Polyhedron 68 (2014) 80–86

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Polyhedron
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Comparison of structural variations of Ln(III) compounds

with (pyrazol-1-yl)acetic acid
Xiao-Yan Chen a, George S. Goff a, Brian L. Scott b, Wolfgang Runde c,⇑
a
Chemistry Division, Los Alamos National Laboratory, Los Alamos, NM 87545, United States
b
Material Physics and Applications Division, Los Alamos National Laboratory, Los Alamos, NM 87545, United States
c
Science Program Office, Los Alamos National Laboratory, Los Alamos, NM 87545, United States

a r t i c l e i n f o a b s t r a c t

Article history: As a continuation of our previous studies of light lanthanides (La, Ce, Pr, and Nd) with (Pyrazol-1-yl)acetic
Received 1 August 2013 acid (L), we reacted L with the heavier lanthanides in aqueous solution at pH 5 and synthesized lantha-
Accepted 14 October 2013 nide complexes of the general formula [Ln(L)3(H2O)2]
H2O (Ln = Eu, 1; Gd, 2; Dy, 3; Ho, 4; Er, 5; Yb, 6; Lu,
Available online 19 October 2013
7) and [HoL(NO3)2(H2O)3] (8). All complexes were characterized by single crystal X-ray diffraction anal-
ysis revealing one-dimensional chain formations. Three distinct crystallographic structures are governed
Keywords: by the different coordination modes of the carboxylate groups in L: terminal bidentate, bridging biden-
Rare earth compounds
tate and tridentate coordination in 1–3, terminal and bridging bidentate coordination in 4–7, and bridg-
(Pyrazol-1-yl)acetic acid
Crystal structures
ing bidentate coordination in 8. The solid state UV–Vis–NIR diffuse reflectance spectra and the solution
Optical spectroscopy UV–Vis–NIR absorption spectra differ, suggesting different coordination environments in solution and
solid state. The coordination-induced shifts of the 13C NMR signals for [Lu(L)3(H2O)2]
H2O (7) in D2O show
that the carboxylate groups of the ligand are coordinated with the Lu(III) ion in solution.
Ó 2013 Elsevier Ltd. All rights reserved.

1. Introduction hydrothermal conditions. Among the known Ln complexes, twelve

The pyrazole heterocycle possesses various biological proper-
ties such as being anti-inflammatory [1], anti-tubercular [2], anti-
microbial [2,3], and anti-cancer [4] etc., which have increased the
interest of pyrazole-metal complexes for pharmaceutical applica-
tions [5]. Since the first report of cis-dichlorobis(pyrazole)plati-
num(II) which possesses cancer-targeting abilities in 2000 [6],
pyrazole-based compounds with palladium, platinum, copper,
gold, zinc, cobalt, nickel, iron, silver and gallium have been inves-
tigated for therapeutic drug development [5]. Among these transi-
tion metal complexes, over 20 different coordination modes of
pyrazole have been revealed [7].
With the increasing applications of lanthanides (Ln) in industry,
technology, and medicine [8], studies of lanthanide compounds
with pyrazole [9] have drawn more and more attention. However,
pyrazoles can only be deprotonated by treatment with lanthanides
and diarylmercurials or iodine activated lanthanides [7,9]. In order
to react with trivalent lanthanides at mild conditions, the pyrazole
ring has been modified by incorporating functional groups such as
carboxylate groups. To date, crystal structures have been reported
for lanthanides with pyrazole-3,5-dicarboxylic acid [10] and 4-iod-
opyrazole-3,5-dicarboxylic acid [11], both synthesized under
⇑ Corresponding author. Tel.: +1 505 667 3350.
E-mail address: runde@lanl.gov (W. Runde).
coordination modes were observed including terminal and bridg-
ing carboxylate groups or bridging and chelating pyrazole N and
carboxylate groups.
Our research group has been developing task-specific ionic
liquids (TSILs) with covalently tethered functional groups to dis-
solve f-elements for the processing of used nuclear fuel [12]. Tak-
ing the advantage of wider electrochemical window of
pyrazolium ILs than some other common ILs such as imidazolium,
sulfonium or guanidinium ILs [13], we incorporated (pyrazol-1-
yl)acetic acid (L) into ILs, which can be deprotonated as a
functionalized pyrazolate anion. Prior to our work, the only re-
ported crystal structure for L with a transition metal was a Cu(II)
complex [14]. We have previously reported four light lanthanide
complexes with L of the general formula [Ln(L)3(H2O)2]
nH2O
(Ln = La, Ce, Pr, n = 2; Ln = Nd, n = 1) [15]. All of the complexes re-
veal a one-dimensional chain structure with tridentate and biden-
tate bridging ligands connecting adjacent lanthanide centers along
the a-axis; however, two different structure types are found with
the structural break occurring between Pr3+ and Nd3+. In addition
to terminal bidentate and bridging tridentate ligands found in La,
Ce and Pr complexes, a third coordination mode (bidentate bridg-
ing) is observed in the Nd complex caused by the lanthanide con-
traction. As a continuation of this study, we report herein eight
complexes with intermediate and heavy lanthanides of the general
formula [Ln(L)3(H2O)2]
H2O (Ln = Eu, 1; Gd, 2; Dy, 3; Ho, 4; Er, 5;

0277-5387/$ - see front matter Ó 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.poly.2013.10.015
 X.-Y. Chen et al. / Polyhedron 68 (2014) 80–86
Yb, 6; Lu, 7) and [HoL(NO3)2(H2O)3] (8) which have been synthe-
sized and structurally characterized by single crystal X-ray diffrac-
tion. Spectroscopic methods (Raman, UV–Vis–NIR absorbance,
diffuse reflectance, and 13C NMR spectroscopies) were used to ex-
plore the coordination chemistry in solution and solid state.
2. Experimental methods
Pyrazole (98%) was used as received from Acros. All other chem-
icals were purchased from Fisher Scientific, Inc., and solutions were
prepared with distilled deionized water (specific resis-
tance P 18.0 MX cm). (Pyrazol-1-yl)acetic acid (L) was prepared
as described in the literature [14]. Stock solutions of L (1 M) were
prepared gravimetrically by dissolving L in water with the pH ad-
justed to 5 by adding NaOH.
Lanthanide stock solutions were prepared by dissolving
Ln(NO3)3
6H2O (99.99% purity) in water. Seven lanthanide(III)
complexes (Eu (1), Gd (2), Dy (3), Ho (4), Er (5), Yb (6), and Lu
(7)) with L were prepared under mild conditions by adding 1 mL
of a 1 M Ln(III) nitrate stock to 3 mL of the L stock solution (1 M)
in a 20 mL borosilicate scintillation vial. The vial was capped and
crystallization of the lanthanide compounds occurred at room tem-
perature within a couple of days. During the crystallization, the
solution pH remained constant at 5. [HoL(NO3)2(H2O)3] (8) was
prepared in the same method using a 1:1 metal to ligand ratio.
Crystals of 1–8 were isolated and their structures were determined
by single crystal X-ray diffraction.
Crystals were removed from the solutions, mounted using a ny-
lon cryoloop and Paratone-N oil, and cooled with a liquid nitrogen
vapor stream. The data were collected on a Bruker D8 diffractom-
eter with an APEX II charge-coupled-device (CCD) detector and a
Bruker Kryoflex low temperature device. The instrument was
equipped with a graphite monochromatized Mo Ka X-ray source
(k = 0.71073 Å). A hemisphere of data was collected using x scans,
with 10-s frame exposures and 0.5° frame widths. Data collection
and initial indexing and cell refinement were handled using APEX
II software [16]. Frame integration, including Lorentz-polarization
corrections, and final cell parameter calculations were carried out
using SAINT+ software [17]. The data were corrected for absorption
using redundant reflections and the SADABS program [18]. Decay of
reflection intensity was not observed as monitored via analysis of
redundant frames. The structure was solved using direct methods
and difference Fourier techniques. Hydrogen atom positions were
idealized on methyl and pyrazole rings, but were not refined on
water molecules. The final refinement included anisotropic tem-
perature factors on all non-hydrogen atoms. Structure solution,
refinement, and creation of publication materials were performed
using SHELXTL [19].
Raman spectra of solid samples were collected for all com-
pounds using a Thermo Scientific DXR SmartRaman spectrometer
with a 780 nm excitation laser. Diffuse reflectance spectra were
measured for ground single crystals using a Cary 5 UV–Vis–NIR
spectrophotometer with a diffuse reflectance attachment, while
solution absorbance spectra were obtained by using a Cary 5
UV–Vis–NIR spectrophotometer. Complex 7 was characterized by
13
C NMR spectroscopy in D2O at room temperature on a Bruker
ARX-300 spectrometer equipped with 5- and 10-mm multinuclear
probes. The frequency was 75 MHz for the 13C nuclei.
3. Results and discussion
The reaction of seven lanthanides with (pyrazol-1-yl)acetic acid
(L) resulted in the formation of crystalline complexes with the gen-
eral formula [Ln(L)3(H2O)2]
H2O (Ln = Eu, 1; Gd, 2; Dy, 3; Ho, 4; Er,
81
5; Yb, 6; Lu, 7) and [HoL(NO3)2(H2O)3] (8). Photographs of the crys-
tals are shown in Fig. 1.
3.1. Single crystal X-ray diffraction studies
Crystal data collection and refinement details for complexes
1–8 are listed in Tables 1 and 2, while selected bond lengths and
angles are provided in the Supporting information (Table S1). Com-
pared to the previously reported structures of lanthanides with
pyrazole-3,5-dicarboxylic acid [10], L only has one carboxylate
group and the acetic acid is substituted directly to one of the
N atom of the pyrazole ring. This substitution excludes the other
N atom from chelating lanthanides, leading to the formation of
one-dimensional chains for complexes 1–8. The different coordina-
tion modes of L observed in 1–3 (terminal bidentate, bridging
bidentate and tridentate), 4–7 (terminal and bridging bidentate),
and 8 (bridging bidentate) result in two distinct crystallographic
structures.
3.1.1. Structural characterization of heavy lanthanide complexes of the
type [Ln(L)3(H2O)2]
H2O
Complexes 4–7 are isostructural, crystallizing in the monoclinic
space group P21/n. Two coordination modes of L are evident in
these complexes: terminal bidentate (Scheme 1a) and bridging
bidentate (Scheme 1b). Fig. 2 shows the coordination environment
of Ho3+ in complex 4 as a representative example. The unit cell of 4
contains the one lanthanide, three L and three water molecules.
The Ho3+ atom is eight-coordinate with two oxygen atoms from
terminal bidentate L, four oxygen atoms from bridging bidentate
L, and two water molecules completing the square antiprismatic
coordination geometry. Bidentate bridging of L in 4 connects Ho1
and Ho1B with a distance of 4.525(1) Å. The least squares planes
of the pyrazole and carboxylate group L show a dihedral angle of
74.55(2)°. The O3–C6–O4 angle is 122.4(2)°. In the second biden-
tate bridging L, the carboxylate group bridges Ho1 and Ho1A with
the Ho–O bond lengths of 2.336(2) and 2.264(2) Å. The resulting
Ho1


Ho1A distance is 4.895(1) Å. The difference between the
two C–O bond lengths in a single carboxylate group of L follows
a different order in 4: terminal bidentate (0.01 Å) > bridging biden-
tate (0.001 Å). Such a trend indicates the weakest electron delocal-
ization occurs in the carboxylate group of the terminal bidentate L,
totally opposite from the previous observation. The bidentate
bridging L links neighboring Ho3+ ions to form a one-dimensional
chain structure with alternating Ho


Ho distances of 4.525(1)
and 4.895(1) Å (Fig. 3).
3.1.2. Structural characterization of [HoL(NO3)2(H2O)3]
Complex 8 was obtained by varying the metal to ligand ratio to
1:1 and crystallizes in the monoclinic space group P21/c. In con-
trast to the eight-coordinate Ho in (4), the Ho in 8 is nine-coordi-
nate with two oxygen atoms from two bridging bidentate L
molecules (Scheme 1b), four oxygen atoms from two nitrate an-
ions, and three coordinated water molecules (Fig. 4). The coordina-
tion geometry of Ho3+ can be described as a tricapped trigonal
prism. Bidentate L bridges the Ho3+ ions to form an extended chain
structure along the c axis with the Ho1–O1 and Ho1A–O2 bond
lengths of 2.293(2) and 2.256(1) Å, respectively. The difference be-
tween the bond lengths of C1–O1 (1.250(2) Å) and C1–O2
(1.264(2) Å) is larger than that of the bidentate bridging ligands
in complex 4, indicating a weaker electron delocalization. The
Ho


Ho distance is 5.704(1) Å, which is significantly larger than
that in complex 4 (4.895(1) Å). The average Ho–O bond length
for coordinated water molecules of 2.391(2) Å is comparable to
that in 4 (2.378(2) Å). The pyrazole rings in the one-dimensional
chain are almost parallel to each other with the dihedral angle of
1.86(9)°.
82 X.-Y. Chen et al. / Polyhedron 68 (2014) 80–86

Fig. 1. Photographs of single crystals [Ln(L)3(H2O)2]
H2O, Ln = Eu (A), Gd (B), Dy (C), Ho (D), Er (E), Yb (F), and Lu (G) and [HoL(NO3)2]
3H2O (H).

Table 1
Selected crystal data and structure refinements for [Ln(L)3(H2O)2]
H2O (Ln = Eu, 1; Gd, 2; Dy, 3; Ho, 4).

1 2 3 4
T (K) 140(1) 140(1) 140(1) 140(1)
Formula C15H21EuN6O9 C15H21GdN6O9 C15H21DyN6O9 C15H21HoN6O9
Formula weight 581.34 586.63 591.88 594.31
Crystal system monoclinic monoclinic monoclinic monoclinic
Space group P21/n P21/n P21/n P21/n
a (Å) 9.2515(5) 9.2490(7) 9.2976(8) 9.348(1)
b (Å) 15.3810(8) 15.3574(11) 15.2803(13) 15.2182(16)
c (Å) 14.4142(7) 14.4077(11) 14.3756(13) 14.3622(15)
b (°) 100.2910(10) 100.360(1) 100.969(1) 101.452(1)
V (Å3) 2018.11(18) 2013.1(3) 2005.0(3) 2002.5(4)
Z 4 4 4 4
q (g/cm3) 1.913 1.936 1.961 1.971
l (mm 1) 3.170 3.357 3.790 4.014
F(0 0 0) 1152 1156 1164 1168
Crystal size (mm) 0.24  0.06  0.02 0.22  0.04  0.02 0.24  0.06  0.04 0.20  0.06  0.04
h (°) 1.95–28.45 1.96–28.43 1.96–28.35 1.97–28.52
Index ranges 12 6 h 6 12, 12 6 h 6 12, 12 6 h 6 12, 12 6 h 6 12,
20 6 k 6 20, 20 6 k 6 20, 20 6 k 6 20, 20 6 k 6 20,
19 6 l 6 19 18 6 l 6 19 19 6 l 6 18 19 6 l 6 19
Minimum and maximum transmission 0.5166 and 0.9393 0.5254 and 0.9359 0.4632 and 0.8632 0.5007 and 0.8559
Goodness-of-fit (GOF) on F2 1.493 0.773 1.569 1.128
R1, R2 [I > 2r(I)] 0.0218, 0.0619 0.0243, 0.0844 0.0220, 0.0634 0.0232. 0.0474
R1, R2 (all data) 0.0263, 0.0637 0.0315, 0.0948 0.0259, 0.0650 0.0302, 0.0501
3
Largest difference in peak and hole (e Å ) 1.032, 0.765 0.948, 1.530 0.889, 0.842 0.666, 0.715

3.1.3. Structural characterization of intermediate lanthanide
complexes of the type [Ln(L)3(H2O)2]
H2O
Complexes 1–3 are isostructural with the previously published
structure of [Nd(L)3(H2O)2]
H2O [15], crystallizing in the mono-
clinic space group P21/n, with bidentate and tridentate bridging
(Scheme 1c) ligands forming an extended one-dimensional chain.
In the following, complex 1 is chosen to discuss the crystallo-
graphic features found in complexes 1–3. The unit cell contains
one unique Eu3+ center, three deprotonated ligands as monoanions
and two coordinated water molecules with one lattice water mol-
ecules (Fig. 5). As observed previously for [Nd(L)3(H2O)2]
H2O [15],
three coordination modes of L are present in complex 1: terminal
bidentate, bridging bidentate and tridentate modes. The tridentate
bridging L links Eu1 and Eu1B with a distance of 4.351(1) Å, which
is slightly shorter than the Nd


Nd distance (4.379(1) Å) in
[Nd(L)3(H2O)2]
H2O [15]. The Eu1–O3 and Eu1–O4 bond lengths
are 2.451(2) and 2.716(2) Å, respectively, which are more diverged
than the corresponding Nd–O distances (2.501(2) and 2.705(2) Å)
in [Nd(L)3(H2O)2]
H2O [15]. The Eu1B–O4 bond length
(2.406(2) Å) with the bridging l3–oxygen atom is shorter than
those of Eu1–O3 and Eu1–O4. The Eu1–O4–Eu1B bond angle is
116.18(7)°, which is similar to that of Nd–O–Nd (115.93(8)°) in
[Nd(L)3(H2O)2]
H2O [15]. For the tridentate bridging L, the C-O
bond lengths of the carboxylate group are 1.247(3) and
1.268(3) Å, which suggest that there is some electron delocaliza-
tion in the carboxylate groups compared with the C–O bond
lengths of the carboxylate group in the free ligand (1.207(2) and
1.309(2) Å) [14]. Such electron delocalization is even larger than
that in [Nd(L)3(H2O)2]
H2O (C–O, 1.243(3) and 1.274(3) Å) [15].
Within the tridentate ligand, the dihedral angle of the least squares
 X.-Y. Chen et al. / Polyhedron 68 (2014) 80–86 83

Table 2
Selected crystal data and structure refinements for [Ln(L)3(H2O)2]
H2O (Er, 5; Yb, 6; Lu, 7) and [HoL(NO3)2(H2O)3] (8).

5 6 7 8
T (K) 293(2) 140(1) 140(1) 140(1)
Formula C15H21ErN6O9 C15H21N6O9Yb C15H21LuN6O9 C5H11HoN4O11
Formula weight 596.64 602.42 604.35 468.11
Crystal system monoclinic monoclinic monoclinic monoclinic
Space group P21/n P21/n P21/n P21/c
a (Å) 9.4051(7) 9.4451(7) 9.4740(8) 11.0734(8)
b (Å) 15.1458(11) 15.0869(12) 15.0368(13) 13.8862(11)
c (Å) 14.3526(10) 14.3477(11) 14.3392(12) 8.7857(7)
b (°) 101.954(1) 102.482(1) 102.857(1) 112.267(1)
V (Å3) 2000.2(3) 1996.2(3) 1991.5(3) 1250.21(17)
Z 4 4 4 4
q (g/cm3) 1.981 2.005 2.016 2.487
l (mm 1) 4.259 4.748 5.020 6.399
F(0 0 0) 1172 1180 1184 896
Crystal size (mm) 0.20  0.14  0.06 0.20  0.04  0.02 0.12  0.08  0.06 0.20  0.06  0.02
h (°) 1.98–28.43 1.98–28.35 1.99–28.37 1.99–28.47
Index ranges 12 6 h 6 12, 12 6 h 6 12, 12 6 h 6 12, 14 6 h 6 14,
19 6 k 6 20, 19 6 k 6 19, 19 6 k 6 19, 17 6 k 6 18,
19 6 l 6 19 18 6 l 6 18 18 6 l 6 19 11 6 l 6 11
Minimum and maximum transmission 0.4830 and 0.7842 0.4502 and 0.9110 0.5841 and 0.7527 0.3610 and 0.8827
Goodness-of-fit (GOF) on F2 1.153 1.206 1.482 1.295
R1, R2 [I > 2r(I)] 0.0204, 0.0429 0.0244, 0.0608 0.0182, 0.0537 0.0140, 0.0341
R1, R2 (all data) 0.0265, 0.0450 0.0331, 0.0642 0.0213, 0.0551 0.0155, 0.0350
3
Largest difference in peak and hole (e Å ) 0.592, 0.608 1.173, 0.854 0.855, 0.725 0.635, 0.648

Scheme 1. Coordination modes of (Pyrazol-1-yl)acetic acid in complexes 1–8.

Fig. 3. One-dimensional chain of [Ho(L)3(H2O)2]
H2O (4). Ho, green; C, grey; O, red;

N, blue. The hydrogen atoms and the lattice water molecules have been removed for
clarity. (Color online.)

The carboxylate group in the bidentate bridging L bridges Eu1

Fig. 2. The coordination environment of Ho(III) in [Ho(L)3(H2O)2]
H2O (4) showing
the relevant atom labeling scheme. The hydrogen atoms and the lattice water
molecules have been removed for clarity.
planes of the pyrazole ring (N3, N4, C8, C9 and C10) and carboxyl-
ate group (C6, O3 and O4) is 75.25(20)°, which is smaller than
those in the free L (80.76(6)°) and in [Nd(L)3(H2O)2]
H2O
(79.68(12)°) [15].
and Eu1A with the Eu–O bond lengths of 2.321(2) and 2.403(2) Å
and the Eu1


Eu1A distance is 4.991(1) Å. The least squares planes
of the pyrazole and carboxylate group of the bidentate bridging L
show a larger dihedral angle of 80.97(20)° than that in the triden-
tate ligand. In the bidentate terminal ligand, the dihedral angle of
the least squares planes of the pyrazole and carboxylate group in
the bidentate L is 88.07(30)°, which is much larger than found in
the tridentate L. The difference between the two C–O bond lengths
in a single carboxylate group of L decreases in the following order:
tridentate bridging (0.021 Å) > bidentate bridging (0.01 Å) > termi-
nal bidentate (0.001 Å). Such a trend indicates that the strongest
electron delocalization occurs in the carboxylate group of the
84 X.-Y. Chen et al. / Polyhedron 68 (2014) 80–86
Fig. 4. The coordination environment of Eu(III) in [Eu(L)3(H2O)2]
H2O (1) showing
the relevant atom labeling scheme. The hydrogen atoms and the lattice water
molecules have been removed for clarity.
Fig. 5. One-dimensional chain of [Eu(L)3(H2O)2]
H2O (1). Eu, green; C, grey; O, red;
N, blue. The hydrogen atoms and the lattice water molecules have been removed for
clarity. (Color online.)
terminal bidentate L, as observed previously for the light lantha-
nide complexes with L [15]. The two coordinated water molecules
are cis to each other with an O7–Eu1–O8 angle of 67.93(7)°. Each
Eu3+ ion is connected to the neighboring Eu3+ ions by alternate tri-
dentate and bidentate bridging L forming one-dimensional chain
along the a-axis (Fig. 6), with the Eu


Eu distances alternating be-
tween 4.991(1) and 4.351(1) Å.
3.1.4. Structural comparison across the lanthanide series
The structural break between Dy (3) and Ho (4) revealed by sin-
gle crystal X-ray diffraction analysis can be explained by the
lanthanide contraction [20]. The lanthanide series can be divided
into three groups according to ionic radii: the lighter La–Pm
(Group 1), the intermediate Sm–Dy (Group 2), and the heavier
Ho–Lu (Group 3). As shown in Fig. 7, the average Ln–O bond
lengths with the terminal bidentate L, bridging bidentate L, and
coordinated water molecules shorten with decreasing ionic radii
[21] in accordance with the well-known lanthanide contraction
[20]. For the carboxylate group in the tridentate bridging L, the
Ln–O3 bond lengths decrease while the Ln–O4 (l3–bridging oxy-
gen) bond lengths increase. With the continuous elongation of
the Ln–O4 bond, the breakage of the Ln–O4 bond was observed
at Ho (4) resulting in the coordination mode change of the triden-
tate bridging to bidentate bridging. The Ln


O4 distances for Ho,
Er, Yb and Lu are shown as unconnected red squares in Fig. 7.
3.2. Spectroscopic characterization of solid-state and solution species
3.2.1. Solid-state Raman spectroscopy
The solid-state FT-Raman spectra for all the lanthanide com-
pounds are very similar (1 is shown in Fig. 8 as an example). We
have previously reported the Raman spectroscopic characteriza-
tion of (pyrazol-1-yl)acetic acid [15]. Consistent with a longer
C@O bond length (1.247(3)–1.261(3) Å), the carboxylate symmet-
ric stretching (m(C@O)) mode in the Eu3+ complex (1) at
1587 cm 1 is shifted to lower frequency compared to the free li-
gand (1707 cm 1, 1.207(2) Å) [14]. The Raman shift at 1463 cm 1
is assigned to the pyrazole ring stretching mode [22]. Upon coordi-
nation with Eu3+, the C–O symmetric and asymmetric stretching
modes are shifted slightly to 1287 and 1167 cm 1 compared to
the free ligand (1300 and 1174 cm 1) [15]. The peak at
1327 cm 1 can be assigned as either the pyrazole ring stretching
mode or the d(C–OH) bending mode. Similar peak shifts and inten-
sity changes have been reported for the light lanthanide complexes
with L [15]. The medium–strong to strong peaks at 1394 and
1097 cm 1 in 1 are due to the pyrazole ring stretching modes
[22]. These ring stretching peaks shift to lower frequencies with
additional shoulder peaks caused by the different coordination
modes of L in the lanthanide complexes compared with those in
the free ligand (1406 and 1098 cm 1) [15]. The strong peak at
1066 cm 1 is assigned as C–H in-plane bending vibration mode
[23]. Similar peak shifts and splitting can be seen for the pyrazole
ring bending mode with multiple peaks around 946 and 930 cm 1
in 1. The weak Raman band at 797 cm 1 is attributed to the d(CH)
bending mode. The multiple peaks around 722 and 709 cm 1 can
be assigned as the bending mode of d(O@CO), which shift to higher
frequency compared to the free ligand (664 cm 1) [15]. In the low
wavenumber region of the complex, we observe a weak band at
431 cm 1, which might be a combination of ring bending modes
and a new Eu–O vibration mode [23,24].
3.2.2. UV–Vis–NIR spectroscopy
In order to compare coordination modes in solid-state and solu-
tion, we compared the solid-state diffuse reflectance spectra of
[Ln(L)3(H2O)2]
H2O (Ln = Eu (1), Dy (3), Ho (4), and Er (5)) with
the UV–Vis–NIR absorption spectra of the corresponding solid dis-
solved in water (Figs. S1–S3). The electronic absorbance spectra for
trivalent lanthanide complexes are characterized by a number of
Laporte-forbidden f–f transitions [25]. In the solution UV–Vis–
NIR spectra, the molar absorptivities of all complexes are similar
with those of the Ln3+(aq) ion in dilute perchloric acid. The
UV–Vis–NIR spectrum of compound 4 dissolved in water (Fig. 9)
displays the characteristic transitions for the Ho3+ aquo ion at
361 (5I8 to 3H6), 416 (5I8 to (5G, 3G)5), 451 (5I8 to 5F1), 468 (5I8 to
5
G4), 473 (5I8 to 5F2), 485 (5I8 to 5F3), 537 (5I8 to 5F4 (5S2)), 641
(5I8 to 5F5), and 656 (5I8 to 5F5) nm. The molar absorptivity of 2.5
L mol 1 cm 1 at 451 nm is comparable to that reported for the
 X.-Y. Chen et al. / Polyhedron 68 (2014) 80–86
Fig. 6. Thermal ellipsoids (50% probability) of [HoL(NO3)2(H2O)3] (8). The hydrogen atoms and the lattice water molecules have been removed for clarity.
Fig. 7. Comparison of the average Ln–O bond lengths with decreasing ionic radii.
Ln–Oterminal bidentate, blue; Ln–O3, purple; Ln–O4, red; Ln–O5, green; Ln–Owater,
black. The Ho–Obridging bidentate bond length in 8 is shown as green triangle. Ionic
radii for eight- and nine-coordinate lanthanide cations were taken from Shannon
[21]. (Color online.)
Fig. 8. Solid-state Raman spectrum of [Eu(L)3(H2O)2]
H2O (1).
Ho(aq)3+ ion in dilute perchloric acid (2.9 L mol 1 cm 1) [25a].
However, the solid state diffuse reflectance spectra of 4 does not
match the absorbance of the corresponding solution species at
pH 5, suggesting different coordination environments around the
lanthanide ion in solution and solid state. Both relative intensity
ratios and peak shapes differ in the solution and solid state spectra
with peaks shifted up to 4 nm.
85
Fig. 9. Solid state UV–Vis–NIR diffuse reflectance spectrum (red) of [Ho(L)3(H2-
O)2]
H2O (4) and UV–Vis–NIR absorbance spectrum of [Ho(L)3(H2O)2]
H2O (4)
dissolved in water (black). The Ho3+(aq) absorbance peaks in dilute perchloric acid
are shown as dotted lines [25a]. (Color online.)
3.2.3. 13C NMR Spectroscopy of Solution Species
13
C NMR spectroscopy was used to further explore the coordi-
nation of L with the Ln(III) ions in solution. The 13C NMR spectrum
of the diamagnetic Lu(III) complex 7 dissolved in D2O (pH 5) dis-
plays 13C NMR features at 54.38, 106.02, 132.09, 139.86, and
176.22 ppm, which shifted from those of the free ligand
(52.24 ppm (CH2), 106.61 (CH), 132.90 (CH), 139.81 (CH),
172.23 ppm (COOH)) [15]. The coordination-induced shift (Dd) of
3.99 ppm for the COOH group is caused by the coordination of
the Ln(III) ion with L via the carboxylate groups and the associated
deshielding of the carboxylate carbon atom. A similar Dd value of
4.08 ppm (COOH) was observed for the La3+ complex reported pre-
viously [15]. The methylene carbon (CH2COOH) exhibits a larger
Dd value of 2.14 ppm than the pyrazole ring carbon (maximum
Dd of 0.81 ppm) due to its closer proximity to the Lu3+ ion. Only
one set of signals was present in the 13C NMR spectrum of 7, indi-
cating that all coordinated ligands in the Lu3+ solution complex are
equivalent. The absence of NMR shifts characteristic of the uncom-
plexed ligand indicates that all ligand is bound to Lu3+ in solution.
4. Conclusion
We have synthesized and characterized eight novel lanthanide
complexes with (pyrazol-1-yl)acetic acid (L) of the general formula
[Ln(L)3(H2O)2]
H2O (Ln = Eu, 1; Gd, 2; Dy, 3; Ho, 4; Er, 5; Yb, 6; Lu,
86 X.-Y. Chen et al. / Polyhedron 68 (2014) 80–86
7) and [HoL(NO3)2(H2O)3] (8). Complexes 1–7 were prepared using
a 1:3 metal to ligand ratio. Although complexes 1–7 possess a one-
[4]
dimensional chain structure along the a-axis, two different struc-
ture types are found with the structural break occurring between
Dy3+ (3) and Ho3+(4). Three coordination modes of L were found [5]
[6]
in 1–3: terminal bidentate, bridging bidentate, and bridging triden-
tate. The tridentate bridging L changes to bidentate bridging in 4–7 [7]
caused by the smaller ionic radii of the Ln(III) ions heavier than [8]
Dy3+. The change from a tridentate bridging to bidentate bridging
mode also decreases the coordination number of the Ln3+ ions from
nine (1–3) to eight (4–7). Complex 8 was prepared using a 1:1 me-
tal to ligand ratio, and contains only bidentate bridging ligands in
the crystal structure.
The shifts and intensity changes between the solid state UV– [9]
Vis–NIR diffuse reflectance spectra and the solution UV–Vis–NIR
spectra suggest a different coordination environment of Ln(III)
with L in solution and solid state. A single set of ligand NMR shifts,
different from those of the free ligand in solution, indicates one
type of Ln3+–L solution species. Both NMR and vibrational spectro-
scopic data clearly identify that the carboxylate group in L partic-
ipates in the Ln(III) bonding. This information on the structure and
bonding of lanthanide(III) with (pyrazol-1-yl)acetic acid in solution [10]
and solid state aids our fundamental understanding of the lantha-
nide coordination with new TSILs composed of deprotonated (pyr-
azol-1-yl)acetic acid as anion for recycling of trivalent f-elements
in used nuclear fuel. [11]
[12]
Acknowledgements
The authors gratefully acknowledge the Laboratory-Directed
[13]
Research and Development Program and the G.T. Seaborg Institute
for Transactinium Science at Los Alamos National Laboratory for
financial support during this project.
[14]
Appendix A. Supplementary data
[15]
CCDC 943459–943466 contain the supplementary crystallo- [16]
graphic data for complex 1–8. These data can be obtained free of [17]
charge via http://www.ccdc.cam.ac.uk/conts/retrieving.html, or [18]
[19]
from the Cambridge Crystallographic Data Centre, 12 Union Road, [20]
Cambridge CB2 1EZ, UK; fax: +44 1223-336-033; or e-mail: depos- [21]
it@ccdc.cam.ac.uk. Supplementary data associated with this article [22]
can be found, in the online version, at http://dx.doi.org/10.1016/
[23]
j.poly.2013.10.015. [24]
[25]
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