MIXEDꢀLIGAND LANTHANIDE COMPLEXES
279
The purpose of this work is the quantumꢀchemical
study of the mixedꢀligand lanthanide complexes with
acetylacetone and various phosphorusꢀcontaining
compounds (pesticides and model objects), as well as
The CHN analysis was carried out on a Fision
Instruments 1108 CHN microanalyzer. The lanꢀ
thanide content was determined by complexonometry.
Commercially accessible 1ꢀphenylꢀ3ꢀmethylpyraꢀ
the synthesis and study of the luminescence properties zolꢀ5ꢀone (Fluka),
ꢀthenoyl chloride and tertꢀbutyꢀ
α
lacetyl chloride (SigmaꢀAldrich), and KOH (Mosꢀ
reaktiv, IMP) were used as received. Calcium oxide
(Reakhim, analytical grade) was calcined in a muffle
of the Sm, Eu, Tb, and Dy complexes with acylpyrazoꢀ
lones and ligand LP. 1ꢀPhenylꢀ3ꢀmethylꢀ4ꢀthienylcarꢀ
bonylpyrazolꢀ5ꢀone (HQS) [3, 11, 12] and 1ꢀphenylꢀ3ꢀ
furnace at 1200 С. Lanthanide nitrates were prepared
°
methylꢀ4ꢀneopentylcarbonylpyrazolꢀ5ꢀone (HQn )
Pe
by the dissolution of the corresponding oxides
(reagent grade) in nitric acid (highꢀpurity grade).
Dioxane (KomponentꢀReaktiv, analytical grade) was
purified and dried according to a standard procedure
using metallic sodium and benzophenone. Ethanol
(Ferein) was purified by distillation over KOH.
Ligands HQS and HQnPe were synthesized accordꢀ
ing to a standard procedure of 1ꢀphenylꢀ3ꢀmethylꢀ
pyrazolꢀ5ꢀone acylation with the corresponding carꢀ
boxylic acid chloride in dioxane [3–5]. Ligand LP was
synthesized using a described procedure [19].
[4], Ln(Q)3(LP)(EtOH) (Q = HQn , HQS; Ln = Sm,
Eu, Tb, Dy), were used as acylpyrazolones.
Pe
O
O
S
HQS
N
N
CH3
H3C
O
O
CH3
HQn
Pe
Synthesis of Eu(QS)3(EtOH)(LP)
. A solution of
CH3
N
Eu(NO3)3 6H2O (52.29 mg, 0.1172 mmol) in ethanol
⋅
(2 mL) and a solution of LP (26.28 mg, 0.1172 mmol)
in ethanol (1 mL) were added dropwise to a solution of
a mixture of HQS (100.00 mg, 0.3517 mmol) and KOH
(19.73 mg, 0.3517 mmol) in ethanol (5 mL). The mixꢀ
ture was refluxed for 15 min and cooled to ambient
temperature. Potassium nitrate was saltedꢀout with
chloroform (2 mL). Precipitated KNO3 was filtered
off. After the solution was evaporated by 3/4 of the volꢀ
ume, a yellow precipitate of the complexes was
formed, filtered off, washed with cool ethanol (two
times, 2 mL each washing) and ether, transferred to a
vacuum desiccator, and dried over P2O5 for 12 h.
N
CH3
EXPERIMENTAL
The Firefly 7.1.G calculation complex [13] in the
DFT method with the B3LYP hybrid exchange correꢀ
lation functional was used. Calculations were perꢀ
formed in the 6ꢀ31G Pople basis set [14–16] for atoms
different from lanthanum. The SBK basis set [17] was
used to describe the lanthanum atom. The Hesse
matrix was calculated to check the correspondence of
the optimized structures of the local minimum points
on the potential energy surface for all compounds. No
imaginary frequencies were found.
For simplification the calculations were performed
for the lanthanum acetylacetonate complexes. The
geometry of molecules of the La(Acac)3(EtOH)(X),
La(Acac)3(H2O)(X), and La(Acac)3(X) complexes,
where X are different ligand molecules, was optimized.
The initial geometry of the complexes was taken from
the Xꢀray diffraction data for lanthanum acetylacetoꢀ
nate dihydrate [18], after which the water molecule
was replaced by the ligand molecule in the preoptiꢀ
mized geometric configuration. Then the energies of
the reactions
IR (
1470, 1456, 1417
(P=O); 1059, 1044, 1014, 902, 858, 817, 779, 751.
Other complexes were synthesized similarly from
the corresponding acylpyrazolone and metal nitrate.
The elemental analysis results are given in Table 1.
IR of Sm(QS)3(EtOH)(LP) ( (О–Н);
, cm–1): 3075
1604, 1591, 1578; 1472, 1457, 1440 (С=О, С=С,
C=N); 1192 (P=O); 1044, 1015, 816, 780, 759, 738.
IR of Tb(Qn ) (EtOH)(LP) ( (О–Н);
, cm–1): 3069
1612, 1593, 1580, 1536; 1498, 1479, 1426 (С=О,
С=С, C=N); 1188, 1176 (P=O); 1093, 1075, 1063,
1014, 840, 754, 730.
, cm–1): 3069
(О–Н);
(С=О, С=С,
ν
, cm–1): 3072
(С=О, С=С, C=N); 1186
ν(О–Н); 1604, 1592, 1576;
ν
ν
ν
ν
ν
ν
ν
ν
Pe 3
ν
ν
IR of Dy(Qn ) (EtOH)(LP) (
ν
ν
Pe 3
La Acac EtOH H O + X ꢀ
)3 ( )(
(
)
2
1612, 1589, 1581, 1535; 1493, 1472
ν
(1)
(2)
ꢀ La Acac EtOH X + H O,
)3 ( )( )
(
2
C=N); 1175
ν(P=O); 1160, 1092, 1070, 1060, 1011,
831, 730.
La Acac EtOH + X ꢀ
)3 (
(
)
Single crystals of complex Sm(QS)3(EtOH)(LP)
were obtained as yellow needles by the slow evaporaꢀ
tion of a solution of the complex in an ethanol–chloꢀ
ꢀ La Acac X + EtOH,
)3 ( )
were determined using the difference scheme.
(
The IR spectra of the complexes were recorded on roform mixture in a sealed Lꢀtype ampule. It should be
a FTIR Spectrum One spectrometer (PerkinElmer) in mentioned that crystals coinciding, according to the
the attenuated total internal reflectance mode in the Xꢀray diffraction data, with the complex described
range from 400 to 4000 cm–1 (resolution 0.5 cm–1). above precipitate from a solution containing
Excitation and luminescence spectra were recorded Sm(NO3)3
⋅
6H2O, HQS, KOH, and LP in a molar
on a PerkinꢀElmer LS55 spectrometer. ratio of 1 : 1 : 1 : 2 upon gradual evaporation.
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 39
No. 3
2013