A robust anionic pillared-layer framework with triphenylamine-based linkers: Ion exchange and counterion-dependent sorption properties

Article abstract of DOI:10.1039/c7ce00369b

A new anionic pillared-layer cobalt(ii) metal-organic framework combining 4,4′,4′′-nitrilotribenzoic acid (H₃ntb) as a linker and terephthalic acid (H₂bdc) as a pillar-ligand with the formula {((CH₃)₂NH₂)₂[Co₃(ntb)₂(bdc)]}_n (JUMP-1, JUMP = Jena University Magnetic Polymer) has been solvothermally synthesized and characterized. The crystal structure of JUMP-1 was determined to belong to the orthorhombic space group Cmca. It displays a three-dimensional (3D) framework for which the topological analysis revealed a 3,8-connected net with a tfz-d topology. The 3-connected organic node is linked to an 8-connected secondary building unit composed of a linear trinuclear cobalt(ii) cluster with a mixed arrangement of coordination geometries (T_d-O_h-T_d) leading to two-dimensional layers which are further linked by terephthalic acid to give the pillared-layer arrangement. The magnetic properties are characterized by an antiferromagnetic coupling between a central octahedrally coordinated cobalt(ii) ion and two outer tetrahedral cobalt(ii) centers, whereas only a very weak inter-cluster coupling is observed. Moreover, a moderate zero-field splitting is detected for the tetrahedral cobalt(ii) ions. The organic counterions could successfully be exchanged by lithium ions under retention of the anionic 3D network leading to JUMP-1(Li). For both compounds JUMP-1 and JUMP-1(Li), N₂ and CO₂ adsorption isotherms were measured. The pore distribution analyses revealed improved microporosity for the lithium exchanged MOF.

Full text of DOI:10.1039/c7ce00369b

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HIGHLIGHT
Tiddo J. Mooibroek, Antonio Frontera et al.
Towards design strategies for anion–π interactions in crystal engineering
rsc.li/crystengcomm

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CrystEngComm
PAPER
Robust anionic pillared-layer framework with
triphenylamine-based linkers: ion exchange and
†
counterion-dependent sorption properties
∗
Oluseun Akintola, Sven Ziegenbalg, Axel Buchholz, Helmar Görls and Winfried Plass
0
00
A new anionic pillared-layer cobalt(II) metal-organic framework combining the 4,4 ,4 -
nitrilotribenzoic acid (H ntb) as linker and terephthalic acid (H bdc) as pillar-ligand with the for-
3
2
mula {((CH ) NH ) [Co (ntb) (bdc)]} (JUMP-1, JUMP = Jena University Magnetic Polymer) has
3
2
2 2
3
2
n
been solvothermally synthesized and characterized. The crystal structure of JUMP-1 was deter-
mined to belong to the orthorhombic space group Cmca. It displays a three-dimensional (3D)
framework for which the topological analysis revealed a 3,8-connected net with tfz-d topology.
The 3-connected organic node is linked to an 8-connected secondary building unit composed of
a linear trinuclear cobalt(II) cluster with a mixed arrangement of coordination geometries (Td–
O –T ) leading to two-dimensional layers which are further linked by terephthalic acid to give the
h
d
pillared-layer arrangement. The magnetic properties are characterized by an antiferromagnetic
coupling between the central octahedrally coordinated cobalt(II) ion and the two outer tetrahe-
dral cobalt(II) centers, whereas only a very weak inter-cluster coupling is observed. Moreover, a
moderate zero-field splitting is detected for the tetrahedral cobalt(II) ions. The organic counterions
could successfully be exchanged by lithium ions under retention of the anionic 3D network leading
to JUMP-1(Li). For both compounds JUMP-1 and JUMP-1(Li) N and CO adsorption isotherms
2
2
were measured. The pore distribution analyses revealed improved microporosity for the lithium
exchanged MOF.
Introduction
as in the case of the isoreticular series.4 While this method has
The field of coordination polymers and in particular that of metal-
organic frameworks (MOFs) has become an ever more popular
area of interest in recent years. This is, no doubt, due to the
many applications of this class of compounds some of which in-
clude catalysis, gas storage, separation and sequestration, ion ex-
change, magnetism and sensing.1 The most common strategy in
obtaining them, so far, has been the simple combination of metals
and polytopic ligands mostly under solvothermal conditions in a
process of self-assembly with emphasis on slim organic linkers to
worked quite well till date, it has also had its drawbacks such as
in the case of interpenetrated or even fragile structures due to the
frameworks being poorly reinforced.
5
Even so total control over the synthesis of MOFs still remains
an elusive goal in particular the ability to tune properties such
as the pore sizes which is most desirable. One of the attempts
to achieve this level of controllability has been the construction
6
of pillared-layer structures. A major advantage of this strategy is
that it offers new levels of functionality in addition to avoiding the
stress of searching for new linkers while at the same time making
the most of existing ones. This approach has subsequently led to
the discovery of MOFs with some of the highest reported surface
2
provide access to high porosity. As the functional groups are con-
cerned polycarboxylate linkers, particularly aromatic based, have
been subjected to frequent use since they confer rigidity and sta-
3
bility on the obtained frameworks. This approach has even been
5,7
2
areas currently known such as the UMCM-1
and MOF-210 of
extended by use of spacer groups to expand the existing ligands
thus increasing the potential for better surface properties such
which the latter was only surpassed by the discovery of the NU-
2
−1 8
.
1
10 with over 7000 m g
These pillared-layer systems have been found to be effective
routes in obtaining three dimensional frameworks in addition to
offering the possibility of chemically functionalizing the channels
for selective adsorption behavior via modification of the pillar lig-
ands. Selecting appropriate pillared ligands can be used to gen-
erate flexible MOFs which have the ability to undergo structural
a
Institut für Anorganische und Analytische Chemie, Friedrich-Schiller-Universität,
Jena, Humboldtstr 8, 07743 Jena, Germany. Fax:+49 (0)3641 948132; Tel:+49
(
†
0)3641 948130; E-mail: Sekr.Plass@uni-jena.de
Structural figures, XRPD patterns, TGA curves, topological data and sorption data
are included in the ESI. See DOI: 10.1039/b000000x/
9
1
–10 | 1

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changes during adsorption and desorption of guests and are in-
teresting for applications in selective gas adsorption/separation
or chemical sensing.10 This approach has also been used to fa-
cilitate the interconnection of layered structures with interesting
magnetic properties and, moreover, to introduce redox-active
organic linkers in relevant frameworks.12
sorption isotherms were measured on an Autosorb-IQ instrument
from Quantachrome Instruments Corporation. Solvothermal re-
actions were carried out in a 23 mL Teflon-lined acid digestion
vessel from Parr Instruments, utilizing a programmable oven by
Binder. X-ray powder diffraction (XRPD) measurements were per-
formed on a Stoe Powder Diffractometer with a Mythen 1K detec-
tor at room temperature. Measurements were done using capil-
lary tubes while the Debye Scherrer Scan Mode was applied with
a 2θ scan type. The X-ray tube was a Cu-long fine focus tube. The
powdered samples were suspended in DMF and transferred in a
0.5 mm glass capillary for measurement, which was carried out
between 2 and 50° with steps of 2.1° per 20 seconds.
1
1
A common approach in synthesizing such mixed-ligand frame-
works has been the coordination copolymerization route usually
involving mixing two different linkers.7,13 When combined, the
organic linkers tend to cooperate thus avoiding formation of two
separate single ligand MOFs.14 Subtle changes in reaction con-
ditions such as reactant ratios, temperature or even solvent of-
1
5
ten lead to slight variations in the final structure obtained.
Common ligands acting as pillars include the dicarboxylates like
terephthalate or its derivatives and nitrogen based ligands such
as imidazoles or bipyridines.16
Synthesis
{
((CH ) NH ) [Co (ntb) (bdc)]}n · 4DMF · 2H O
3
2
2 2
3
2
2
We herein report the construction of a new anionic pillared-
layer MOF, named JUMP-1 (JUMP = Jena University Magnetic
(JUMP-1 · 4DMF · 2H O). Terephthalic acid (H bdc, 33 mg,
2
2
0
.199 mmol) and H ntb (50 mg, 0.13 mmol) were dissolved
3
0
00
Polymer), which is based on the redox-active ligand 4,4 ,4 -
and stirred in DMF (5 mL) for 15 min. Cobalt(II) chloride
hexahydrate (126 mg, 0.52 mmol) was then added and stirred
for a further 15 min after which all solid was dissolved. The
solution was then placed in a Parr acid digestion vessel and
heated at 140 °C for 72 h under autogenous pressure. It was
then allowed to cool at a rate of 5 °C h
crystals could be seen in the room temperature sample which
were washed repeatedly with DMF (3 × 5 mL) and subsequently
dried in vacuo for 1h, leading the further denoted as-synthesized
nitrilotribenzoic acid (H ntb) with the inclusion of terephthalic
3
acid as pillar ligand containing a linear trinuclear cobalt(II) clus-
ter as secondary building unit (SBU). The anionic nature of the
resulting framework will be used for post-synthetic modification
via cation exchange and the resulting sorption properties before
and after exchange will be reported.
−1
.
Deep blue-violet
Experimental section
Materials
material JUMP-1 · 4DMF · 2H O. Employing extended periods
2
Triphenylamine (Alfa Aesar) and cobalt(II) chloride hexahydrate
for the drying process lead to lower solvent content of the
resulting material, as evidenced by CHN elemental analysis and
(
Aldrich) were obtained commercially and used without further
purification. All other chemicals were of AR grade. The tribro-
motriphenylamine used was prepared from triphenylamine by a
reported procedure. The final ligand 4,4 ,4 -nitrilotribenzoic
TG measurements. Yield for JUMP-1 · 4DMF · 2H O: 71.0 mg,
2
0.047 mmol, 72 % based on ligand. CHN elemental analysis calcd
1
7
0
00
for JUMP-1 · 4DMF · 2H O C66H76Co N O (M = 1510.34): C,
2
3
8
22
acid (H ntb) was obtained in good yield following procedures
52.5; H, 5.1; N, 7.4 %. Found: C, 52.35; H, 5.0; N, 7.7 %.
3
1
8,19
−1
already described in literature.
Selected IR data ( ν˜ max/cm ): 1657s, 1592s, 1504w, 1385vs,
1
Analytical Data for H ntb. H NMR (400 MHz, [D ]DMSO,
1312s, 1275s, 1171m, 1130m, 1092w, 834w, 779s, 675m.
3
6
3
3
2
=
5 °C, δ in ppm): 7.13 (d, J
= 8.7 Hz, 6H), 7.89 (d, J
H,H
H,H
8.7 Hz, 6H), 12.76 (s, 3H). 1 C NMR (100 MHz, [D ]DMSO,
3
6
2
5 °C, δ in ppm): 123.7, 125.9, 131.2, 149.8, 166.7. Selected IR
−
1
Cation exchange
data (ATR, cm ): 1672s, 1591s, 1509m, 1417s, 1314s, 1275vs,
+
1173s, 1129m, 932m. EI-MS: m/z 377 (M , 100%).
{
Li [Co (ntb) (bdc)]}n · 4EtOH · 8H O (JUMP-1(Li) · 4EtOH
2
3
2
2
·
8H O). The as-synthesized JUMP-1 · 4DMF · 2H O was im-
2
2
Physical measurements
mersed in a saturated ethanolic LiNO solution for 10 d. During
3
Simultaneous TG/DTA analyses were performed under static air
atmosphere using a Netzsch STA Luxx PC analyzer up to 1000 °C.
The FT-IR spectra were measured on a VERTEX 70 IR spectrom-
eter by Bruker Optics using the Specac Diamond ATR optional
accessory. Mass spectrometry was performed on a MAT SSQ710
mass spectrometer made by Bruker. NMR spectra were recorded
with a Bruker AVANCE400 spectrometer. The elemental analy-
ses were done on a VARIO EL III analyzer. The magnetic sus-
ceptibilities were measured on the bulk vacuum dried materi-
als in the 2–300 K temperature range with a Quantum Design
MPMS-5 superconducting SQUID magnetometer. The data were
corrected for diamagnetic contributions. The N and CO physi-
this period the soaking solution was replaced every 24 h. After
the 10 d period the lithium ion exchanged material was subse-
quently soaked for one week in ethanol to remove any residual
free LiNO3 molecules. According to the elemental analysis of
the final product the organoammonium cations present in the
as-synthesized JUMP-1 · 4DMF · 2H O were fully replaced by the
2
lithium cations. The obtained lithium ion exchanged framework
is further denoted as JUMP-1(Li). CHN elemental analysis calcd
for C58H68Co Li N O (M = 1431.84): C, 48.65; H, 4.8; N,
3
2
2
28
2.0 %. Found: C, 48.3; H, 4.95; N, 1.8 %. Selected IR data
−
1
( ν˜ max/cm ): 3326br, 1589s, 1506w, 1378vs, 1313s, 1273s,
1174m, 1147m, 1087w, 1045m, 833w, 780s, 675m.
2
2
2
|
1–10

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X-ray structure determination
and the lithium ion exchanged JUMP-1(Li) samples resulting in
the products JUMP-1 and JUMP-1(Li) , respectively.
scd
scd
The intensity data were collected on a Nonius KappaCCD diffrac-
tometer, using graphite-monochromated Mo-Kα radiation. Data
were corrected for Lorentz and polarization effects, but not
Sorption measurements. The isotherms of all pretreated and
dried products were measured immediately after degassing the
samples for 30 min at room temperature. Pore size distribution
curves were calculated by fitting the experimental data using a
quenched solid density functional theory (QSDFT) kernel based
on adsorption models for N2 on carbon at 77 K with cylindri-
cal/slit pores, which was provided by QUANTACHROME Instru-
2
0
for absorption.
The structure was solved by direct methods
2
1
(
SHELXS) and refined by full-matrix least squares techniques
against Fo (SHELXL). The crystal structure of JUMP-1 contains
2
21
large voids, filled with disordered dimethylammonium cations
and solvent molecules. The total size of the voids is 13846 Å /unit
3
2
4
ments.
The Brunauer-Emmett-Teller (BET) surface areas for
cell. Their contribution to the structure factors was secured by
back-Fourier transformation using the SQUEEZE routine of the
both materials were determined from the adsorption data over
different relative pressure ranges all between 0.005–0.28 while
ensuring compliance with the consistency criteria.2
2
2
program PLATON resulting in 2787 electrons/unit cell. All hy-
drogen atoms were included at calculated positions with fixed
thermal parameters. All non-disordered, non-hydrogen atoms
5
Results and discussion
21
were refined anisotropically. Diamond 4.2.2 was used for struc-
ture representations.23
Synthesis
The title compound JUMP-1 was prepared utilizing the copoly-
merization technique. It was shown earlier that this reaction tech-
nique requires a subtle balance between geometry and statistics.
Crystallographic and refinement parameters for JUMP-1.
Formula C50H28Co N O , M = 1089.53, orthorhombic Cmca, a =
3
2
16
5
3
3
3.6004(6), b = 26.9604(5), c = 23.2138(5) Å, V = 21028.9(7) Å ,
T = 133 K, Z = 8, ρcalc = 0.688 g cm , µ = 0.501 mm , 69315
measured reflections, θmax = 27.34°, 11978 unique reflections
−3
−1
To evaluate these conditions it was found that the geometric ra-
tio between the length of the ditopic (L ) and tritopic (Lt) linkers
d
is an important parameter (see Scheme 1). It was reported that
the ratio L /L should not be too high with the ideal value of just
d
t
(
Rint = 0.0856) and 7595 observed reflections (I > 2σ(I)), 321 pa-
2
rameters, goodness of fit on F S = 1.020, R = 0.0649 (observed
1
around one, as using a higher ratio might lead to the formation of
two distinct coordination polymers based on the individual link-
ers rather than the expected copolymer. Moreover, when using a
mixture of ditopic and tritopic linkers, reported results show that
an excess of the ditopic linker is beneficial for the generation of
reflections), wR = 0.1984 (all unique reflections). More details
can be found in the deposited cif file CCDC 1508581 which con-
tains additional crystallographic data.
2
Sample pretreatment and sorption measurements
5
the desired copolymerization product.
Dichloromethane activation. The as-synthesized JUMP-1 was
activated by carrying out solvent exchange with dichloromethane.
This was done by soaking the sample (50–70 mg) in
dichloromethane (10 mL) for 7 d during which the solvent was
replaced by decanting every 24 h. Finally the supernatant liq-
O
OH
HO
O
HO
O
O
N
uid was removed and the sample dried in air. The final resulting
dcm
Lt
Ld
product is further denoted as JUMP-1
.
Supercritical carbon dioxide activation. In an alternative
pretreatment procedure the as-synthesized JUMP-1 (50–70 mg)
was soaked in ethanol (10 mL) for one week during which the
solvent was replaced every 24 h by decanting the supernatant.
Subsequently this was followed by a drying process using su-
O
OH
OH
Scheme 1 Linkers used for the synthesis of JUMP-1. Ld and Lt define
the characteristic lengths for the ditopic and tritopic linkers, respectively
(L /L = 1.01).
d
t
percritical CO . For this drying procedure the ethanol-immersed
samples were decanted and the resulting slurry transferred into
2
0 00
The tritopic linker 4,4 ,4 -nitrilotribenzoic acid being utilized
an autoclave (100 mL volume) and sealed. Liquid CO was then
in our synthesis leads to an almost ideal L /Lt ratio when com-
2
d
introduced into the autoclave at a final pressure of 60 bar and
allowed to stand 30 min. To ensure removal of any possible non-
bined with terephthalic acid (see Scheme 1). The ditopic linker
was used in slight excess of approximately 6:4 (M /Mt). The link-
d
occluded ethanol, the liquid CO was slowly removed over a pe-
ers were predissolved in DMF solution followed by the addition
of four equivalents of cobalt(II) chloride hexahydrate, all under
continuous stirring. The solvent DMF was deliberately chosen, as
to provide a source for the in situ generation of organic cations to
stabilize the desired anionic framework. Solvothermal treatment
of the resulting solution at 140 °C for 3 days followed by slow
cooling (5 °C h ) leads to the formation of a violet crystalline
material in rather high yields. Based on elemental and thermal
analysis performed on samples dried in vacuo the composition
of the final material corresponds to the dimethylammonium salt
2
riod of 20 min. A second batch of liquid CO2 was then intro-
duced into the reactor (60 bar), but this time allowed to stand
for 24 h. The temperature of the reactor was subsequently raised
to 40 °C to bring the CO2 to supercritical conditions and main-
tained at this temperature for one hour. The CO was then slowly
2
−1
released over 30 min with the temperature continuously main-
tained at 40 °C in order to prevent any cooling that might result
from expansion of the gas during evaporation. This supercritical
drying (scd) procedure was applied to the as-synthesized JUMP-1
1
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Fig. 1 Cut-out view of the trinuclear SBU showing the coordination en-
vironments around the cobalt(II) ions. Only carboxylate groups are de-
1
3
1
picted for clarity. Symmetry codes: A = – /2 – x, + y, /2 – z; B = − /2 – x,
3
3
1
1
1
1
/
2 – y, 1 – z; C = + x, /2 – y, /2 + z; D = /2 – x, /2 + y, + z; E = + x, /2 + y,
3
/
2 – z.
{
((CH ) NH ) [Co (ntb) (bdc)]} (JUMP-1) which contains ad-
3
2
2 2
3
2
n
ditional four molecules of DMF and two molecules of water per
formula unit.
Fig. 2 3D framework of JUMP-1 viewed along [010] direction. 2D net-
X-ray crystal structure
3−
works composed of linear trinuclear cobalt(II) SBUs and ntb ligands are
arranged along the (100) plane and interconnected by the bdc2 pillars.
−
Crystals suitable for structural analysis were obtained directly
from the solvothermal synthesis and are found to crystallize in the
orthorhombic space group Cmca. The data reveals the presence
of a 3D network with a pillared-layer structural arrangement.
The crystallographic asymmetric unit contains two independent
Red polyhedra represent cobalt(II) centers.
mode (O3) and two in a bidentate syn–syn µ1,3 mode (O1/O2 and
O5/O6), leading to a Co1–Co2 distance of 327 pm. The bridging
angle Co1–O3–Co2 at the monodentate carboxylate is found to
be 103°. This leads to only slight distortions from the octahedral
coordination at the central Co1 ion with bond lengths and angles
within the expected range (see Tables S1 and S2). On the other
hand a significant distortion from the tetrahedral coordination is
observed for the Co2 ions which is evident from the bond angles.
In fact, the largest O–Co2–O bond angle is found to be about 133°,
whereas the smallest is only about 96°. This is caused by steric
effects of the non-coordinated oxygen atoms of the monodentate
carboxylate ligands.
3
−
cobalt atoms, one ntb linker and the half of a terephthalic acid
moiety (see Fig. S1). One of the cobalt(II) ions (Co1) is located
on a crystallographic inversion center leading to the overall for-
2n–
mula {[Co (ntb) (bdc)]}
for the anionic 3D framework.
3
2
n
The two crystallographically independent cobalt(II) ions show
distinct differences in their coordination geometry. The atom Co1
is situated on an inversion center and shows an octahedral co-
ordination provided by six carboxylate oxygen atoms each from
3
−
a different ntb linkers. Whereas the Co2 center possesses a
distorted tetrahedral coordination geometry and is surrounded
by three oxygen atoms from three different ntb3 ligands with
the fourth position being taken up by an oxygen atom (O7) from
the terephthalic acid. The central Co1 ion together with the two
crystallographically equivalent Co2 and Co2A ions at the terminal
positions are giving rise to a linear trinuclear cluster which can
be regarded as an SBU (see Fig. 1). Although linear trinuclear
arrangements have been reported as SBUs in coordination frame-
−
The linear trinuclear SBUs within the 2D networks are well
separated with distances of about 1350 pm between their cen-
tral Co1 centers. For the SBUs also a large interlayer separation
is observed with a distance of about 1076 pm between the ter-
minal Co2 centers of corresponding SBUs bridged by a tereph-
thalate ligand. The charge of the resulting anionic 3D frame-
work (see Scheme 2) needs to be balanced. This is attributed
to the presence of two dimethylammonium cations in the void
formed by the well-known thermal decomposition of DMF un-
2
6,27
works,
the observed mixed coordination geometries at the
cobalt(II) ions (T –O –T ) in JUMP-1 are unusual with respect to
d
h
d
2
8–30
the carboxylate ligand environment.
SBUs are linked together via the ntb3 ligands leading to the for-
The trinuclear cluster
−
31
der the given reaction conditions. Although these counterions
mation of neutral 2D networks with the formula {[Co (ntb) ]} .
could not be located in the crystal structure, due to the presence
of large amounts of diffuse solvent molecules in the void of the
framework structure, their formation is evidenced by elemental
and thermogravimetric analysis.
3
2
n
These layers are then in turn connected with each other via the
terephthalic acid linkers which serve as pillars holding up the
structure. A representation of the resulting anionic 3D framework
structure is depicted in Fig. 2 (see also Figs. S2 and S3).
The overall anionic 3D framework can be described as a stack
of 2D sheets separated by terephthalic acid ligands to give the
3D cage-structure as shown in Fig. 2 (see also Figs. S2 and S3).
The topological analysis of the crystal structure of JUMP-1 uti-
The Co1 and Co2 ions within the trinuclear cluster are solely
bridged by the carboxylate groups of the ntb3 linkers. Overall
−
there are three carboxylate bridges, one in a monodentate µ1,1
4
|
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on the single crystal structure, except for intensity differences that
might be attributed to the presence of extra framework species
within the pores (see Fig. S6).
O
O
O
O
3
3
The thermal analysis of JUMP-1 showed a gradual weight loss
up to about 380 °C before the compound starts to thermally de-
compose (see Fig. S7). The first step consists of two individual
partially overlapping events as indicated by the differential ther-
mal gravimetric analysis, which can be attributed to the loss of
solvent molecules. The lower mass loss at the first event (about
bdc2-
2
[
D sheet of
Co3(ntb)2]n
3
.7 %) suggest the water molecules to be more loosely bonded
Scheme 2 Schematic representation showing the build up of the anionic
D framework of JUMP-1.
than the DMF molecules. The overall mass loss of 21.9 % for the
temperature range up to about 200 °C nicely compares to the cal-
culated value for two water and four DMF molecules (21.7 %).
The following temperature range up to the onset of the decom-
position of the organic ligand framework at about 380 °C corre-
sponds to a weight loss of about 7 % and can be attributed the
loss of the two dimethylammonium counterions (calcd 6.1 %).
The further decomposition of the organic ligand framework con-
sists of several steps which finally led to a rest mass of 15.0 % at
3
lizing TOPOS 5.032 revealed a binodal net (Tables S3 and S4).
The simplification of the network results in two different types of
nodes which are eight- and three-connected. The corresponding
topological net is depicted in Fig. 3 (cf. Figs. S4 and S5). The
eight-connected node represents the linear trinuclear cobalt clus-
ter, i.e. the SBU with eight attached carboxylate groups. Six of
6
1
00 °C which is in good agreement with the theoretical value of
4.9 % expected for CoO.
3
−
these connecting carboxylate groups originate from the ntb lig-
ands. The central nitrogen atom of the latter can be regarded
as the three-connected node (see also Fig. S5). The other two
carboxylate groups belong to the terephthalic acid pillars solely
linking the eight-connected nodes. The analysis of the topology
thus reveals a 3,8-connected net with tfz-d topology and the point
Magnetic properties
The magnetic susceptibility data for JUMP-1 were measured in the
temperature range from 2 to 300 K with an applied field of 2 kOe
and is depicted in Fig. 4 as a temperature-dependent plot of χMT
3
6
18
4
symbol (4 ) (4 .6 .8 ).
2
−
1
3
−1
and χM . The room temperature χ T value of 8.5 cm K mol
M
is significantly higher than the corresponding spin-only value
3
−1
,
for three magnetically isolated cobalt(II) ions (5.63 cm K mol
3
S = /2, g = 2) which clearly indicates strong spin-orbital cou-
pling. Upon decreasing the temperature the χ T value slowly
3
4
M
decreases down to a temperature of 8 K with a slightly increas-
ing slope below 100 K and a further significant drop down to a
3
−1
value of 5.8 cm K mol at 2 K. The observed behavior can basi-
cally be attributed to spin-orbit coupling as well as the presence
of antiferromagnetic exchange interactions between the cobalt(II)
2
7–29
−1
As indicated by the χM vs. T data JUMP-1 displays
ions.
paramagnetic behavior for temperatures above 50 K with a Curie
3
−1
constant of 8.86 cm K mol and a Weiss constant of −12.3 K.
The latter being consistent with the presence of antiferromagnetic
coupling.
The field-dependent magnetization was measured in a temper-
ature range from 2 to 5 K and up to fields of 5 T (see Fig. S8).
The expected behavior for increasing field strength is observed
with a value of about 6.3 Nβ at 2 K and 5 T. The data indicates
that saturation has not been reached under the given conditions.
Nevertheless, this value is consistent with the presence of an oc-
Fig. 3 Representation of the tfz-d topology of the network of JUMP-1
viewed approximately along the crystallographic [010] direction. The red
and blue spheres represent the trinuclear cobalt clusters (8-connected
nodes) and the nitrogen atoms of the ntb3− ligands (3-connected nodes),
respectively.
35
36,37
tahedral and two distorted tetrahedral cobalt(II) ions
as
found in the crystal structure for the central and the two terminal
cobalt centers, respectively.
The trinuclear cobalt(II) SBUs are found to be well-separated
from each other within the framework structure, which suggests
that the magnetic data of JUMP-1 can be analyzed based on the
treatment of these isolated units. Nevertheless, additional ex-
change coupling between these SBUs through the bridging car-
Powder diffraction and thermal analysis
The phase purity of the bulk material of JUMP-1 was confirmed
by X-ray powder diffraction (XRPD) measurements. Their is close
agreement of the experimental data with the simulations based
1
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exchange coupling constants J within the trinuclear SBU is com-
parable to values reported for similar trinuclear systems. More-
over, the antiferromagnetic coupling between the central and the
8
6
4
2
0
40
30
20
10
0
29
terminal cobalt(II) ions is consistent with the observed syn–syn
2
and µ –η carboxylate bridging modes. This is based on the
2
observation that syn–syn and anti–anti conformations generally
favor antiferromagnetic coupling, while syn–anti promotes ferro-
4
1
2
magnetic coupling. On the other hand, for µ –η carboxylate
2
bridges a dependence on the Co–O–Co bridging angle is reported
with values above 100° related to antiferromagnetic interactions
4
2
between the adjacent cobalt(II) ions. This, in fact, is constituent
with the corresponding angle of about 103° observed for JUMP-1
(see Table S2).
0
50
100 150 200 250 300
To further address the magnetic properties of JUMP-1
alternating-current susceptibility measurements as well as the a
set of zero-field cooled and field cooled magnetization measure-
ments have been performed. However, neither a signature for
slow magnetization dynamics nor any kind of ordering could be
detected.
T / K
Fig. 4 Temperature dependence of the magnetic susceptibility χMT
black squares) and χM (black circles) for JUMP-1. The solid line rep-
resent the best fits (see text for parameters).
−
1
(
boxylate ligands cannot be fully excluded. However, a full treat-
ment for the in turn resulting extended three-dimensional ex-
change coupled system is not feasible. Moreover, the occurrence
Cation exchange studies
The possibility of replacing the organic cations present within
the void of the framework was probed by immersing samples
of JUMP-1 in solutions of the salt of a small monovalent cation
such as lithium. This was done by soaking a sample of JUMP-1
in saturated ethanolic lithium nitrate solution for a period of 10 d
followed by washing with ethanol. In order to remove any resid-
ual free lithium salt from the sample the resulting material was
further soaked in ethanol for another 7 d. The corresponding
lithium ion exchanged sample is further denoted as JUMP-1(Li).
Post-exchange XRPD spectra obtained for JUMP-1(Li) are in good
agreement with the patterns observed for the as-synthesized bulk
material indicating that the framework was left intact even upon
exchange of the organic counterions (see Fig. S9). The uptake of
the lithium cation was further confirmed by CHN elemental analy-
sis (see Experimental Section), which is consistent with the pres-
ence of two lithium ions per formula unit of the anionic frame-
work. Additional evidence for a full exchange of the organic
counterions comes from the thermal analysis of lithium ion ex-
changed sample JUMP-1(Li) which is lacking an corresponding
mass loss (see Fig. S10). This nicely confirms the possibility of
post-synthetic replacement of the counterions within the anionic
framework of JUMP-1 without any detectable impact on the sta-
bility of the framework.
of two geometries (Oh and T ) within the trinuclear clusters re-
d
quires a multi-parameter approach including spin-orbit coupling
to allow a consistent description of the distinct magnetic prop-
erties of the corresponding cobalt(II) ions,3
4,35,38
i.e. individual
sets of zero-field splitting (ZFS) parameter D and g-factor for both
the octahedral and the tetrahedral cobalt(II) centers. Correspond-
ing attempts to fit the susceptibility data over the entire tempera-
ture range were unsuccessful due to an overparameterization and
led to an inadequate description of the system.
On the other hand, it is well-known that octahedral cobalt(II)
0
1
ions can be treated as effective spin S = /2 systems at low temper-
3
5
atures. This in turn should allow to analyze the corresponding
field-dependent magnetization data, which is measured at suffi-
ciently low temperatures, by a simplified interaction model for
the trinuclear cobalt(II) units. Since an effective spin of S = /2
is assumed for the central octahedral cobalt(II) ion, only the ZFS
effects of the two terminal tetrahedral cobalt(II) centers are to be
considered within this model by including an axial ZFS parame-
0
1
2
8
ter D in the fit. The resulting Hamiltonian utilized in fitting the
field-dependent magnetization data are given in Eq. (1).
ꢀ
ꢁ
1
3
2
H = J (S S +S S )+2D S (z) − S (S +1)
(1)
1
2
1
2A
2
2
2
The fitting of the magnetization data were performed with
3
9
Gas-sorption properties
the routine MagProp included in the software package DAVE.
An additional self-consistent mean-field approximation as imple-
The porosity of the anionic framework JUMP-1 was studied by
measuring the N2 and CO2 adsorption isotherms of the as-
synthesized and lithium ion exchanged materials. The activation
of the as-synthesized sample was first attempted by a solvent-
exchange process utilizing dichloromethane followed by gentle
4
0
mented in MagProp was introduced in the fitting to account
for possible intercluster exchange within the framework. To
avoid overparameterization only a single g-factor was used for
both types of cobalt(II) ions. The experimental data are repro-
−
1
duced with the following fit parameters g = 2.75, D = −2.9 cm
,
outgassing of the air-dried sample at room temperature to obtain
−
1
0
−1
dcm
J = −6.5 cm , and zJ = −0.06 cm (see Fig. S8).
JUMP-1
(see Experimental Section for more details). How-
The obtained intercluster exchange is consistent with the pre-
vious assumption of only weakly interacting trinuclear units. The
ever, this treatment led to the collapse of the accessible pores
with a very low available surface area for gas sorption (see Ta-
6
|
1–10

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DOI: 10.1039/C7CE00369B
0
.06
.04
.02
.00
0.06
0.04
0.02
0
0
0
0.00
2
4
6
8
10 12 14 16 18 20
Pore width / nm
0.5
1.0
1.5
2.0
2.5
3.0
Pore width / nm
1.0
Fig. 5 N isotherms of JUMP-1scd (red) and JUMP-1(Li)scd (blue) at 77 K.
Open shapes denote desorption.
2
0.8
1.0
0
0
0
0
.8
.6
.4
.2
Table 1 Characteristic adsorption parameters for the as-synthesized and
lithium ion exchanged samples JUMP-1 and JUMP-1(Li) after pre-
treatment by supercritical drying with CO2
0
.6
.4
scd
scd
0
Parameter
JUMP-1scd
JUMP-1(Li)scd
0.0
1
2
3
4
5
Pore width / nm
2
−1
)
a(BET) (m g
113
0.13
4.7
355
0.22
2.5
0.2
3
−1
)
Total Pore Volume (cm g
Pore Width (Mean) (nm)
Pore Width (Mode) (nm)
0
.0
0
1.0
0.6
.5
1.0
1.5
2.0
2.5
3.0
Pore width / nm
Fig. 6 Pore size distribution data for JUMP-1scd (top) and JUMP-1(Li)scd
ble S5), as indicated by the N2 isotherm and the corresponding
pore size distribution (Figs. S11 and S12). We therefore explored
an alternative activation procedure which is based on the treat-
(bottom).
scd
ment of the samples with supercritical CO2 to obtain JUMP-1
demand of the organic cations when present in the framework,
as they should hamper the accessibility of the internal pores for
incoming guest molecules. Interestingly, the lithium ion exchange
led to a considerable increase in porosity, as it is indicated by both
the significantly increase BET surface area and the larger total
pore volume. This can be attributed to a reduced steric demand
of the counterions upon replacement of the organic by the smaller
scd
and JUMP-1(Li)
form the as-synthesized and the lithium ion
exchanged samples, respectively (see Experimental Section for
more details). This has been reported earlier to be a milder form
of treating materials, which is attributed to a more gentle evacu-
ation of the pores preventing mesopore collapse and thereby en-
suring the accessibility of micropores.4
3
The N2 isotherms for the materials JUMP-1scd and
45
lithium ions, thereby enabling greater access to the micropores.
scd
JUMP-1(Li)
are presented in Fig. 5 and the relevant data
To further elucidate this point a pore size analysis of the pre-
scd
scd
scd
are summarized in Table 1. For JUMP-1 an appreciable BET
treated samples JUMP-1
and JUMP-1(Li)
was performed.
2
−1
surface area of about 113 m g
together with a total pore
was obtained. Upon replacement of
the organic cations by the lithium ions, a more than threefold
The resulting pore size distribution plots are displayed in Fig. 6.
The comparison clearly indicates a massive increase in the pop-
ulation of micropores for the lithium ion exchanged sample
3
−1
volume of 0.13 cm g
2
−1
scd
increase in BET surface area to a value of 355 m g
was
JUMP-1(Li) , especially in the range below 1 nm. This is con-
observed. However, this is related with only a slight gain in the
sistent with the above indicated stabilization of the mesopore
3
−1
total pore volume to a value of 0.22 cm g . With respect to
structure by the gentle pretreatment with the supercritical CO
drying. This clearly shows that the accessibility to micropores
2
3
−1
43
the overall void given by the anionic framework (0.96 cm g
calculated from the crystal structure of JUMP-1), the total pore
within an anionic framework can be adjusted via the variation of
scd
scd
46
volume determined for JUMP-1 and JUMP-1(Li) corresponds
to about 14 and 23 %, respectively.
the size of cations residing in the pores.
A similar basic trend can be seen form the CO adsorption
2
scd
scd
The isotherms shown in Fig. 5 can be classified as Type II
isotherms according to IUPAC rules.44 The hysteresis loops ob-
served can be described as Type H4 which are somewhat charac-
teristic for the presence of slit-shaped pores. The lower surface
area of the as-synthesized material can be attributed to the steric
isotherms of the pretreated samples JUMP-1 and JUMP-1(Li)
(see Fig. S13), as for the latter a slightly higher volume in total
adsorbed CO2 is observed. However, the ratio of adsorbed CO2
does not follow that obtained in the case of the N isotherms. This
2
can be attributed to characteristics of the CO adsorption process
2
1
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which does neither generally scale with the pore volume nor with
the available BET surface area as obtained from N2 adsorption.
Wu and W. Lin, J. Am. Chem. Soc., 2012, 134, 9050–9053.;
(h) M. Tonigold, Y. Lu, A. Mavrandonakis, A. Puls, R. Staudt,
J. Möllmer, J. Sauer and D. Volkmer, Chem. Eur. J., 2011, 17,
8671–8695; (i) M. Tonigold, Y. Lu, B. Bredenkötter, B. Rieger,
S. Bahnmüller, J. Hitzbleck, G. Langstein and D. Volkmer,
Angew. Chem. Int. Ed., 2009, 48, 7546–7550; (j) M. Alvaro,
E. Carbonell, B. Ferrer, F. X. L. i Xamena and H. Garcia, Chem.-
Eur. J., 2007, 13, 5106–5112.
In fact, the CO adsorption rather tends to prefer smaller pores,
2
which is due to the possibility of increasing adsorbate−adsorbent
4
6
interactions. Furthermore, as indicated from the N adsorption
2
data there is only a moderate difference in the total pore volume
scd
scd
between JUMP-1
and JUMP-1(Li) . A combination of both
factors is assumed to be responsible for the absence of apprecia-
ble variations in the amount of adsorbed CO for the pretreated
as-synthesized and lithium ion exchanged materials.
2 H. Furukawa, N. Ko, Y. Go, N. Aratani, S. Choi, E. Choi,
A. Yazaydin, R. Snurr, M. O’Keeffe, J. Kim and O. Yaghi, Sci-
ence, 2010, 329, 424–428.
2
Conclusions
3
J. Hong, M. Cheng, Q. Liu, W. Han, Y. Zhang, Y. Ji, X. Jia and
A pillared-layer cobalt(II) MOF JUMP-1 based on the redox-active
Z. Li, Transition Met. Chem., 2013, 38, 385–392.
triphenylamine linker H ntb was synthesized by a solvothermal
reaction. The structure of JUMP-1 can be viewed as constructed
3
4 M. Eddaoudi, J. Kim, N. Rosi, D. Vodak, J. Wachter,
M. O’Keeffe and O. M. Yaghi, Science, 2002, 295, 469–472.
5 K. Koh, A. Wong-Foy and A. Matzger, J. Am. Chem. Soc., 2010,
from neutral 2D networks {[Co (ntb) ]} , which in turn are
3
2
n
linked by terephthalic acid as anionic pillar ligand. The charge
of the resulting anionic 3D framework is compensated by in situ
generated dimethylammonium cations. For the 3D framework
this leads to a 3,8-coordinated net with tfz-d topology. The linear
trinuclear SBUs observed in JUMP-1 exhibit mixed coordination
geometries for the three cobalt(II) ions, i.e. octahedral for the
central and tetrahedral for the two terminal ions. Such mixed
geometries are uncommon for a solely carboxylate based coordi-
nation environment as observed in JUMP-1. The trinuclear SBUs
were found to be magnetically well-separated and show an an-
tiferromagnetic exchange coupling between the octahedral and
the tetrahedral cobalt(II) ions. The porous material JUMP-1 is
susceptible to exchange of the counterions present in the void of
the 3D network indicating the robust nature of the anionic frame-
work. Pretreatment prior to the gas-sorption experiments with
1
32, 15005–15010.
6
7
8
X.-L. Hu, F.-H. Liu, H.-N. Wang, C. Qin, C.-Y. Sun, Z.-M. Su
and F.-C. Liu, J. Mater. Chem. A, 2014, 2, 14827–14834.
K. Koh, A. Wong-Foy and A. Matzger, Angew. Chem. Int. Ed.,
2
008, 47, 677–680.
O. K. Farha, I. Eryazici, N. C. Jeong, B. G. Hauser, C. E. Wilmer,
A. A. Sarjeant, R. Q. Snurr, S. T. Nguyen, A. Ö. Yazaydın and
J. T. Hupp, J. Am. Chem. Soc., 2012, 134, 15016–15021.
(a) B.-B. Ding, Y.-Q. Weng, Z.-W. Mao, C.-K. Lam, X.-M. Chen
and B.-H. Ye, Inorg. Chem., 2005, 44, 8836–8845; (b) Z.-H.
Xuan, D.-S. Zhang, Z. Chang, T.-L. Hu and X.-H. Bu, Inorg.
Chem., 2014, 53, 8985–8990; (c) B. Arstad, H. Fjellv o˚ g, K. O.
Kongshaug, O. Swang and R. Blom, Adsorption, 2008, 14,
9
7
55–762.
1
1
1
0 (a) S. Henke, A. Schneemann, A. Wütscher and R. A. Fischer,
J. Am. Chem. Soc., 2012, 134, 9464–9474; (b) J. T. Culp,
M. R. Smith, E. Bittner and B. Bockrath, J. Am. Chem. Soc.,
supercritical CO turned out to be very effective in making micro-
2
pores accessible. The comparison of the as-syntheszied and the
lithium ion exchanged sample clearly shows that the accessibil-
ity to micropores within the anionic framework can be adjusted
by variation of cation size residing within the pores. In fact, this
2
008, 130, 12427–12434.
1 (a) M.-H. Zeng, Y.-L. Zhou, M.-C. Wu, H.-L. Sun and M. Du,
Inorg. Chem., 2010, 49, 6436–6442; (b) Y.-L. Zhou, M.-C. Wu,
M.-H. Zeng and H. Liang, Inorg. Chem., 2009, 48, 10146–
led to a massive increase in the population of micropores for the
scd
lithium ion exchanged material JUMP-1(Li)
.
1
0150.
Acknowledgements
2 (a) N. Sikdar, K. Jayaramulu, V. Kiran, K. V. Rao, S. Sampath,
S. J. George and T. K. Maji, Chem. Eur. J., 2015, 21, 11701–
O.A. thanks the Evangelisches Studienwerk Villigst e.V. for a
scholarship. We thank Mr. Reinhardt for the measurement of
the thermogravimetric and magnetic data and Mrs. Wermann for
measuring the powder diffraction data.
1
1706; (b) Y. Takashima, S. Furukawa and S. Kitagawa, Crys-
tEngComm, 2011, 13, 3360–3363; (c) P. Wu, C. He, J. Wang,
X. Peng, X. Li, Y. An and C. Duan, J. Am. Chem. Soc., 2012,
1
34, 14991–14999; (d) Y. E. Cheon and M. P. Suh, Angew.
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CrystEngComm
Page 10 of 10
View Article Online
DOI: 10.1039/C7CE00369B
Graphical Abstract
Tricarboxyltriphenylamine and terephthalic acid act as linkers in a pillared-layer anionic cobalt(II) framework. The counterions can be
exchanged while keeping the framework intact, leading to improved sorption properties for the small lithium ions.
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