MOF formation vs. reversible high ligand uptake in anhydrous halides: Two opposing aspects of ∞3 [La2CI6(4,4'-bipy) 5]·4(4,4'-bipy)

Article abstract of DOI:10.1002/zaac.200900359

Construction of the framework, structure ∞³ (bipy)5]· 4bipy (1), bipy = 4,4'-bipyridine, C₁₀H ₈N₂, is achieved by reaction of the anhydrous halide LaCl₃ with molten 4,4'-bipyridine. Five equivalents of bipyridine are used for the framework construction linking LaCl₃ units to give an extended, three-dimensional MOF. Furthermore, four additional equivalents of bipyridine per LaCl₃ unit are incorporated within the crystalline MOF, which is thereby completely filled with bipy molecules. This compound formation results in the extraordi-nary high uptake of nine equivalents of bipyridine per equivalent of the formula and a volume increase of eight times the volume of LaCl₃. Further heating of the MOFs results in a stepwise release of all nine equivalents of bipyridine and reformation of the anhydrous chloride at 425 °C. Formation and disassembly can be run in cycles and are reversible. Thus two interesting yet opposing aspects are the reversible construction and disassembly of the MOF framework.

Full text of DOI:10.1002/zaac.200900359

ARTICLE
DOI: 10.1002/zaac.200900359
MOF Formation vs. Reversible High Ligand Uptake in Anhydrous Halides:
3
Two Opposing Aspects of [La Cl (4,4'-bipy) ]·4(4,4'-bipy)
∞
2
6
5
[a]
[a]
[b]
Christoph J. Höller, Philipp Matthes, Jens Beckmann, and
Klaus Müller-Buschbaum*[
a]
Dedicated to Professor Hans-Jörg Deiseroth on the Occasion of His 65th Birthday
Keywords: Lanthanum; Metal-organic frameworks; Ln–N-MOFs; Reversibility; 4,4'-Bipyridine
3
Abstract. Construction of the framework structure ∞[La
2
Cl
6
(bipy)
5
]· nary high uptake of nine equivalents of bipyridine per equivalent of
4
bipy (1), bipy = 4,4'-bipyridine, C10
the anhydrous halide LaCl with molten 4,4'-bipyridine. Five equiva- Further heating of the MOFs results in a stepwise release of all nine
lents of bipyridine are used for the framework construction linking equivalents of bipyridine and reformation of the anhydrous chloride at
LaCl units to give an extended, three-dimensional MOF. Furthermore, 425 °C. Formation and disassembly can be run in cycles and are re-
four additional equivalents of bipyridine per LaCl unit are incorpo- versible. Thus two interesting yet opposing aspects are the reversible
8 2 3
H N , is achieved by reaction of the formula and a volume increase of eight times the volume of LaCl .
3
3
3
rated within the crystalline MOF, which is thereby completely filled construction and disassembly of the MOF framework.
with bipy molecules. This compound formation results in the extraordi-
Introduction
MOFs and disassembly into the reagents can be directed de-
pending on the temperature. We now found that the number of
Usually, the construction of MOFs is described as an in-
tended one way reaction of metal salts and complexes with a
suitable linker to give a multi-dimensional framework structure
equivalents that are reversibly incorporated in LnX can be fur-
3
ther increased for lanthanum up to nine equivalents per for-
mula unit including the reversible character of the reactions.
Accordingly, formation and disassembly reactions of MOFs
can be equally interesting for such a high and reversible ligand
uptake in anhydrous halides of the rare earth elements.
[1–6]. The way back and thereby decomposition of the MOF
structures is fairly unwanted. This includes the N ligand con-
taining Ln–N-MOFs we have elaborated from ligand melts [7].
Nonetheless decomposition is a prominent feature of all sol-
vent containing MOFs that enforce a thermal activation in or-
der to gain porous materials by evaporation of incorporated
solvate ligands [8–10]. As collapse of the referring frameworks
is likely for highly solvent containing MOFs it is also limiting
the interest in such materials. We discovered for the series of
two-dimensional 4,4'-bipyridine containing Ln–N-MOFs of the
Scheme 1. The amine ligand 4,4'-bipyridine.
2
formula [Ln Cl (bipy) ]·2bipy, with Ln = Ce, Pr, Nd, Sm, Eu,
∞
2
6
3
Tb, bipy = 4,4'-bipyridine (C H N , see Scheme 1) [11] that
their formation is thermally reversible. Construction of the
10
8
2
Experimental Section
All manipulations were carried out under inert atmospheric conditions
using glove box, ampoule as well as vacuum line techniques. Heating
*
PD Dr. K. Müller-Buschbaum
Fax: +49-89-2180-77851
furnaces were equipped with Al
2
O
3
tubes and EUROTHERM 2416
]·4bipy (1), the trichloride LaCl
E-Mail: kmbch@cup.uni-muenchen.de
3
control elements. For [La
2
Cl
6
(bipy)
5
3
,
[
a] Department für Chemie und Biochemie
Ludwig-Maximilians-Universität München
Butenandtstr. 5–13 (D)
∞
was prepared according to the known ammonium halide route [12]
–1
using the oxide La
2
O
3
(ChemPur, 99.9 %), HCl solution (10 mol·l ,
81377 München, Germany
reagent grade) and ammonium chloride (Fluka, 99.5 %), and purified
by decomposition of the trivalent ammonium chlorides under vacuum
and subsequent sublimation of the products. 4,4'-bipyridine (ACROS,
[
b] Institut für Chemie und Biochemie
Anorganische Chemie
Freie Universität Berlin
Fabeckstraße 34–36
9
8 %) was used as purchased. All products are air and moisture sensi-
14195 Berlin, Germany
tive. The IR spectra were recorded using a BRUKER FTIR-IS66V-S
spectrometer. KBr pellets for Mid IR investigation and PE pellets for
Far IR were used under vacuum. Only the crystalline product was
Supporting information for this article is available on the WWW
under http://dx.doi.org/10.1002/zaac.200900359 or from the
author.
Z. Anorg. Allg. Chem. 2010, 636, 395–399
© 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
395

C. J. Höller, P. Matthes, J. Beckmann, K. Müller-Buschbaum
ARTICLE
used for micro analyses on a Vario Microcube (Elementar) elemental Crystal Structure Determination
analyzer. The yield of the reaction was calculated according to the
3
∞
2 6
The best suitable single crystal of the compound [La Cl (4,4'-
amount of ligand used for the synthesis. For thermal analysis the bulk
3
bipy) ]·4(4,4'-bipy) (1) was selected for single-crystal X-ray investiga-
5
product of [La
2
Cl
6 5
(4,4'-bipy) ]·4(4,4'-bipy) was studied using simulta-
∞
3
tion under glovebox conditions and sealed in a glass capillary. Data
neous DTA/TG (TG-DTA92 Setaram). 17,5 mg of [La
2
6
Cl (4,4'-
∞
collection was carried out on a STOE IPDS-II diffractometer (Mo-K
α
5
bipy) ]·4(4,4'-bipy) were heated from 25 °C to 700 °C in a constant
–
1
–1
radiation λ = 0.7107 Å) at 170 K. The structure was determined using
direct methods [13]. All non hydrogen atoms were refined anisotropi-
cally by least-squares techniques [14]. All hydrogen positions were
calculated into pre-set positions adjusting their thermal parameters to
helium flow of 50ml·min with a heating rate of 10 °C·min .
3
Synthesis of [La Cl (bipy) ]·4bipy
∞
2
6
5
1
.2 of the referring carbon atoms. The compound crystallizes in the
LaCl
3
(0.25 mmol, 62 mg) and 4,4'-bipyridine (bipy, 1.25 mmol,
¯
triclinic space group P1. Because of the free rotation of the pyridine
rings in 4,4'-bipyridine one incorporated bipy molecule is disordered
TM
195 mg) were sealed in an evacuated DURAN glass ampoule and
heated to 90 °C in 7 h and then to 120 °C within 30 h. The temperature
was held for 48 h and afterwards cooled to 95 °C in 250 h and finally
to room temperature in further 14 h. The reaction resulted in high
reflecting colorless crystals of the product and an amount of unreacted
(
see Supporting Information). Integrity of symmetry and extinction
were checked and no higher symmetry could be found [15]. A numeri-
cal absorption correction was applied [16]. For crystallographic data
see Table 1. Further information was deposited at the Cambridge Crys-
tallographic Data Centre, CCDC, 12 Union Road, Cambridge CB2
LaCl
La Cl
Found: C, 56.74; N, 12.98; H, 3,95 %. MIR (KBr): (3129 s, 1591 m,
3
in the bulk. Yield: 199 mg
C H N18; M = 1896.22 g·mol : C, 57.01; N, 13.30; H, 3.83.
6 90 72
=
84 %. Anal. calcd.
–
1
2
1
EZ, UK (Fax: +44-1223336033 or E-Mail: deposit@ccdc.cam.ac.uk)
and may be requested by citing the deposition number CCDC-740032,
the names of the authors and the literature citation.
1
8
2
532 w, 1489 w, 1403 s, 1231 w, 1066 w, 1011 w, 868 w, 822 msh,
01 s, 733 w, 614 m, 571 w, 474 w) cm . FIR (PE): (570 m, 474 m,
–
1
–
1
36 w, 214 m, 179 m, 160 w, 143 w) cm .
Results and Discussion
Studies concerning the reversibility of formation and disassembly of
the framework compound were performed with the same amounts of Reversible Formation and High Ligand Uptake
the reagents but shortened in annealing and reaction times for each
step. Only one tenth annealing (24 h) and the half reaction time (24 h)
were applied. Therefore, no complete reaction occurred and the crystal-
We elaborated that the use of melts of organic ligands like
N-heterocyclic amines is a suitable alternative to solvent treat-
linity degrades. These conditions were chosen in order to keep a rea- ments if co-coordination of the solvent is to be avoided [17].
sonable timeframe for multiple repetitions. Therefore an amount of Depending on the ligands used and the reaction conditions a
2
5 % of unreacted halide LaCl
3
remains.
large structural variety ranging from small molecular com-
plexes [17a, 18] to coordination polymers and MOFs [19] can
be obtained. The ligand melt can be directly used for oxidizing
reactive metals like the lanthanides acting as weak N–H acids
using various activation methods for the metals [17a, 20]. The
method can also be used for other ligands like phenols [21] or
thioles [22] to yield amides, phenolates and thiolates of the
rare earth elements together with hydrogen gas. It can be fur-
ther expanded to ligands that cannot be utilized in a redox
reaction. Instead of metals, we successfully used anhydrous
halides of the rare earth elements to yield nitriles [23] of the
lanthanides including the first dinitrile Ln–N-MOFs of the re-
ferring elements [24, 25]. Accordingly, the 4,4'-bipyridine li-
gand that has been used for MOF constructions of transition
metals already [26–28] was most promising for our synthesis
strategy together with lanthanide halides. 4,4'-bipyridine acts
as chemical scissors and cuts down the halide structure. It also
controls the formation of coordination polymers by interlink-
3
Table 1. Crystallographic data for [La
2
Cl
6
(bipy)
5
]·4bipy. Deviations
∞
are given in brackets.
formula
C
90
H
72
N18La
2
Cl
6
formula weight
crystal system
space group
a /pm
1896.18
triclinic
¯
P1
1344.7(3)
1371.5(3)
1430.1(3)
79.48(3)
63.90(3)
65.68(3)
2158.3(11)
1
b /pm
c /pm
α /°
β /°
γ /°
6
3
V /10 pm
Z
d
calcd. /g· cm–3
1.459
–
1
μ/cm
T /K
data range
12.2
173(2)
3.18 ≤ 2θ ≤ 54.66
ing LnCl units. For numerous lanthanides this can lead to 2D-
3
X-ray radiation /pm
diffractometer
α
Mo-K , λ = 71.073
2
nets of the formula [Ln Cl (bipy) ]·2bipy, with Ln = Ce, Pr,
STOE Image Plate Diffraction Sys-
∞
2
6
3
tem II
9557
Nd, Sm, Eu, Tb, [11]. In addition to three interlinking ligands
no. of unique reflections
per two LnCl units, two equivalents of bipy are incorporated
3
no. of refined parameters / refl./
in cavities within and in between the sheets. For the larger
trivalent ion La3+ we now found that an extraordinary increase
in the 4,4'-bipyridine uptake is observed according to the reac-
tion [Equation (1)]:
parameter ratio
567 / 17
a)
R
F
R
1
o
1
wR
for n reflections with
>4σ (F
(all)
o
); n
0.0447; 5743
0.0965
0.0951
b)
2
(all)
C10H N melt
3
8
2
2
LaCl
3
+ 9 C10
H
8
N
2
→ [La
2
Cl
6
(C10
H
8
N
2
)
5
]·4(C10
H
8
N
2
) (1)
∞
remaining electron density
e· pm·10
120 °C
–
6
/
+0.85/–2.13
At temperatures starting from 155 °C the MOF begins to
release the incorporated bipyridine equivalents in three steps.
1 o c o 2 o c o
a) R = Σ[|F |–|F |]/Σ [|F |. b) wR = (Σw(F
2–F 2)2/(Σw (F 4))1/2 [14].
3
96
www.zaac.wiley-vch.de
© 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 2010, 395–399

MOF Formation vs. Reversible High Ligand Uptake in Anhydrous Halides
Removal of the template bipyridine is in principle possible by
evaporation, as thermal investigations reveal. But as this does
not lead to suitable crystals, it has yet not been possible to
refine the structure of this new template free high temperature
compound. At temperatures between 330–425 °C also the link-
ing bipyridine equivalents are released in two steps under re-
formation of LaCl [Equation (2)], as observed by simultane-
3
ous DTA/TG (see Figure 1):
3
Figure 2. Simulated powder pattern (1) of [La
2
Cl
6
(bipy)
5
]·4bipy (1)
∞
(
from bottom to top) as well as powder diffractogram of the bulk pro-
duct of the MOF formation (2) in comparison to diffractograms after
3
disassembly of the MOF to LaCl (3). Both reactions can be run in
cycles as the repetitions of patterns indicate (Mo-Kα1 radiation, λ =
0.7107 Å).
3
Figure 1. Simultaneous DTA/TG of [La
2
Cl
6
(bipy)
5
]·4bipy (1) reveals
∞
a five step release of 4,4'-bipyridine from the framework. The first
Anhydrous halides LnX can show an extraordinary high up-
three signals correspond to intercalated bipy equivalents; the forth and
3
fifth signal above 350 °C indicate the framework disassembly and ref- take of the organic ligand 4,4'-bipyridine with formation of N-
ormation of the reagents.
donor complexes as thermal intermediates and re-formation of
the halides at suitable temperatures.
3
∞
155–425 °C
[La
2
Cl
6
(C10
H
8
N
2
)
5
]·4(C10
H
8
N
2
)
3 8 2
→2 LaCl + 9 C10H N ↑ (2)
If the bipy equivalents released from the MOF are recovered, Crystal Structure
the formation reaction can be started over. Thus formation and
disassembly of the framework are reversible. Formation and
disassembly can be run in cycles as powder diffraction indi-
3
The crystal structure of [La Cl (bipy) ]·4bipy (1), bipy =
∞
2
6
5
4
,4'-bipyridine, C H N , constitutes to a three-dimensional
10 8 2
framework. It is built up by trivalent lanthanum ions linked by
cates, (see Figure 2) [29]. Some unreacted LaCl in the product
3
3
4
4
,4'-bipyridine ligands and chloride ions. ∞[La Cl (bipy) ]·
2 6 5
pattern originates from incomplete reaction because of shorter
reaction and annealing times, which had to be chosen in order
to allow multiple reversible processes in a reasonable time-
frame. Reversibility is further supported by IR spectroscopy.
Mid IR spectra of the product contain bands that can be identi-
fied with the ν(C–N) stretching modes. They are shifted to
smaller wave numbers compared to the free ligand because of
binding to the metal ions and thus weakening of the C–N
bipy exhibit a CN of eight consisting of three halide atoms
each as well as two additional nitrogen atoms, resulting in a
–
1
bonds at 1011 cm . The ν(C=N) ring vibrations of the uncoor-
–1
dinated 4,4'-bipyridine are observed at 1591 cm . Further-
more, the Far IR spectra of framework 1 contain bands that
indicate ν(Ln–N) stretching modes between 236–214 cm–1
[
30]. Only the Ln–Cl stretching and deformation bands at 571
–
1
and 474 cm [31] are found after disassembly.
That leads us to describing the compound presented here
with two equally interesting features: As the first feature a
MOF structure is formed that is able to incorporate a large
number of additional bipy equivalents as well as these incorpo-
rated molecules can all be thermally released. Moreover, as the
linking bipyridine equivalents can also be released reversibly,
Figure 3. The double capped trigonal prismatic coordination sphere of
III
3
∞
2 6 5
nitrogen and chlorine atoms around La in [La Cl (bipy) ]·4bipy as
well as the thermal ellipsoids of the atoms reflecting 50 % probability.
Symmetry operations: I: 1 –x, 2 –y, 1 –z, II: 2 –x, 1 –y, 1 –z, III: 2
another interesting point can be raised as the second feature: –x, 2 –y, 1 –z, IV: –x, 2 –y, 2 –z.
Z. Anorg. Allg. Chem. 2010, 395–399
© 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.zaac.wiley-vch.de
397

C. J. Höller, P. Matthes, J. Beckmann, K. Müller-Buschbaum
ARTICLE
double nitrogen capped trigonal prism around lanthanum.
Three bipyridine ligands coordinate rather symmetrically
1
1
μ-η :η to two different lanthanide cations with each nitrogen
atom of the pyridine rings. The double capping nitrogen atoms
exhibit an N–La–N angle of 135.7(2)° (ideal 120°). A fourth
1
bipyridine molecule coordinates end-on η to only one lantha-
nide ion. Four chloride ions complete the coordination sphere
of every lanthanide atom (see Figure 3, for selected intera-
tomic distances and angles see Table 2). Edge sharing of the
double capped trigonal prisms leads to the formation of a
three-dimensional framework. The CN of lanthanum in 1 is
higher than for the series of lanthanides of the formula
2
[
Ln Cl (bipy) ]·2bipy, with Ln = Ce, Pr, Nd, Sm, Eu, Tb [11],
∞
2 6 3
which exhibit pentagonal-bipyramidal coordination. This cor-
roborates the fact that La3 is the largest of the Ln ions [32].
+
3+
Double capped trigonal prisms around lanthanum atoms can
also be found in La OCl[AsO ]
as well as in
3
3 2
[
La (aib) (H O) ](ClO ) (aib = α-aminoisobutyric acid) [33,
2 4 2 8 4 6
3
4], although the most numerous coordination polyhedron for
3+
La with CN eight is the square antiprism, especially regard-
ing nitrogen coordination [35]. The La–N distances in 1 range
3+
from 274.9(4) to 281.8(4) pm. Because of the large La -ion
and the high coordination number of eight, the La–N distances
are about 20 pm larger than the ones e.g. found for
2
[
Sm Cl (bipy) ]·2bipy
of
258–263 pm
[11].
In
3
∞
2
6
3
3
Figure 4. The crystal structure of
∞
2
[La Cl
6
(bipy)
5
]·4bipy with a view
[
La Cl (bipy) ]·4bipy two of the chloride ions also link be-
∞
2
6
5
along [001] (top) and [010] (bottom). Incorporated bipyridine molecu-
les are either emphasized by ellipsoids (top) or omitted for clarity (bot-
tween different lanthanide ions forming a “double bridge” [36].
The La–Cl distances range from 276.0(2) to 296.4(2) pm and tom). Lanthanum atoms are depicted as large grey balls, nitrogen atoms
as dark, carbon atoms as well as chlorine atoms as light grey balls.
match with the trichloride [37]. Figure 4 depicts the crystal
Hydrogen atoms are omitted for clarity as well.
structure of 1.
Table 2. Selected distances /pm and angles /deg between atoms of
3
∞
2 6 5
[La Cl (bipy) ]·4bipy. Deviations are given in brackets.
atoms
distances
atoms
angles
La1–N1
La1–N2
La1–N3
La1–N4
La1–Cl1
La1–Cl1
La1–Cl2
La1–Cl3
279.4(4)
281.8(4)
274.9(4)
276.4(4)
288.7(2)
296.4(2)
276.0(2)
280.6(2)
N1–La1–N2
N3–La1–N4
Cl1–La1–Cl1
Cl2–La1–Cl3
Cl1–La1–N3
135.70(13)
66.63(13)
68.05(5)
102.49(5)
98.00(10)
#
1
#
1
Symmetry operation: #1 1 –x, 2 –y, 1 –z.
3
Figure 5. Topological drawing of [La
2
Cl
6
(bipy)
5
]·4bipy with a view
∞
As the linkage leads to a complicated crystal structure, it is
reasonable to reduce it to topological description.
La Cl (bipy) ]·4bipy can be identified with two perpendicu-
along [100]. The framework can be identified with a three-dimensional
6,4) net that consists of two two-dimensional 6,3 nets.
a
(
3
[
∞
2
6
5
lar 2D-nets that each have a 6,3 topology. Viz., three sixfold
bridged rings form a 2D-layer. This gives an overall 3D (6,4)
topology (see Figure 5). This topology is e.g. also found for
–
MOFs like Co(Im)2 (Im
=
N C H , imidazolate) or Acknowledgement
2
3
3
–
[
Eu(pdc) (dmf)]·dmf·(H O) (pdc2 = pyridine-3,5-dicarbox-
1,5 2 0.5
We thank the Deutsche Forschungsgemeinschaft for supporting this
work by the project “3D-Raumnetze komplexer Selten-Erd-Amide, ein
Weg zu neuartigen MOFs”, Prof. Dr. W. Schnick and the LMU Mün-
ylate, dmf = dimethylformamid) [38, 39]. The topology de-
scription however is based on counting the chloride “double-
bridges” as one bridge only. Otherwise the connectivity would chen for the excellent conditions, and the Wilhelm-Klemm- and the
be five.
Dr.Otto-Röhm-Gedächtnis-Foundation for their support.
3
98
www.zaac.wiley-vch.de
© 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 2010, 395–399

MOF Formation vs. Reversible High Ligand Uptake in Anhydrous Halides
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Received: July 28, 2009
Published Online: December 3, 2009
Z. Anorg. Allg. Chem. 2010, 395–399
© 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.zaac.wiley-vch.de
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