\;Tb_2(L)_3$ were successfully prepared. The ligand and complexes were characterized in detail based on FT-IR spectra, $^1H$ NMR and elemental analysis. The observed UV-Vis absorption and photoluminescence properties of the complexes were investigated, it shows that the Eu(III) and Tb(III) ions can be sensitized efficiently by the ligand ($H_2L$) to some extent, in particular, the complex $Tb_2(L)_3$ exhibits a more excellent luminescence property than the Eu(III) complex. Meanwhile, the introduction of the carbazole moiety can enlarge the $\Pi$-conjugated system of the ligand and enhance the luminescent intensity of the complexes. The results show that the complexes would be used as excellent luminescent materials.

• Bulletin of the Korean Chemical Society
• /
• v.34 no.11
• /
• pp.3481-3484
• /
• 2013

• Journal of the Korean Chemical Society
• /
• v.43 no.5
• /
• pp.596-600
• /
• 1999

• Analytical Science and Technology
• /
• v.28 no.3
• /
• pp.204-211
• /
• 2015

Lanthanide complexes have attracted much attention because of their unique light emitting property. The light-emitting efficiencies of europium β-diketonate complexes were compared with those of complexes coordinated by the ligands of amines or phosphine oxides. The results demonstrated that the complexes that were coordinated by phosphine oxides had higher light-conversion performance than those coordinated by amines. The highest light-emitting efficiency was observed when the ligand of trioctylphosphine oxide was coordinated. In order to determine the coordination equivalency of trioctylphosphine oxide in the above complexes, 31P-NMR and their photoluminescence spectra were measured. The findings showed that the europium β-diketonate complex had one or two coordination equivalencies of trioctylphosphine oxide according to the steric hindrance of its original ligand.

• Journal of the Korean Chemical Society
• /
• v.33 no.5
• /
• pp.496-503
• /
• 1989

The chemical behavior of trivalent lanthanide (Pr(III) and Yb(III)) and 2, 2, 6, 6-tetramethyl-3, 5-heptanedione(dipivaloylmethane) complexes was investigated by the use of direct current, differential pulse polarography and cyclic voltammetry. In this study, it was founded that the reduction of trivalent lanthanide complexes was observed by one electron transfer process at Epc = -0. 13 V and -0.80 V of Pr(III), and -0.02 V of Yb(III) vs. Ag-AgCl electrode. Also, it was founded that the treatment of DP and CV to the case of a first-order chemical equilibrium reaction preceding a reversible and irreversible one electron transfer reaction, (a >0. 5) the socalled ErCr electrode process. The equilibrium constant (lnK) obtained, of various solvents, these constant were founded to be increases with decreasing dielectric constant of the solvents. Plots of lnK for these reaction against ln(l/D) for the solvents was fairly straight lines, and the behavior of the heavier lanthanides was decreased equilibrium constant with increasing atomic number.

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