• Bulletin of the Korean Chemical Society
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• v.32 no.5
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• pp.1745-1747
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• 2011

• 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.

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

• Bulletin of the Korean Chemical Society
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• v.27 no.5
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• pp.687-693
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• 2006

Chromium(III) complexes, cis-[Cr([14]-decane)$(HOC _6H _4COO) _2$]$ClO _4$ I and cis-[Cr([14]-decane)(OH) $(OC _6H _4NO _2)$]$ClO _4{\cdot}H _2O$ II ([14]-decane = rac-5,5,7,12,12,14-hexamethyl-1,4,8,11-teraazacyclotetradecane) are synthesized and structurally characterized by a combination of elemental analysis, conductivity, IR and VIS spectroscopy, and X-ray crystallography. The complexes crystallizes in the monoclinic space groups, $C2 _1$/a in I and $P2 _1$/n in II. Analysis of the crystal structure of complex I reveals that central chromium(III) ion has a distorted octahedral coordination environment and two hydrogensalicylato ligands are unidentate to the chromium(III) ion via the carboxyl groups in the cis-position. For monomeric complex I the hydrogensalicylato coordination geometry is as follows: Cr-O(average) = 1.984(3) $\AA$;Cr-N range = 2.105(3)-2.141(4) $\AA$;C(24)-O(4) = 1.286(5) $\AA$;N(2)-Cr-N(4) (equatorial position) = 96.97(15)${^{\circ}}$; N(1)-Cr-N(3) (axial position) = 168.27(15)${^{\circ}}$; O(1)-Cr-O(4) = 85.70(13)${^{\circ}}$. The crystal structure of II has indicated that chromium(III) ion is six-coordinated by four secondary amines of the macrocycle, hydroxide anion and nitrophenolate anion.

• Journal of the Korean Chemical Society
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• v.45 no.6
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• pp.507-512
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• 2001

The hydrothermal reaction between lanthanum(Ⅲ) nitrate $(La(NO3)3${\cdot}$6H_2O)$ and benzene-1,3-dicarboxylic acid $(H_2BDC)$ in the presence of 1,2-bis(4-pyridyl)ethane gave a 2-D lanthnum-BDC coordination polymer with an empirical formula of $〔La_4$(BDC)_6(H_2O)_5$〕(H_2O)$ (1). X-ray structure analysis of compound 1 revealed that this polymer contains four distinct La metals. The three La metals are 7-coordinate with three different structures: a capped trigonal prism, a capped octahedron, and a pentagonal bipyramid. The remaining La metal has a 8-coordinate, square antiprismatic structure.

• Bulletin of the Korean Chemical Society
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• v.15 no.11
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• pp.990-996
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• 1994

New ferrocene-based chelate amines, $Fe[C_5H_4CH(Me)NMe_2]_2\;(3), \;Fe[C_5H-3(CH(Me)NMe_2)(PPh_2)-1,2]_2\;(4),\;(C_5H_5)Fe(C_5H_3(CH_2NMe_2)(CH(CN)NMe_2-1,2)\;(6),\;and\;(C_5H_5)Fe(C_5H_3(CH_2NMe_2)(CH(Me)NMe_2-1,2)$ (7) have been prepared. The reaction and the coordination chemistry of 4 and other related compounds (S,R)-(1-N,N-dimethylaminoethyl)-2-dicyclohexylphosphino)ferrocene (CPFA) and 1,1'-bis-(diphenylphosphino)ferrocene (BPPF) with $Rh_2(OAc)_4(MeOH)_2$ were investigated. The reaction of the chiral ligand (S,R)-CPFA forms a complex of the type (${\eta}^1$-(S,R)-CPFA-P)$_2Rh_2(OAc)_4$ (8) in which the ligand is coordinated to both rhodium centers in a monodentate fashion through phosphorus. In contrast, the bisphosphine analogues such as BPPF and 4 afford chelate complexes of the type (${\eta}^2-PP)Rh_2(OAc)_4$ (9 & 10) where both ligands act as a chelate bidentate to a single rhodium atom. All these complexes were characterized by microanalytical and spectroscopic techniques. In one case, the structure of 8 was determined by X-ray crystallography. Crystals are monoclinic, space group C2 (No. 5), with a=26.389 (3), b=12.942 (1), c=11.825 (1) A, ${\beta}$=111.22(1)$^{\circ}$, V=3964.7 (8) $A^3$, Z=4, and $D_{calc}$=1.58 g $cm^{-3}$. Two Rh(II) centers are bridged by four $AcO^-$ groups in the ${\eta}^1$ : ${\eta}^1$ mode across a Rh-Rh single bond, and octahedral coordination at Rh(1) and Rh(1') is completed by axially coordinating (S,R)-CPFA and a briding $AcO^-$, respectively.

• Bulletin of the Korean Chemical Society
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• v.33 no.10
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• pp.3361-3367
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• 2012

Two novel Eu(III) complexes with notable properties have been successfully prepared with hydrazone Schiff base ligands, (E)-2-hydroxy-N'-[(2-hydroxynaphthalen-1-yl)methylene]benzohydrazide (3a) and (E)-4-hydroxy-N'-[(2-hydroxynaphthalen-1-yl)methylene]benzohydrazide (3b). DFT, FMO energy and Mulliken charge distribution studies of the ligands allowed us to hypothesize that their HC=N, > C=O and -OH (naphthyl) groups were involved in coordinating with the $Eu^{3+}$ ion. The eight coordination sites of the $Eu^{3+}$ ion were occupied by the three functional groups of the two ligands (3a or 3b) mentioned above and two water molecules. Similar UV, IR and fluorescence spectra indicated the presence of comparable coordination environments for the $Eu^{3+}$ ion in both complexes. Both the ligands and their complexes exhibited moderate DPPH radical scavenging activity. Moreover, it was found that the Eu(III) complexes exhibited fluorescence properties.

• Bulletin of the Korean Chemical Society
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• v.31 no.9
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• pp.2598-2602
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• 2010

Two 3-D zinc framework compounds, $[Zn_6(BTB)_4(4,4'-bipy)_4(H_2O)_4]{\cdot}9H_2O$ (1) and $[Zn_3(BTB)_2(4,4'-bipy)_2(H_2O)_2]{\cdot}5H_2O$ (2) ($H_3BTB$ = 1,2,3-benzenetricarboxylic acid, 4,4'-bipy = 4,4'-bipyridine), are obtained from the diffusion method and hydrothermal reaction respectively. Though 1 and 2 has the same coordination geometries of zinc atoms and coordination mode of $BTB^{3-}$, their 2-D layers are different: mirror symmetric layers in 1; parallel ones in 2, further connecting by 4,4'-bipy into 3-D frameworks. The hydrothermal reaction of 2 results in a more stable 3-D framework than the one in 1, which is supported by the single point energy calculations. 1 and 2 show similar blue fluorescence at 417 nm, which can be assigned to LMCT.

• Bulletin of the Korean Chemical Society
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• v.31 no.12
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• pp.3600-3604
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• 2010

Rhodium(III)-$Cp^*$ complexes containing labile ligands, $[Cp^*RhCl_2]_2$, [$Cp^*Rh({\eta}^2-NO_3)$(OTf)], and $[Cp^*Rh(OH_2)_3](OTf)_2$, reacted with potential linking ligands [$L^1$ = (2-thiophene)-CH=N-N=CH-(2-thiophene); $L^2$ = (2-furan)-CH=N-N=CH-(2-furan)] to give two molecular compounds, [$Cp^*Rh(L^1)Cl_2$] (1) and [$Cp^*Rh({\eta}^2-NO_3)(L^1)$]$(OTf){\cdot}CH_2Cl_2$ ($2{\cdot}CH_2Cl_2$), and one 1-dimensioanl coordination polymer, $\{[Rh(L^2)]{\cdot}(OTf)}_{\infty}$ (3). Whereas one imine nitrogen atom within the ligand is coordinated to the Rh metal in compounds 1 and 2, both nitrogen atoms are bound to two neighboring Rh metals in compound 3 to lead to a 1-D chain polymer.

• Bulletin of the Korean Chemical Society
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• v.27 no.11
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• pp.1839-1843
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• 2006

Hydrothermal reactions of $Ln(NO_3)_3{\cdot}5H_2O $ (Ln = Eu (1), Sm (2), Ho (3), Dy (4)) with 3,5-pyridinedicarboxylic acid (3,5-pdcH2) in the presence of 4,4'-bipyridine led to the formation of the 3-D Ln(III)-coordination polymers with a formula unit of $[Ln_2(3,5-pdc)_2(C_2O_4)(H_2O)_4]{\cdot}2H_2O$. These polymers contain a bridging oxalate ligand ($C_2O_4\;^2$). On the basis of GCMS study of the mother liquor remaining after the reaction, we proposed that the $C_2O_4\;^2$ formation proceeds in three steps: (1) Ln(III)-mediated decarboxylation of $3,5-pdcH_2$ to give $CO_2$, (2) the reduction of $CO_2$ to $CO_2\;^{\cdot}$ by the Ln(II) species, and (3) the reductive coupling of the two $CO_2\;^{\cdot}$ radicals to the oxalate ($C_2O_4\;^2$) ion. All polymers were structurally characterized by X-ray diffraction.