Article

pubs.acs.org/crystal

Hydrogen Bonding Dependent Mesoscale Framework in Crystalline

Ln(H2O)9(CF3SO3)3
Congting Sun, Xiaoyan Chen, and Dongfeng Xue*
State Key Laboratory of Rare Earth Resource Utilization, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences,
Changchun 130022, China
*
S Supporting Information

ABSTRACT: Structurally, hydrogen bonding is identified as a key factor to

domain the construction of a crystallographic frame during the
crystallization of the Ln(H2O)9(CF3SO3)3 (Ln = La−Lu) system. In situ
Raman spectroscopy is used to capture the hydrogen bonding dependent
mesoscale frameworks that are formed during Ln(H 2O)9(CF3SO3)3
crystallization in aqueous solution by continuously collecting the spectra
of structural fragments. The spectral characteristics show that the isolated
Ln(H2O)93+ tricapped trigonal prisms cannot exist in the aqueous solution.
With the concentration of aqueous solution, the hydrated Ln3+ and CF3SO3−
tend to share common H2O molecules, and new hydrogen bonding will be
built surrounding Ln3+. Especially, for the Nd, Eu, Yb, and Lu system, Ln(H2O)n(CF3SO3)3 (n = 8−9) clusters instead of
hydrated Ln3+ and CF3SO3− are formed in the solution. Under the guiding of intermolecular hydrogen bonds, both bond lengths
and bond angles of Ln−O may be regulated, leading to the initial formation of Ln(H2O)63+ prisms and the following Ln(H2O)93+
tricapped trigonal prisms. Meanwhile, the symmetry of both CF3 and SO3 groups decreases from C3h to C2 accompanied by the
formation of Ln(H2O)63+ triprism. The present study opens up the chemical bonding behaviors of rare earth ions in aqueous
solution, which provides basic data for the study of the coordination of rare earth complexes and the design of novel rare earth
materials.

■ INTRODUCTION
Uncovering the materials formation process serves as a
theoretical cornerstone in the design of novel functional
materials with particular components and structures.1,2 In
kinetics, the possible nucleation approaches become more
complex with increasing the inorganic materials components
from binary to ternary, quaternary, and multicomponent,
increasing the difficulty in initial judgment and identification
of their formation mechanism. Two pathways have been
clarified in the formation of crystalline materials, the classical
nucleation process in the monomer-by-monomer addition
mode3,4 and the oriented-attachment by the addition of
particles.5 Especially, the prenucleation clusters have been
identified before the formation of crystalline nuclei, and the
phase transition from amorphous to crystalline state occurs at
the nucleation stage.6 In the design of required crystalline
structure, more details about the structural formation and
evolution before the long-range ordered crystallographic
structure are always urgently needed.7 It favors to disclose
the formation mechanism of multicomponent materials at the
atom or molecule level.
In order to identify the formation approach of multi-
component materials in aqueous solution, both initial and final
existence forms should be ascertained primarily. Progress has
been made in Ln3+ (Ln = lanthanide) complexation separation
chemistry and in the field of coordination and structural
chemistry of hydrated Ln3+ ions in both solid and solution
states.8,9 However, the identification of the structure of metal
aqua ions in solution still faces challenges since it has no long-
range ordered structure, and we cannot deduce it on the basis
of the apparently simple distribution of water molecules around
a monatomic cation.10 Moreover, the liquid state usually
presents more diffuse coordination geometries around a metal
ion in solution. Ln(H2O)9(CF3SO3)3 (Ln = La−Lu) acts as a
representative system to study the structural chemistry of
hydrated Ln3+.11 The hydration of Ln3+ in aqueous solution and
crystalline was studied by extended X-ray absorption fine
structure (EXAFS) spectroscopy.12,13 The results show that the
Ln K- and L3-edge EXAFS spectra of hydrated Ln3+ in aqueous
solution are similar to that of hydrated trifluoromethanesulfo-
nate salt. The structure of hydrated Ln3+ in aqueous solution is
therefore proposed in analogy to that in crystalline Ln-
(H2O)9(CF3SO3)3, i.e., possessing tricapped triple prism
geometry. However, a recent study shows that a square
antiprism coordination geometry is preferred for 8-coordinated
hydrated Lu3+, while 9-coordinated hydrated Ln3+ (such as
La3+) favors adoption of a Gyro-elongated square antiprism
geometry instead of a tricapped trigonal prism on the basis of
angular distribution function associated with the oxygen−metal
ion-oxygen angle.14
Received: January 28, 2017
Revised: April 10, 2017
Published: April 13, 2017

© XXXX American Chemical Society A DOI: 10.1021/acs.cgd.7b00145

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Crystal Growth & Design
Previous studies show that molecular vibrational spectrosco-
py is instrumental in revealing detailed information on inter-
and intramolecular interactions during crystallization via
tracking subtle changes in the vibrational bands.15−18 However,
when Ln(H2O)9(CF3SO3)3 samples are dissolved in the water,
the free CF3SO3− group and H2O will promote the hydrolysis
in solution to produce a large amount of H3O+, resulting in the
strongly acidic aqueous solution. For example, the concen-
tration of H+ in 1 mol/L Ln(H2O)9(CF3SO3)3 aqueous
solution is in the range of 0.16−2.88 mol/L. Attenuated total
reflection-infrared (ATR-IR) spectral measurements require the
samples to be soft, noncorrosive, and close to neutral. Strongly
acidic Ln(H2O)9(CF3SO3)3 aqueous solution will react with
Fe-based sample holder, limiting the in situ ATR-IR
observation of the formation process of crystalline Ln(H2O)9-
(CF3SO3)3. Consequently, in situ Raman spectroscopy has
been selected to record the formation and evolution of the
mesoscale framework in Ln(H2O)9(CF3SO3)3 solution, since
the strongly acidic aqueous solution can be dropped onto the
glass substrate in the measurement. Compared with IR
spectroscopy, Raman measurements always need longer
collection time, i.e., several minutes and even over 10 min.19
This will miss much more important structural information for
the dynamic mesoscale frameworks during the crystallization of
Ln(H2O)9(CF3SO3)3. In order to shorten the measurement
time, successive Raman spectra were collected within a short
range of wavenumbers.20,21
In the present study, in situ Raman spectroscopy was applied
to observe in real time the formation process of crystalline
Ln(H2O)9(CF3SO3)3 (Ln = La−Lu) in aqueous solution.
Successive Raman measurements were carried out within a
smaller range of wavenumbers in order to collect the structural
information within a short time. The spectral characteristics can
be used to identify the coordination geometry of constituent
groups, such as Ln(H2O)n3+ and CF3SO33−. Moreover, the
aggregation between these groups can also be deduced by
tracking the evolution of Raman vibration bands since the
geometric features of constituent groups are directly influenced
by the surrounding local structure in hydrated ions, clusters,
and crystalline nuclei.
■ EXPERIMENTAL SECTION
Crystalline Ln(H2O)9(CF3SO3)3 (Ln = La, Pr, Nd, Sm−Lu) samples
were self-synthesized in the lab. Ln2O3 powders (purity is higher than
99.99%) were first dissolved in HCF3SO3 aqueous solution, in which
the molar ratio between Ln2O3 and HCF3SO3 is 1:6. Then the as-
obtained mixture was filtered to obtain pellucid aqueous solution. The
pellucid solution was concentrated in oven at 80 °C, and then the solid
Ln(H2O)9(CF3SO3)3 samples would be obtained. In order to remove
the excess HCF3SO3 in our as-prepared Ln(H2O)9(CF3SO3)3 samples,
we continuously heated the solid Ln(H2O)9(CF3SO3)3 until no gas
volatilized from the glass beaker. Finally, the solid samples were
dissolved in deionized water, and Ln(H2O)9(CF3SO3)3 (Ln = La, Pr,
Nd, Sm−Lu) would be crystallized from the supersaturated aqueous
solution. Especially, the crystalline Ce(H2O)9(CF3SO3)3 sample was
prepared via dissolving Ce(NO3)3·6H2O in HCF3SO3 to obtain
Ce(H2O)9(CF3SO3)3 aqueous solution, and then crystallized as the
other Ln(H2O)9(CF3SO3)3 samples. Finally, we prepared Ln(H2O)9-
(CF3SO3)3 (Ln = La−Nd, Sm−Lu) aqueous solutions with a
concentration of 1 mol/L.
In situ Raman spectral measurements of the as-prepared Ln-
(H2O)9(CF3SO3)3 (Ln = La−Nd, Sm−Lu) solution were carried out
at 22 °C by laser Raman spectrometry. The green line of Ar+ laser
(514.5 nm radiation) serves as the laser source, and in situ Raman
spectra of Ln(H2O)9(CF3SO3)3 (Ln = La−Nd, Sm−Lu) solution were
B DOI: 10.1021/acs.cgd.7b00145
Article
recorded using a Jobin-Yvon Horiba T64000 Raman triple grating
spectrometer (Horiba Ltd., France). The frequency was calibrated by
the Raman band of silicon at 520 cm−1 before the Raman
measurements. 2.5 μL Ln(H2O)9(CF3SO3)3 solution was added on
the glass substrate with a diameter of about 2 mm, and then successive
Raman measurements were carried out using Mapping properties
mode per 1 min (Figures S1−S14) until the formation of crystalline
Ln(H2O)9(CF3SO3)3 on the glass. For crystalline Ln(H2O)9-
(CF3SO3)3 samples, the Raman spectra were recorded in the 200−
1400 cm−1 frequency range with a precision of 1 cm−1, and the Raman
spectral assignments are shown in Figure S15, which can be used to
identify the group information on mesoscale structures in the
crystallization of Ln(H2O)9(CF3SO3)3.
■
RESULTS AND DISCUSSION
Crystallographic structure of Ln(H2O)9(CF3SO3)3 (Ln = La−
Nd, Sm−Lu) shows interesting Ln(H2O)93+ tricapped trigonal
prisms in the lattice with the highest D3h point group symmetry
(Figure S16).11 These Ln(H2O)93+ tricapped trigonal prisms
are linked with CF3SO3− groups by hydrogen bonding,
resulting in the formation of hexagonal lattice within the P63/
m space group. Such a structure will be formed via the
nucleation process in aqueous solution system with concen-
tration. Materials formation is a multiscale phase transition
process, involving the transition from constituent ions/
molecules to clusters and crystalline materials. During such a
phase transition, a variety of dynamic mesoscale frameworks
will be generated and disappeared. Their scale locates in the
range from ions/molecules to clusters. As shown in Scheme 1,
Scheme 1. Possible Routes in the Formation of Crystalline
Ln(H2O)9(CF3SO3)3 Nuclei from Aqueous Solution
two approaches may exist in the nucleation. In approach 1, the
hydrated Ln3+ with tricapped trigonal prism structure (Ln-
(H2O)93+) can be stabilized in the aqueous solution. With the
concentration of solution, the hydrated CF3SO3− group
dehydrates and links with the Ln(H2O)93+ tricapped trigonal
prism by reforming hydrogen bonding. The whole process only
involves the regulation of relative position between Ln(H2O)93+
and CF3SO3−. In approach 2, a more complex nucleation
process will occur. No Ln(H2O)93+ tricapped trigonal prisms
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Crystal Growth & Design Article

Figure 1. In situ Raman spectra of the nucleation process in La(H2O)9(CF3SO3)3 (A), Ce(H2O)9(CF3SO3)3 (B), Pr(H2O)9(CF3SO3)3 (C),
Nd(H2O)9(CF3SO3)3 (D), Sm(H2O)9(CF3SO3)3 (E), Eu(H2O)9(CF3SO3)3 (F), Gd(H2O)9(CF3SO3)3 (G), Tb(H2O)9(CF3SO3)3 (H),
Dy(H2O)9(CF3SO3)3 (I), Ho(H2O)9(CF3SO3)3 (J), Er(H2O)9(CF3SO3)3 (K), Tm(H2O)9(CF3SO3)3 (L), Yb(H2O)9(CF3SO3)3 (M), and
Lu(H2O)9(CF3SO3)3 (N) aqueous solutions in the range of 280−400 cm−1. The red dotted line guides the v5(Trifl) and E′v(LnO6), the blue dotted
line guides the shift of Raman bands at ∼328 cm−1 after the structural transition.

C DOI: 10.1021/acs.cgd.7b00145
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exist in the aqueous solution, and only hydrated Ln3+− indicating no hydrated Ln3+ with trigonal prism or tricapped
CF3SO3− solvent-separated ion pairs exist in the solution. With trigonal prism configuration that exists in the solution. With
the concentration of aqueous solution, hydrated Ln3+− prolonging the measurement time, v5(Trifl) shifts toward lower
CF3SO3− solvent-separated ion pairs begin to share common wavenumbers. This can be attributed to the formation of
H2O molecules, and new hydrogen bonding will be built. hydrogen bonding between hydrated Ln3+ and CF3SO3−.
Under the guiding of these intermolecular hydrogen bonds, Owing to the smaller ionic electronegativity (EN) of La3+
both bond length and bond angle of Ln−O may be regulated, than that of H,26,27 the v(C−S) vibration band shifts toward
leading to the formation of Ln(H2O)63+ prisms and even lower wavenumbers with the linkage between hydrated La3+
Ln(H2O)93+ tricapped trigonal prisms. Moreover, the relative and CF3SO3−. The rocking vibration of SO3 at ∼354 cm−1
position between Ln3+, CF3SO3−, and H2O will be changed to remains nearly unchanged,28,29 indicating the unchanged
construct crystalline Ln(H2O)9(CF3SO3)3. Clarifying the symmetry of SO3. In such a case, the ratio between the relative
mesoscale structures during the crystallization process will intensity of v(C−S) and ρr(SO3) remains identical. Once the
favor enclosing of the formation mechanism of Ln(H2O)9- La(H2O)63+ triple prism is formed in the aqueous system,
(CF3SO3)3 (Ln = La−Nd, Sm−Lu) crystalline samples. E′v(LaO6-prism) at 315 cm−1 appears in Raman spectra. As
In situ Raman experiments have been carried out to track the shown in Figure 2, there is a sharp shift from 321 to 315 cm−1.
formation process of Ln(H2O)9(CF3SO3)3 (Ln = La−Nd, Sm−
Lu) in aqueous solution. The assignment of Raman frequencies
in the spectra of Ln(H2O)93+ complexes is more difficult than
that for octahedral hexaaqua complexes, owing to the
appearance of very strong bands of the CF3SO3− (trifluor-
omethanesulfonate, trifl.) in the Ln−O stretching region.22
Moreover, three capping “equatorial” water molecules with
slightly weaker Ln−O bonding will result in very weak Raman
vibration bands at lower wavenumbers. Previous work has
demonstrated that Raman vibration bands at ∼315 cm−1 can be
assigned to E′v(LnO6) prism.22 From La(H2O)93+ to Lu-
(H2O)93+, E′v(LnO6) shifts toward higher wavenumbers.
Moreover, v5(Trifl) (i.e., v(C−S)) vibration band appears at
∼328 cm−1 and v11(Trifl) (i.e., ρr(SO3)) vibration band appears
at ∼350 cm−1 in Raman spectra.22,23 For the CF3SO3− group,
the evolution of Raman vibration bands would remain
consistent. Therefore, we can identify the E′v(LnO6) and
v5(Trifl) by comparing the shift of vibration bands in Raman
spectra. Figure 1 shows the time-dependent Raman spectra of
the nucleation process in Ln(H2O)9(CF3SO3)3 aqueous
solution in the range of 280−400 cm−1. In such a detection
region, the structural information on LnO6 prism, C−S, and
SO3 will be reflected. For light rare earth trifluoromethanesul-
fonate aqueous solution (Ln = La−Gd) except Nd and Eu
(Figure 1A−C,E,G), Raman vibration bands at ∼315 cm−1 Figure 2. Possible molecular configuration evolution of hydrated La3+
shifts toward lower wavenumbers, while v11(Trifl) nearly in La(H2O)9(CF3SO3)3 aqueous solution deduced by in situ Raman
remains unchanged during the nucleation process. Moreover, spectra. (A) Time-dependent Raman spectra of La(H2O)9(CF3SO3)3
the ratio between the heights of two Raman bands respectively aqueous solution in the range of 225−400 cm−1. (B) Molecular
at ∼315 cm−1 and ∼350 cm−1 increases with the proceeding of configuration evolution of hydrated La3+ from the initial hydrated state
to La(H2O)6 trigonal prism and La(H2O)9 tricapped trigonal prism.
nucleation. However, for Nd(H2O)9(CF3SO3)3 (Figure 1D)
and Eu(H2O)9(CF3SO3)3 (Figure 1F) aqueous solutions, no
changes are found in the position and relative height of two Moreover, the relative intensity of vibration band at 315 cm−1
Raman vibration bands in the range of 280−400 cm−1. For also enhances dramatically. These spectral characteristics imply
heavy rare earth trifluoromethanesulfonate aqueous solution the formation of LaO6 triple prism in La(H2O)9(CF3SO3−)3
(Ln = Tb−Lu) except Yb and Lu (Figure 1H−L), only the cluster. Finally, a broad and weak Raman band at ∼240 cm−1
ratio between the heights of two Raman bands increases appears in the spectrum collected at 11 min (Figure S17). In
without the band shifts. For Yb(H2O)9−x(CF3SO3)3 (Figure Figure 2, the baseline correction was carried out to all Raman
1M) and Lu(H2O)9−x(CF3 SO3) 3 (Figure 1N) aqueous spectra, which can solve the baseline skew but will decrease the
solutions, the Raman band at ∼325 cm−1 shifts toward higher intensity of the weak band at ∼240 cm−1. The Raman band at
wavenumbers. ∼240 cm−1 can be assigned as v(La−O) capping in crystalline
According to the in situ Raman spectra, we can initially infer Ln(H2O)9(CF3SO3)3 (as shown Figure S15);22 therefore, the
the configuration of hydrated Ln3+ in aqueous solution. The time-dependent Raman spectrum collected at 11 min indicates
aqueous chemistry of Ln3+ ions illustrates that Ln3+ is hard the formation of the La(H2O)93+ tricapped trigonal prism in
Lewis acids and mainly interacts with water via electrostatic crystalline La(H2O)9(CF3SO3)3.
interactions; therefore, their hydration numbers are governed The hydrogen bonding between hydrated La3+ and CF3SO3−
largely by their ionic radii.24,25 Taking La(H2O)9(CF3SO3)3 guides the formation of La(H2O)93+ tricapped trigonal prism.
aqueous solution as an example, Raman bands at 327 and 354 In order to study the hydrogen bonding in the nucleation, we
cm−1 can be assigned to v5(Trifl) and v11(Trifl), respectively, further track the evolution of both La−O and CF3SO3−
D DOI: 10.1021/acs.cgd.7b00145
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vibration bands. As shown in Figure 3, only v(C−S), ρr(SO3),
and δs(SO3) Raman vibration bands can be observed in
Figure 3. Formation mechanism of La(H2O)93+ tricapped trigonal
prism in aqueous solution. According to the structural information on
LaO6 and CF3SO3 groups, the interaction between hydrated La3+ and
CF3SO3− will be identified, and the cluster structure can consequently
be obtained.
aqueous solution. Previous studies show that free hydrated SO3
and CF3 groups have C3h symmetry.30 In aqueous solution, the
deformation vibration of SO3 and CF3 groups would be
influenced by their surrounding hydrogen bonding. The
appearance of the symmetry deformation vibration of SO3
(δs(SO3)) shows the interaction between CF3SO3− and
hydrated La3+, while CF3 group retains its higher symmetry
under the highly symmetric hydrogen bonding with H2O
molecules. With continuously increasing the volume of
La(H2O)n(CF3SO3)m clusters, each O atom in SO3 tends to
link with two hydrated La3+, and two O atoms in SO3 are
hydrogen bonded with one hydrated La3+. The number of
hydrogen bonding surrounding the hydrated La3+ increases,
and the intensity of these surrounding hydrogen bonds
becomes stronger, inducing the formation of the LaO6 triple
prism. In such a case, the CF3 group will be dehydrated with
free H2O (continuously volatilizing solvent H2O) and will be
further bonded with the hydrated La3+ cluster, constructing the
configuration of a particular triple prism or tricapped trigonal
prism. It leads to the decrease of symmetry for CF3 from C3h to
C2, and we can find a δ(CF3) vibration band in the Raman
spectra (for example, the Raman spectra in Figure 3 after 6
min). Moreover, the more stronger hydrogen bonding between
La(H2O)93+ and SO3 may also decrease the intensity of both
stocking and deformation vibration bands for the SO3 group,
inducing the variation in relative height ratio between SO3 and
CF3.
In order to obtain more complete structural information, we
also carried out in situ Raman observation of Ln(H2O)9-
(CF3SO3)3 aqueous solution system in the range of 725−1150
cm−1, as shown in Figure 4. The intense Raman band at ∼1048
cm−1 is assigned to the symmetric stretching mode of SO3. In
aqueous solution, the intensity of v(SO3) band is larger than
that of δ(CF3). Especially for light rare earth trifluorometha-
E DOI: 10.1021/acs.cgd.7b00145
Article
nesulfonate aqueous solution (Ln = La−Gd) except Nd and Eu
(Figure 4A−C,E,G), nearly no δ(CF3) can be found at the
initially stage of nucleation. However, for heavy rare earth
trifluoromethanesulfonate aqueous solution (Ln = Tb−Lu),
δ(CF3) with weak intensity appears in Raman spectra (Figure
4H−N), similar to that in Nd(H2O)9(CF3SO3)3 and Eu-
(H2O)9(CF3SO3)3 (Figure 4D,F). This can be attributed to the
fact that the hydrated Ln3+ (Ln = La−Pr, Sm, Gd) prefers to
separate with hydrated CF3SO3− or the aggregation degree
between hydrated Ln3+ and CF3SO3− is very low, while the
hydrated Nd3+, Eu3+, and Tb3+−Lu3+ prefer to be bonded with
CF3SO3− to form clusters. Moreover, there are two evolution
trends for vs(SO3) in the formation of crystalline Ln(H2O)9-
(CF3SO3)3 (Ln = La−Lu). For La−Pr, Sm, Gd−Dy, Yb, and Lu
trifluoromethanesulfonate aqueous solution, vs(SO3) splits to
two Raman peaks accompanied by the formation of LnO6
prism. While the number and position of vs(SO3) remain
unchanged in the nucleation of Nd, Eu, and Ho−Tm
trifluoromethanesulfonate aqueous solutions. Two vs(SO3)
Raman vibration bands may be originated from two Ln−O
bond lengths in Ln(H2O)93+, which produces different
hydrogen bonding modes between Ln(H 2 O) 9 3+ and
CF3SO3−. As a consequence, the symmetry of SO3 decreases
from C3h to C2, and two S−O bond lengths exist in SO3.
In order to illustrate the hydrogen bonding dependent
mesoscale framework more intuitively, Ce(H2O)9(CF3SO3)3
aqueous solution was taken as an example. As shown in Figure
5, no δ(CF3) band can be found in Raman spectra, indicating
the existence of hydrated CF3SO3− at the initial stage of
nucleation. Later, the aggregation between hydrated Ce3+ and
CF3SO3− leads to the slight appearance of δ(CF3) and
increased intensity of vs(SO3).31 Each CF3SO3− can link with
three hydrated Ce3+; the hydrogen bonding will modulate the
molecular configuration and relative position in the aggregated
molecules in a very short time. As shown in Figure 5,
accompanied by the formation of CeO6 prism, the symmetry of
SO3 decreases from C3h to C2, and the intensity of both δ(CF3)
and vs(SO3) bands increases. Moreover, it can also be found
that both δ(CF3) and vs(SO3) bands split into two bands.
Furthermore, Ce(H2O)93+ tricapped trigonal prisms are
formed, and the intensity of two vs(SO3) bands converge.
Especially, for both the Nd(H2O)9(CF3SO3)3 and Eu(H2O)9-
(CF3SO3)3 nucleation system, nearly unchanged time-depend-
ent Raman spectra indicates the initially formation of
Ln(H2O)9(CF3SO3)3 (Ln = Nd and Eu) clusters with LnO6
prism configuration, which further transform to Ln(H2O)93+
tricapped trigonal prism in crystalline nuclei (Figure 6).
It is notable that there is a sharp shift at ∼320 cm−1 before
and after the formation of LnO6 triple prism. Two adjacent
time-dependent Raman spectra of Ln(H2O)9−x(CF3SO3)3 (x =
0−1, Ln = La−Lu) that reflect this sharp shift were selected,
and the Raman shifts were calculated as shown in Figures 7 and
S18. Totally, the Raman shift decreases from La−Lu in
Ln(H2O)9−x(CF3SO3)3 nucleation system. This can be
attributed to the fact that ionic EN of 9-coordinated Ln3+
increases from La to Lu, leading to the shift of Ln−O prism and
capping vibration bands toward high wavenumbers. Therefore,
the Raman shift decreases from La−Lu at ∼320 cm−1. On the
other hand, the lanthanoid aqua ion contraction is a well-
known structural property,13 resulting in the coordination
number of Ln3+ to decrease from 9 to nearly 8 with increasing
the number of 4f electrons in Ln3+ from 0 (La) to 14 (Lu).24
The decreased coordination number of Ln3+ ((Ln(H2O)9−x3+))
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Crystal Growth & Design Article

Figure 4. In situ Raman spectra of the nucleation process in La(H2O)9(CF3SO3)3 (A), Ce(H2O)9(CF3SO3)3 (B), Pr(H2O)9(CF3SO3)3 (C),
Nd(H2O)9(CF3SO3)3 (D), Sm(H2O)9(CF3SO3)3 (E), Eu(H2O)9(CF3SO3)3 (F), Gd(H2O)9(CF3SO3)3 (G), Tb(H2O)9(CF3SO3)3 (H),
Dy(H2O)9(CF3SO3)3 (I), Ho(H2O)9(CF3SO3)3 (J), Er(H2O)9(CF3SO3)3 (K), Tm(H2O)9(CF3SO3)3 (L), Yb(H2O)9(CF3SO3)3 (M), and
Lu(H2O)9(CF3SO3)3 (N) aqueous solutions in the range of 725−1150 cm−1. Raman band at ∼1048 cm−1 is assigned as vs(SO3), and Raman band at
∼780 cm−1 is assigned as δ(CF3).

F DOI: 10.1021/acs.cgd.7b00145
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Crystal Growth & Design Article

Figure 7. Raman shifts of Ln(H2O)9(CF3SO3)3 at ∼320 cm−1 before

Figure 5. Evolution of dynamic hydrogen bonding between the
hydrated Ce and CF3SO3 group in the nucleation process of
Ce(H2O)9(CF3SO3)3 from aqueous solution. Hydrogen bonding
between hydrated Ce3+ and CF3SO3 directs the decreased symmetry
of both CF3 and SO3 groups in CF3SO3, as well as the formation of
CeO6 prism and Ce(H2O)93+ tricapped trigonal prism.
will lead to the increased chemical bonding with surrounding
H2O ligands, and consequently the increased wavenumber of
E′v(LnO6 prism) and v(LnO3) capping bands as shown in
Figure S18B. Moreover, the increased chemical bonding of Ln3+
with surrounding H2O ligands can also weaken the hydrogen
bonding surrounding CF3SO3− with the hydrated Ln3+,
resulting in the shift of v5(Trifl) toward a higher wavenumber
(Figure S18A). Especially, the increased wavenumber of
E′v(LnO6 prism) with decreased coordination number from
La to Lu will even produce a negative shift for Yb- and Lu-
based trifluoromethanesulfonate complex as shown in Figure 7.
Moreover, these Raman shifts also show a “tetrad grouping”
phenomena, which is a typical performance for rare earth
and after the appearance of nuclei in aqueous solution. The results
show an obvious tetra-group phenomenon, originating from different
numbers of 4f electrons in Ln3+. Black dotted lines are used to divide
tetra-groups for the Raman shifts at ∼320 cm−1.
elements that possess the electron states respectively near 1/4-
filled, half-filled, 3/4-filled, and full-filled 4f orbits. That is, such
a phenomenon can be considered only related to the 4f
electrons. The result shown in Figure 7 can provide some
experimental data to indicate the participation of 4f electrons in
Ln−O bonding in Ln(H2O)93+.
■ CONCLUSION
In situ Raman spectroscopy was applied to observe in real-time
the formation of a mesoscale framework at the nucleation stage
of Ln(H2O)9(CF3SO3)3 (Ln = La−Lu) in aqueous solution.
The spectral characteristics can be used to identify the
hydrogen bonding dependent coordination geometry of
constituent groups, such as hydrated Ln3+ and CF3SO3−.
Moreover, the aggregation between these groups can also be
deduced by tracking the evolution of Raman vibration bands
since the geometric features of constituent groups are directly
influenced by the surrounding local structure in hydrated
groups, clusters, and crystalline nuclei. In Ln(H2O)9(CF3SO3)3

Figure 6. In situ Raman spectral identification of molecular configuration evolution of La(H2O)9(CF3SO3)3 clusters in the nucleation. (A) Evolution
of E′v(LnO6), v5(Trifl), and v11(Trifl) vibration bands in Raman spectra at the nucleation stage of La(H2O)9(CF3SO3)3 in aqueous solution. (B)
Evolution of δ(CF3) and vs(SO3) vibration bands in Raman spectra at the nucleation stage of La(H2O)9(CF3SO3)3 in aqueous solution. (C)
Mesoscale configuration evolution of La(H2O)9(CF3SO3)3 clusters.

G DOI: 10.1021/acs.cgd.7b00145
Cryst. Growth Des. XXXX, XXX, XXX−XXX
Crystal Growth & Design Article

aqueous solution, the Ln(H2O)93+ tricapped trigonal prisms
cannot exist in solution. With the concentration of solution,
Ln(H2O)n(CF3SO3)3 clusters are formed by sharing common
H2O molecules between hydrated Ln3+ and CF3SO3−. Under
the guiding of intermolecular hydrogen bonds, the phase
transition is promoted by structural evolution from cluster to
nucleus with Ln(H2O)93+ tricapped trigonal prism. During such
a phase transition process, the symmetry of Ln(H2O)n3+
increases but the symmetry of CF3SO3− decreases. Especially,
for the Nd, Eu, Yb and Lu system, Ln(H2O)n(CF3SO3)3
clusters instead of hydrated Ln3+ and CF3SO3− exist in the
aqueous solution. The present study opens up the chemical
bonding behaviors of rare earth ions in aqueous solution, which
provides basic data for the study of the coordination of rare
earth complexes and the design of novel rare earth materials.
(12) D’Angelo, P.; Spezia, R. Chem. - Eur. J. 2012, 18, 11162−11178.
(13) Persson, I.; D’Angelo, P.; De Panfilis, S.; Sandstrom, M.;
Eriksson, L. Chem. - Eur. J. 2008, 14, 3056−3066.
(14) Morales, N.; Galbis, E.; Martinez, J. M.; Pappalardo, R. R.;
Sánchez Marcos, E. S. J. Phys. Chem. Lett. 2016, 7, 4275−4280.
(15) Takekiyo, T.; Yoshimura, Y.; Ikeji, Y.; Hatano, N.; Koizumi, T. J.
Phys. Chem. B 2008, 112, 13355−13358.
(16) Goncalves, M. C.; Fernandes, I. C.; Hummer, J.; de Zea
Bermudez, V. Vib. Spectrosc. 2011, 57, 187−195.
(17) Sun, C.; Xue, D. CrystEngComm 2015, 17, 2728−2736.
(18) Sun, C.; Xue, D. J. Phys. Chem. C 2014, 118, 16043−16050.
(19) Feng, D.; Zheng, G.; Zhao, Y.; Zhang, B.; Wan, S.; You, J.; Hu,
Z. CrystEngComm 2015, 17, 9357−9362.
(20) Zhang, K.; Bao, C.; Gu, Q.; Ren, X.; Zhang, H.; Deng, K.; Wu,
Y.; Li, Y.; Feng, J.; Zhou, S. Nat. Commun. 2016, 7, 13552.
(21) Fujioka, Y.; Frantti, J.; Puretzky, A.; King, G. Inorg. Chem. 2016,

■
55, 9436−9444.
(22) Mink, J.; Skripkin, M. Y.; Hajba, L.; Nemeth, C.; Abbasi, A.;
ASSOCIATED CONTENT Sandstrom, M. Spectrochim. Acta, Part A 2005, 61, 1639−1645.
*
S Supporting Information (23) Paul, P.; Ghosh, M.; Neogy, D.; Mallick, P. K. Spectrochim. Acta,
The Supporting Information is available free of charge on the Part A 2011, 78, 59−63.
ACS Publications website at DOI: 10.1021/acs.cgd.7b00145. (24) Apostolidis, C.; Schimmelpfennig, B.; Magnani, N.; Lindqvist-
Reis, P.; Walter, O.; Sykora, R.; Morgenstern, A.; Colineau, E.;
Additional Figures S1−S18 depicting experimental Caciuffo, R.; Klenze, R.; Haire, R. G.; Rebizant, J.; Bruchertseifer, F.;
results (PDF) Fanghanel, T. Angew. Chem., Int. Ed. 2010, 49, 6343−6347.

■
(25) Kovacs, A.; Apostolidis, C.; Walter, O.; Lindqvist-Reis, P. Struct.
AUTHOR INFORMATION Chem. 2015, 26, 1287−1295.
(26) Li, K.; Xue, D. Phys. Status Solidi B 2007, 244, 1982−1987.
Corresponding Author (27) Li, K.; Xue, D. J. Phys. Chem. A 2006, 110, 11332−11337.
*E-mail: dongfeng@ciac.ac.cn. (28) Silva, R. A.; Silva, G. G.; Pimenta, M. A. J. Raman Spectrosc.
ORCID 2001, 32, 369−371.
Congting Sun: 0000-0002-6949-6417 (29) Eltayeb, S.; Guirgis, G. A.; Fanning, A. R.; Durig, J. R. J. Raman
Spectrosc. 1996, 27, 111−126.
Notes (30) Mondal, J.; Acharya, S.; Bisui, D.; Chattopadhyay, K. N.; Ghosh,
The authors declare no competing financial interest. M.; Chakrabarti, P. K. J. Appl. Phys. 2009, 105, 063921.

■ ACKNOWLEDGMENTS
Financial support from the National Natural Science
(31) Abbasi, A.; Lindqvist-Reis, P.; Eriksson, L.; Sandstrom, D.;
Lidin, S.; Persson, I.; Sandstrom, M. Chem. - Eur. J. 2005, 11, 4065−
4077.
Foundation of China (Grant Nos. 51125009, 91434118, and
21401185), National Natural Science Foundation for Creative
Research Group (Grant No. 21521092), Hundred Talents
Program of Chinese Academy of Sciences, and Jilin Province
Science and Technology Development Project (Grant Nos.
20170101092JC and 20160520006JH) is acknowledged.

■ REFERENCES
(1) Dideriksen, K.; Frandsen, C.; Bovet, N.; Wallace, A. F.; Sel, O.;
Arbour, T.; Navrotsky, A.; De Yoreo, J. J.; Banfield, J. F. Geochim.
Cosmochim. Acta 2015, 164, 94−109.
(2) Jeanvoine, Y.; Miro, P.; Martelli, F.; Cramer, C. J.; Spezia, R. Phys.
Chem. Chem. Phys. 2012, 14, 14822−14831.
(3) Sun, C.; Xue, D. Cryst. Growth Des. 2015, 15, 2867−2873.
(4) Petaja, T.; Sipila, M.; Paasonen, P.; Nieminen, T.; Kurten, T.;
Ortega, I. K.; Stratmann, F.; Vehkamaki, H.; Berndt, T.; Kulmala, M.
Phys. Rev. Lett. 2011, 106, 228302.
(5) Sivakumar, R.; Kwiatoszynski, J.; Fouret, A.; Nguyen, T. P. T.;
Ramrup, P.; Cheung, P. S. M.; Cintas, P.; Viedma, C.; Cuccia, L. A.
Cryst. Growth Des. 2016, 16, 3573−3576.
(6) Gebauer, D.; Kellermeier, M.; Gale, J. D.; Bergstrom, L.; Colfen,
H. Chem. Soc. Rev. 2014, 43, 2348−2371.
(7) Farhadi-Khouzani, M.; Chevrier, D. M.; Zhang, P.; Hedin, N.;
Gebauer, D. S. Angew. Chem., Int. Ed. 2016, 55, 8117−8120.
(8) Rudolph, W. W.; Irmer, G. Dalton Trans. 2015, 44, 18492−
18505.
(9) Rudolph, W. W.; Irmer, G. Dalton Trans. 2015, 44, 295−305.
(10) Helm, L.; Merbach, A. E. Chem. Rev. 2005, 105, 1923−1959.
(11) Furet, E.; Costuas, K.; Rabiller, P.; Maury, O. J. Am. Chem. Soc.
2008, 130, 2180−2183.

H DOI: 10.1021/acs.cgd.7b00145
Cryst. Growth Des. XXXX, XXX, XXX−XXX