Article

pubs.acs.org/crystal

Exploring the System Lanthanide/Succinate in the Formation of

Porous MetalOrganic Frameworks: Experimental and Theoretical
Study
Richard F. DVries,*, Ihosvany Camps, and Javier Ellena

Instituto de Fsica de Sao Carlos, Universidade de Sao Paulo, CP 369, 13560-970 Sao Carlos, Sao Paulo, Brasil
Laboratorio de Modelagem ComputacionalLaModel, Instituto de Ciencias Exatas, Universidade Federal de AlfenasUnifal-MG,
37130-000 Alfenas, Minas Gerais, Brazil

S Supporting Information
*

ABSTRACT: Exploring the Ln/succinate system and the template eect in

hydrothermal synthesis made it possible to obtain [La2(Succ)3(H2O)3]2H2O and
[Ln2(Succ)3(H2O)2] where Ln = La, Pr, Nd, Sm, Eu, Gd, and Tb. The rst case is
a 2D network with a sql plane net topology. The 3D supramolecular network is
formed by strong hydrogen bonds, which give rise to a pcu network. In the second
case, a family of 3D compounds with a bnn topology could be synthesized. Both
compounds can be obtained in the presence of 5-sulfosalicylate (5-SSA3) as a
template agent, and the presence of toluene in the reaction enables formation only
of [Ln2(Succ)3(H2O)2] compounds. This paper addresses a systematic synthetic
and theoretical study of the formation equilibrium of the molecules reported. The
inuence of the template agent on the formation of porous MOFs and the
luminescent behavior are addressed.

INTRODUCTION
Since the appearance of metalorganic frameworks
(MOFs),13 several types of connectors (metallic centers)
and linkers (organic ligands) have been used in their design, in
search of new compounds with new architectures, topologies,
and interesting properties.410 Lanthanide metals exhibit
properties that make them excellent candidates for the
synthesis of new MOFs. Lanthanides have electrons in f
orbital, which enables them to generate ff transitions when
interacting with the appropriated radiation.6 Due to the
electronic nature of these metals and high positive charge,
they show high Lewis acidity.1113 The lanthanide inuence on
MOF structure can be applied to the manufacture of materials
with luminescent or electroluminescent properties, materials for
telecommunications, and light-emitting diodes, heterogeneous
catalysis, magnetic devices, sensors, and contrast agents.1421
Moreover, the selection of linkers in the MOF design depends
on two types of factors: (i) structural factors, such as exibility
or stiness, coordination modes, connectivity, and size, among
others, and (ii) functional factors, such as aromatic rings,
functional groups, and electronic delocalization. Succinic acid is
a exible linker that has the ability to have dierent
coordination modes. Therefore, dierent phases or structural
isomers of general formula [Ho2(C4H4O4)3(H2O)n](H2O)m
have been synthesized.2232
This paper reports a synthetic study of the Ln/succinate
system for obtaining Ln-based MOFs using organic templates
as reaction drivers.33 Also, the formation equilibrium and the
thermodynamical stability of the crystal phases and its eect on
XXXX American Chemical Society

the crystallization process were studied by DFT for periodical

systems methodology. The rst compound is a 2D network
with [La2(Succ)3(H2O)3]2H2O formula obtained using 5sulfosalicylic acid as template. The family of 3D isostructural
compounds [Ln2(Succ)3(H2O)2], where Ln = La, Pr, Nd, Sm,
Eu, Gd, and Tb results from a hydrothermal synthesis that uses
5-sulfosalicylic acid or toluene as template.

EXPERIMENTAL SECTION

General Information. All reagents and solvents employed were

commercially available and used as supplied without further
purication: Succinic acid (99%, Sigma-Aldrich); 5-sulfosalicylic acid
hydrate (95%, Sigma-Aldrich); Ln(NO3)36H2O where Ln = La, Pr,
Nd, Sm, Eu, Gd, and Tb (99%, Sigma-Aldrich). IR spectra were
recorded from KBr pellets in the 4000250 cm1 range on a Bomem
Michelson FT MB-102. The thermogravimetric analyses (TGA) were
performed in Shimadzu TGA-50 equipment at 25900 C temperature range, under nitrogen (100 mL/min ow) atmosphere and 10
C/min heating rate. A Fisons EA-1108 CHNS-O was employed for
the elemental analysis. The luminescence excitation and emission
spectra were obtained with a Horiba Jobin Yvon model Fluorolog FL3222 spectrophotometer equipped with an R928 Hamamatsu photomultiplier and 450 W Xe lamp, in front face mode. The spectra were
corrected with respect to the Xe lamp intensity and spectrometer
response.
Synthesis. Methodology 1. The molar composition of the initial
reaction mixture in all cases was set as succinate2/La3+/5-SSA3/
Received: March 27, 2015
Revised: April 24, 2015

DOI: 10.1021/acs.cgd.5b00426
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Table 1. Crystallographic and Renement Data for Compounds [La2(Succ)3(H2O)3]2H2O and [Ln2(Succ)3(H2O)2] Obtained
by Two Dierent Methodologies
Methodology 1
[La2(Succ)3(H2O)3]2H2O

emp formula
FW (g/mol)
temp (K)
()
cryst. syst.
space group
unit cell
a ()
b ()
c ()
(deg)
(deg)
(deg)
vol (3)
Z
calcd (mg/m3)
abs coe (mm1)
F(000)
range (deg)
rens collected/unique [R(int)]
completeness (%)
Data/restraints/params
GOF on F2
R1 [I > 2(I)]
wR2[I > 2(I)]

[La2(Succ)3(H2O)2]

C12H22O17La2
716.12
298
0.71073
orthorhombic
Pbnm

emp formula
FW (g/mol)
temp (K)
()
cryst syst
space group
unit cell
a ()
b ()
c ()
(deg)
(deg)
(deg)
vol (3)
Z
calcd (mg/m3)
abs coe (mm1)
F(000)
range (deg)
rens collected/unique [R(int)]
completeness (%)
data/restraints/params
GOF on F2
R1 [I > 2(I)]
wR2 [I > 2(I)]

C12H16O14La2
662.07
298
0.71073
triclinic
P1

10.2108(5)
13.7312(7)
14.7406(9)
90
90
90
2066.7(2)
4
2.302
4.162
1376
2.926.4
4020/2197 [0.034]
99.9
2197/0/154
1.079
0.0412
0.0927
Methodology 2

7.976(8)
12.006(1)
12.284(1)
112.01(2)
90.05(3)
100.58(5)
1068.9(2)
2
2.057
4.005
628
2.926.4
14114/5027 [0.076]
98.4
5027/0/255
0.944
0.0532
0.1674

[La2(Succ)3(H2O)2]

[Pr2(Succ)3(H2O)2]

[Nd2(Succ)3(H2O)2]

C12 H16 O14 La2

658.04
298
0.71073
triclinic
P1

C12 H16 O14 Pr2

664.05
298
0.71073
triclinic
P1

C12 H16 O14 Nd2

668.70
298
0.71073
triclinic
P1

298
0.71073
triclinic
P1

7.979(2)
12.095(3)
12.297(4)
111.68(1)
89.93(2)
100.16(2)
1082.8(5)
2
2.018
3.953
620
3.026.4
31102/4384 [0.097]
99.3
4384/0/255
0.82
0.0393
0.0991

7.877(1)
12.060(3)
12.275(1)
112.12(4)
89.98(3)
99.95(5)
1061.0(3)
2
2.7079
4.600
632
2.926.3
30410/4310 [0.137]
99.7
4310/0/250
1.501
0.1219
0.3637

7.8354(7)
12.0496(2)
12.2524(2)
112.015(5)
89.967(7)
99.921(7)
1053.8(2)
2
2.107
4.935
632
3.026.6
26997/4179 [0.214]
94.8
4179/0/243
0.969
0.0844
0.2392

7.7050(3)
11.9893(7)
12.1828(6)
112.143(2)
89.979(3)
99.580(3)
1025.48(9)
2
2.263
6.592
656
3.026.2
7825/4063 [0.053]
98.9
4063/0/232
1.12
0.1365
0.3801

[Gd2(Succ)3(H2O)2]
C12 H16 O14 Gd2

room temperature for 30 min. The mixture was then placed into
Teon-lined stainless steel autoclaves for reaction under hydrothermal
conditions. After cooling to room temperature, the crystalline products
were ltered and washed with water and acetone.
[La2(Succ)3(H2O)3]2H2O (phase 1) was obtained as a mixture

4915H2O. The synthesis procedure in all cases is described as follows:

Succinic acid (0.013 g, 0.115 mmol) and 5-sulfosalicylic acid (0.025 g,
0.115 mmol) were added to a solution of La(NO3)36H2O (0.05 g,
0.115 mmol) in 10 mL of water; the reaction mixture was adjusted to
pH 4.4 by the addition of NaOH (1 M) under constant stirring at
B

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Figure 1. ORTEP diagram with 50% probability for compounds (a) [La2(Succ)3(H2O)2] and (b) [La2(Succ)3(H2O)3]2H2O. Hydrogen atoms were
removed for clarity, and only the atoms present in the asymmetric unit were labeled.
with a small amount of [La2(Succ)3(H2O)2] (phase 2) when the
reaction was heated to 160 C for 18 h. When the temperature was
increased to 170200 C, compound [La2(Succ)3(H2O)2] appeared
as the main reaction product (yield 42.38%), with small amounts of
the previously reported compounds [La2(Succ)3(H2O)2]2H2O
(phase 3)29 and [Ln2(Succ)2(SO4)(H2O)2] (phase 4 = RPF-16La). 3 4 Elemental Anal. Calcd for [La 2 (Succ) 3 (H 2 O) 2 ]
(C12H16O17La2): C, 21.7; H, 2.4. Found: C, 21.22; H, 3.1.
Methodology 2. The molar composition of the initial reaction
mixture in all cases was set as succinate2/Ln3+/1474H2O/250toluene.
Succinic acid (0.013 g, 0.115 mmol) was added to a solution of
La(NO3)36H2O (0.05 g, 0.115 mmol) in 3 mL of water; the reaction
mixture was adjusted to pH 4.4 by the addition of NaOH (1 M)
under constant stirring at room temperature for 30 min. Finally, 3 mL
of toluene was added to the reaction mixture, and the mixture was
placed into Teon-lined stainless steel autoclaves for reaction under
hydrothermal conditions at 200 C. After cooling to room temperature, the crystalline products were ltered and washed with water and
acetone, and product was obtained in 78.01% yield. The same
procedure was followed for the synthesis of all compounds
[Ln2(Succ)3(H2O)2], where Ln = La, Pr, Nd, Sm, Eu, Gd, and Tb.
Elemental Anal. Calcd for [La2 (Succ) 3 (H2 O) 2 ]0.33(toluene)
[(C12H16O17La2)0.33(toluene)]: C, 22.84; H, 2.46. Found: C,
23.56; H, 2.93. Anal. Calcd for (C12H16O17Pr2)0.33(toluene): C,
22.72; H, 2.45. Found: C, 23.31; H, 2.82. Anal. Calcd for
(C12H16O17Nd2)0.33(toluene): C, 22.52 ; H, 2.43. Found: C, 23.90;
H, 3.17. Anal. Calcd for (C12H16O17Gd2)0.5(toluene): C, 22.93; H,
2.44; found: C, 23.46; H, 3.05.
Single-Crystal Structure Determination. Single-crystal X-ray
data for all the compounds were collected at room temperature (298
K) on an Enraf-Nonius Kappa-CCD diractometer using Mo K
radiation (0.71073 ) monochromated by graphite. The cell was
rened by Collect and Scalepack software, and the nal cell parameters
were obtained on all reections. A data reduction was carried out using
Denzo-SMN and Scalepack software.35 The structure was solved by
SHELXS-2013 software and then rened by SHELXL-2013,36
included in WinGX37 and Olex2.38 Non-hydrogen atoms of the
molecules were clearly resolved, and the full-matrix least-squares
renement of these atoms, with anisotropic thermal parameters, was
carried out. All hydrogen atoms were stereochemically positioned and
rened with the riding model.36 Hydrogen atoms of the water
molecules were localized in the density map and xed (with Uiso(H) =
1.5Ueq). ORTEP diagram was prepared with Diamond.39 TOPOS,40
Mercury,41 and Diamond39 programs were used in the preparation of
the artwork of the polyhedral and topological representations.
X-ray Powder Diraction. PXRD patterns were measured with a
Rigaku Ultima IV diractometer of 0.02 step size and 2 s/step
exposure time. PXRD measurements were used to prove the
isostructurality of the series and check the purity of the obtained
microcrystalline products through the comparison of the experimental

results with the simulated pattern obtained from single crystal X-ray
diraction data.
Computational Details. To study the structural and electronic
properties of the solid phase, the calculations were performed
considering the density functional theory (DFT) for periodical
systems methodology.42,43 DFT was used as implemented in the
SIESTA code,44 and the generalized gradient approximation (GGA)
was employed for the exchange-correlation potential using the PBE
scheme.45 To avoid the need for explicit treatment of the core
electrons, the norm-conserving TroullierMartins pseudopotentials46
were used. For the valence electrons, we used a split-valence double-
basis set with polarization functions (DZP).47 To obtain results
suciently accurate, convergence studies were done for the mesh
cuto energy and the number of k-points. The total energy
convergence for the systems was obtained for a mesh cuto of 600
Ry and for a k-point set of 8 8 8. In the case of the La atom, we
used the nonlinear core corrections48 and the 5s2 and 5p6 semicore
states explicitly included in the calculations. The structure
optimizations were done until the HellmanFeynman forces were
below 0.01 eV/ and the energy convergence criterion was equal to
106. To calculate the lattice formation energy (Eform) of each phase,
we have to calculate the energy of the reagents (ER) and the energy of
the nal product (EP), that is, of the crystals. From these calculations,
the lattice formation energy is obtained as Eform = EP ER.49

RESULTS AND DISCUSSION

Structural Description. Details of data collection, renement, and crystallographic data for the compounds are
summarized in Table 1. Figure 1 shows the ORTEP diagram
for [La2(Succ)3(H2O)2] and [La2(Succ)3(H2O)3]2H2O compounds. High values of R(int), R1, and wR2 were obtained for
Pr, Nd, and Gd compounds due to the particular squared
tubular needles crystal shape (Section S5, Supporting
Information) intrinsic to all the series of compounds; this
fact produces quality problems in the nal data.
The compound [La2(Succ)3(H2O)3]2H2O is formed by two
crystallographycally independent LaIII cations. The one named
La1 exhibits an uncommon 11-coordinated environment
formed by ten oxygen atoms of succinate anions and one
water molecule. The cation named La2 displays a 9-coordinated
environment that consists of seven oxygen atoms of succinate
anions and two water molecules forming a trigonal prism
square-face tricapped polyhedron (TPRS-9).50 Two types of
succinate anions can be seen: (i) one joining three metallic
centers by coordination in oxo-carboxylate mode 2323;
this conguration enables the junction of two metallic centers
to obtain a face sharing SBU (Ln2O17) (distance La1La2 =
C

DOI: 10.1021/acs.cgd.5b00426
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2.6802(7) distances. The additional connectivity enables the

formation of a 3D supramolecular network, where SBUs act as
6-connected nodes and obtain a primitive cubic (pcu)
topology40 with point symbol (41263) (Figure 4).

4.1032(8) ) and linkage of the SBUs along the [010]

direction forming innite chains (Figure 2a); (ii) another

Figure 2. (a) Coordination environment of Ln2O17 SBUs and innite

chains along [010]; (b) coordination modes of the two types of
succinate anions in the compound [La2(Succ)3(H2O)3]2H2O.
Figure 4. (a) Representation of interlayer hydrogen bonds and (b) 3D
supramolecular network simplied on pcu for [La2(Succ)3(H2O)3]
2H2O.

joining the innite chains along the [100] direction by the

coordination of three metallic cations in 223 mode (Figure
2b). Both succinate anions show signicant dierences in the
torsion angles of aliphatic carbons C5C6C7C8 = 71.8(8)
and C1C2C3C4= 180.0(6) and carboxylate groups
O5C5C7C8 = 177.7(6), O7C8C7C6 = 97.9(8), and
O1C1C2C3 = O3C4C3C2 =0.0 for type I and ii succinates,
respectively.
This new crystalline phase has been formed as a 2D
polymeric network in the plane (110). Such a network can be
topologically simplied by taking the centroid between the
metallic centers in the dimeric units (SBUs);51 it is possible to
observe that these units act as a tetraconnected node (Figure
3). Each succinate anion links two 4-connected nodes, which
give rise to a 2D network with sql plane net topology
(topos&RCSR.ttd)40 and point symbol (4462).

Similarly to the previous case, the family of compounds

[Ln2(Succ)3(H2O)2] (where Ln = La, Pr, Nd, Sm, Eu, Gd, and
Tb) shows two crystallographycally independent LnIII cations;
in this case, both have the same 9-coordinated environment
with eight oxygen atoms of the succinate anions and one
coordinated water molecule that form a trigonal prism squareface tricapped polyhedron (TPRS-9).50 Three structurally
dierent succinate anions are present in this molecule. Two
of them (succinates A and B) play an important role, joining
the metallic centers to obtain innite chains of edge sharing
SBUs (Ln2O16) along the [100] direction (Figure 5a) by their

Figure 5. (a) Coordination environment of Ln2O16 SBUs and innite

chains along [100] and (b) the three types of succinate anions present
in the compounds [Ln2(Succ)3(H2O)2].

coordination in oxo-carboxylate mode 23. Innite chains are

linked by a 2 coordination mode along the [001] direction.
The third anion (succinate C) joins the chains along the [010]
by an oxo-carboxylate 2323 coordination mode. Dierences in the torsion angles are found in the three succinate
anions. For clarity the succinate anions were denominated A, B,
and C (Figure 5b). Types A and B show quite similar torsion
angles with values C5C6C10C9 = 68.7(1), O15C5C6C10 =
129.6(9), and O10C9C10C6 = 19.8(1) and C1C2C3C4 =
67.6(1), O3C4C3C2 = 127.8(9), and O8C1C2C3 =

Figure 3. Decorated and simplied 2D network type sql for

[La2(Succ)3(H2O)3]2H2O compound.

The interstitial water molecules present in the crystalline

structure generate hydrogen bonds that enable the binding of
layers and give rise to a 3D supramolecular network. The
strongest hydrogen interaction occurs between the water
molecules and the oxygen atoms of the succinate anion with
O5HBO11 = 2.750(8) and O8H11AO11 =
D

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Study of the Eect of Synthesis Conditions on the LnSuccinate Formation. Methodology 1. In order to study the
system succinate2/La3+/5-SSA3, the reaction stoichiometry
was xed as is shown in the Experimental Section. Several
experiments were conducted to nd the optimal reaction pH:
with pH values <4 no reaction product was observed. At pH
4, the new compounds (phases 1 and 2) were obtained as a
function of the temperature and reaction time, while with pH
values >5, the previously reported compounds (phases 3 and 4)
were observed as main reaction products. Once we found and
set up the reaction stoichiometry and pH, several variable
studies were performed: (i) First, it was found that with long
reaction time the reported phases 3 and 4 are obtained; for this
reason, the reaction time used ranged between 18 and 24 h. (ii)
Heating the reaction mixture between 140 and 160 C for 18 h
produced the compound [La2(Succ)3(H2O)3]2H2O (phase 1)
always as a mixture with phase 2 (Figure 8). (iii) When the
temperature was increased to values between 170 and 190 C
for 18 h of reaction, the compound [La2(Succ)3(H2O)2] (phase
2) was obtained with a small amount of phase 3. (iv) As
mentioned in the synthesis section, at temperatures above 190
C and long reaction times, mixtures of phase 4 with traces of
phase 2 are found (Figure 8).
Methodology 2. The next step of the synthetic study was to
test what happened when the organic molecule changed in the
reaction. Dierent aromatic molecules, namely, benzoic acid,
acetylsalycilic acid, aniline, toluene, 6-hydroxypicolinic acid, and
sulfate anion, were tested (Table 3). The template eect has
been extensively studied and demonstrated in several works.33
Templating by guests (TBG) consists of a guest molecule that
act as a template;33 this could be the case for the selected
molecules for this test (Table 3).
According to Table 3, in three cases the main product is
phase 3, which is thermodynamically more stable and whose
formation is favored. The presence of water molecules in the
cavities stabilize the structure through interactions with the
coordinated water molecules. In this case, the water acts as a
template to give rise to small channels.
Using 6-hydroxypicolinic acid, acetylsalycilic acid, and aniline
resulted in the formation of the compound [Ln(succ)(Oxal)0.5(H2O)2]H2O.55 This occurs possibly due to the
total decomposition of these molecules at high temperature
(200 C), which allows the formation of oxalate anion.
Finally, in the presence of toluene, the formation of phase 2
is almost total, which suggests that toluene can be a template
giving structural support to the MOF formation. The toluene
template shifts the formation equilibrium to phase 2 and acts as
a support changing the formation energy and mechanism.
Theoretical Stability Studies. The crystal structural
stability study was performed through the lattice geometry
optimization calculations of the reaction products obtained
under synthesis methodology 1 (phases 1, 2, 3, and 4). These
calculations were carried out in three dierent approaches using
as the initial geometry the single-crystal X-ray structures (see
Experimental Section for details). In the rst approach, only the
atom positions were optimized. In the second approach, the cell
parameters together with the atoms positions were optimized at
a xed volume. Finally, in the third approach, a full cell
optimization was performed without any constraints. Our
results are summarized in Table 4.
The results in Table 4 indicate that the crystal structures
correspond to the more stable structures. This is based on the
fact that the calculated crystal energies are very similar, even

18.5(1) for A and B, respectively. Type C shows torsion angles

with values C8C7C11C12 = 168.5(8), O5C8C7C11 =
109.6(1), and O1C12C11C7 = 167.6(9).
The family of crystalline Ln-succinate compounds can be
identied as a 3D covalent network. This network presents the
particularity of having large pores or channels whose calculated
void volumes (by PLATON)52 range between 205.1 and 247.6
3 per unit cell, which correspond to values around 2024% of
the cell volume (Figure 6). Table 2 shows the void space

Figure 6. Crystal void and void surface (0.002 au) for compound
[La2(Succ)3(H2O)2] (crystal voids calculate with CrystalExplorer).53

Table 2. Void Space and Topology Comparison for

Compounds Obtained in This Work and Others Previously
Reported
compound

space
group

[La2(Succ)3(H2O)2]
[La2(Succ)3(H2O)2]b
[Pr2(Succ)3(H2O)2]b
[Nd2(Succ)3(H2O)2]b
[Gd2(Succ)3(H2O)2]b
[La2(Succ)3(H2O)3]2H2O
[Ce2(Succ)3(H2O)2]54
[La2(Succ)3(H2O)2]H2O
(phase 3)29
[Ho2(Succ)3(H2O)2]24
[Ho2(Succ)3(H2O)2]
0.33(C7H6O3)24
[Sm2(2,2dimethylSucc)3(H2O)2]21
[Ln2(Succ)2(SO4)(H2O)2]
(phase 4)34

P1

P1
P1
C2/c
P1
P1
P1
P21/n

void space (3)

220.6
254.6
235.3
247.6
205.1
c
91.6
166.6

(20.6%)
(23.5%)
(22.2%)
(23.5%)
(20.0%)
(10.3%)
(8.5%)

102.9 (12.0%)
215 (21.5%)

topology

bnn

sql
3,4T1
fsc
pcu
bnn

52.5(4.6%)

bnn

125.6 (8.2%)

pcu

a
Synthesized under methodology 1. bSynthesized under methodology
2. cNo void space.

(solvent accessible volume) of dierent lanthanide/succinatebased compounds, and the synthesized [Ln2(Succ)3(H2O)2]
MOF shows the largest solvent accessibility relative value found
until now (Section S6, Supporting Information, shows a wide
search in CCDC of Ln/succinate compounds).
Making a simplied model of the 3D network is made
possible by rod-packing construction.51 It could be observed
that the intermetallic centroid may act as a 5-connected node
(Figure 7), while the succinate anions link this node give rise to
a 5-connected network type bnn with point symbol (4664).40
E

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Figure 7. Polyhedral representation and topological simplication of the bnn network of compound [Ln2(Succ)3(H2O)2].

200 C is observed, which agrees with the release of the

coordination water molecules, followed by a mass loss
corresponding to the total decomposition of the structure at
around 420 C (Section S2, Supporting Information). This
thermal curve shows the high thermal stability of the
compound. It also shows that the strong intramolecular
hydrogen bonds of the coordination water molecule inside
the structure cause an increase in the decomposition temperature. However, no loss of organic molecules in the pores is
observed (from the template molecule), which suggests that the
cavities are empty. The TG curves for the series of compounds
synthesized with toluene (Section S2, Supporting Information)
show similar behavior, with a mass loss corresponding to the
release of the coordination water molecules but also showing a
possible small amount of toluene being released at around
240280 and 330360 C, respectively. This behavior agrees
with the elemental analysis results that showed that 0.33 equiv
of toluene was present in all of the samples. Finally, the total
decomposition of the compound is observed at 420500 C.
IR Analysis. The IR spectra of [La2(Succ)3(H2O)3]2H2O
(phase 1) and [La2(Succ)3(H2O)2] (phase 2) (Figure 10) show
the following vibrational bands: The CH aliphatic vibrations
of the succinate are assigned to the bands around 2920 cm1
in both cases. The OH vibrations of coordination water
molecules are present in the region around 32003220 cm1.
The compound [La2(Succ)3(H2O)3]2H2O presents a broad
band around 3400 cm1 due to OH vibrations of free water
molecules. The as(OCO) are observed as two bands at 1520
and 1570 cm1 for the compound [La2(Succ)3(H2O)2]. For the
compound [La2(Succ)3(H2O)3]2H2O, three bands are observed at higher energy, 1530, 1560, and 1600 cm1. The
dierence in the splitting in these vibrational bands can be
explained by the dierent binding modes, 23 mode in the rst
and 2 and 23 modes in the second compound.25 The band
associated with the symmetric OCO mode is located between
at 13001325 cm1. The characteristic bands of the
compound [La2(Succ)3(H2O)2]H2O compound are present
according to that previously reported.29 All the compounds of
the [Ln2(Succ)3(H2O)2] series, where Ln = La, Pr, Nd, Sm, Eu,
Gd, and Tb, present the same IR spectrum as shown in Section
S3, Supporting Information. The comparison of the spectra for
the compound [La2(Succ)3(H2O)2] synthesized with toluene
and 5-SSA3 do not present dierences in its vibrational prole
(Section S4, Supporting Information).
Luminescent Properties. We performed a general overview of the solid state, room temperature luminescent behavior
for [Ln2(Succ)3(H2O)2] where Ln = La, Pr, Sm, Eu, and Tb. As
a result of the exploration of this property, only compounds
with Sm, Eu, and Tb showed luminescent properties when the

Figure 8. (a) Scheme of the reaction and crystalline products and (b)
scanning reaction conditions for the succinate2/LaIII/5-SSA3 system.

when the lattice optimizations were carried out using dierent

approaches. Each phase has a dierent number of molecular
units and dierent number of atoms. In order to compare the
stability of the phases, we calculate the relative energy, that is,
thelattice energy per atom. From Table 4 and Figure 9, we can
see that the most stable phase is phase 3 and the least stable is
phase 2, which agrees with our experimental ndings. On the
other hand, the order of increasing stability is phase 3 > phase 4
> phase 1 > phase 2 (Figure 9). These values indicates that
phases 1 and 2 are kinetic products that only can be isolated
under special reaction conditions such as relatively low
temperatures, short reaction time (Figure 8b), and most
importantly, the presence of the template molecule that
thermodynamically stabilizes the network. Once phases 1 and
2 form, the evolution of the reaction gives rise to the
thermodynamically most stable product, phase 3. Finally, the
decomposition of the template molecule (5-SSA3) produces
sulfate anions and the condensed phase 4.
Thermal Analysis. The thermal stability of
[Ln2(Succ)3(H2O)2] was determinated by TGA. For the
compound synthesized with 5-SSA3, a mass loss at around
F

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Article

Table 3. Summary of the Templates and Reaction Conditions Studied in This Work

Reference 55.

Table 4. Energy (in eV) for the Dierent Phases

phase
phase
phase
phase

1
2
3
4

energya

energyb

energyc

10337.883504
12353.424257
5750.462236
47824.996056

10337.817257
12353.492220
5750.654977
47824.703158

10337.848130
12354.506532
5750.654977
47824.564723

Relaxing only the atoms coordinates. bRelaxing the cell at constant

volume. cFull cell relaxation.

Figure 10. IR spectra for the dierent phases found in the La/succ/5SSA3 reaction.

red emission corresponding to the radiative decay bands of

transitions 5D0 to 7F0, 7F1, 7F2, 7F3, and 7F4 levels (Figure 11b)
was found for [Eu2(Succ)3(H2O)2]. The same occurs with
[Tb2(Succ)3(H2O)2], in which the transition bands 5D4 to 7Fn
(n = 63) are observed (Figure 11c). According to the results,
an antenna eect of the aliphatic ligand in a highly LnIII
populated media occurs, which promotes the energy transitions
and the emission phenomena. Also, experimentally it seems
that the quenching eect by structural water molecules
decreases or disappears in extended molecules, such as LnMOFs compounds.19,21,34

Figure 9. Relative formation energies calculated for the dierent

phases obtained under methodology 1.

samples were excited at a wavelength around 280 nm.

[Sm2(Succ)3(H2O)2] showed a weak yellow emission with
characteristic bands attributed to the radiative decay from the
4
G5/2 to 6H5/2, 6H7/2, and 6H9/2 levels (Figure 11a). A strong

CONCLUSION
This study has addressed the synthesis and characterization of a
new La/succinate-based 2D compound named phase 1, whose
G

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Article

Figure 11. Room-temperature emission spectra of compounds (a) [Eu2(Succ)3(H2O)2], (b) [Tb2(Succ)3(H2O)2], and (c) [Sm2(Succ)3(H2O)2]
excited to 280 nm.

formula is [La2(Succ)3(H2O)3]2H2O. 5-SSA3 acts as a

template in the formation of phases 1 and 2, in competition
with the more compact and stable phases 3 and 4. The new
phases are the result of the thermodynamic inuence of the
template on the reaction mechanism. The theoretical study
showed a strong correlation between the formation energy and
the relative stability of the compounds synthesized under
methodology 1 following an increasing stability order: phase 3
> phase 4 > phase 1 > phase 2.
General synthesis procedures could be obtained for the
whole [Ln2(Succ)3(H2O)2] family of compounds with excellent
yields and present as unique phases. Also a complete synthetic
study was developed using dierent template molecules, nding
that the use of the toluene is essential for the formation of
phase 2. Room-temperature luminescence measurements show
strong emissions for the Eu and Tb compounds. These
emissions are promoted by the combination of an emitting
center (lanthanide metals) and the organic linker, which causes
an antenna eect on the MOF.

obtained free from the Cambridge Crystallographic Data

Centre via: www.ccdc.cam.ac.uk/data_request/cif.

AUTHOR INFORMATION

Corresponding Author

*E-mail: ridvries@ifsc.usp.br. Fax: +55 (16) 3373-9758.

Notes

The authors declare no competing nancial interest.

ACKNOWLEDGMENTS
R.D. acknowledges Coordenacao de Aperfeicoamento de
Pessoal de Nivel Superior for the CAPES/PNPD scholarship
from the Brazilian Ministry of Education, the Crystallography
Group of IFSC-USP, and M.J. Davila from UFSCAR and E.C.
Muniz from UNESP for the spectroscopic analysis. I.C.
acknowledges Brazilian agency FAPEMIG for the nancial
support. J.E. thanks CNPq for research fellowships.

ASSOCIATED CONTENT

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