A robust viologen and Mn-based porous coordination polymer with two types of Lewis acid sites providing high affinity for H2O, CO2 and NH3

Article abstract of DOI:10.1039/c7dt03541a

A novel porous coordination polymer [Mn(pc3)(H₂O)₂]·xH₂O (3 < x < 4) is synthesized in water at pH = 7 using the anionic viologen-carboxylate ligand 4,4′-bipyridinium,1,1′-bis-(2,4-dicarboxyphenyl) (pc3^2-). Dehy

Full text of DOI:10.1039/c7dt03541a

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10.1039/C7DT03541A.
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Joseph T. Hupp, Omar K. Farha et al.
Efficient extraction of sulfate from water using
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A robust Viologen and Mn-based porous coordination polymer
with two types of Lewis acid sites providing high affinity for H2O,
CO2 and NH3
Received 00th January 20xx,
Accepted 00th January 20xx
A. Leblanc, a N. Mercier,*a M. Allain,a M.-C. Dul,a G. Weber,b N. Geoffroyb, J.-P. Bellatb and I.
Bezverkhyy*b
DOI: 10.1039/x0xx00000x
www.rsc.org/
Novel porous coordination polymer [Mn(pc3)(H2O)2].xH2O (3<x<4) frameworks7,10-15 instead of porous ones. The known porous
is synthesized in water at pH = 7 using the anionic viologen- materials16-25 have shown interesting properties such as strong
carboxylate ligand 4,4’-bipyridinium,1,1’bis-(2,4-dicarboxyphenyl) adsorption of methanol,18 hydroquinone20 or NH3 25,26 as well as
(pc32-). Dehydration of the material results in formation of open O2 16 or NH3 21 detection. However, they are not stable in liquid
pores containing two types of accessible Lewis acid sites: exposed water and collapse during NH3 adsorption process.25-26 Up to
Mn2+ cations and N+ atoms of viologen units. Due to this property now, most of the viologen-carboxylate ligands used in this field
the PCP shows high affinity and capacity in adsorption of H2O, CO2 are zwitterionic, either symmetrical with two carboxylate
and NH3. Despite the presence of strong adsorption sites the groups at each side, or asymmetrical with one pyridyl chelating
material is stable in liquid water and in gaseous NH3.
unit and one carboxylate group at each side. In contrast,
materials based on anionic viologen carboxylate ligands such as
4,4’-bipyridinium,1,1’bis-(2,4-dicarboxyphenyl) (pc32-) are
scarce15,17,19 although they are suitable to be engaged with
metal ions in simple metal/ligand system.
Here, we report the first example of a robust PCP
[Mn(pc3)(H2O)2].xH2O (3<x<4) whose dehydrated form contains
two types of Lewis sites: open Mn(II) cations and N+ atoms of
viologen units. Due to a large number of Lewis sites the material
shows high affinity and uptake in adsorption of water, carbon
dioxide and ammonia.
Porous coordination polymers (PCP) whose framework
possesses Lewis acidic sites have attracted considerable
attention due to their promising properties in adsorption and in
catalysis. When present in the pores of adsorbents these sites
strongly bind guest species providing high adsorption enthalpy.
Thus this property allowed to increase significantly the storage
density of H2 1 or CH4 2 and also to enhance the capture of CO2.3,4
In the field of catalysis PCP with Lewis acid sites have been
shown to possess a high activity outperforming in some cases
traditional homogeneous and heterogeneous acid catalysts.5 In
all the cited applications the role of Lewis acid sites was played
by the open metal cations which were initially coordinated to
solvent molecules and become coordinatively unsaturated after
desolvation.
Recently, another type of Lewis sites has been introduced into
PCP structures based on bipyridinium (also called viologen)6
carboxylate linkers.7 The positively charged N atoms of viologen
units can act as a Lewis site with strong abilities to interact with
electron rich units or molecules.8,9 It is worth however noting
that the main consequence of potential strong donor-acceptor
interactions involving viologen is the formation of dense
Crystals of [Mn(pc3)(H2O)2]x.H2O (3<x<4) (
in water by hydrothermal method (T= 160 °C), starting from
a oversaturated water solution of (H4pc3)(Cl)2 whose pH ( 3)
was adjusted at 7 through addition of triethylamine, in which
1) were synthesized

MnCl2.4H2O was added. The X-ray crystal structure of
1 has
been refined in the P21/c space group,‡ revealing all non-H
atoms including three water molecules present in channels of
the structure (formulation [Mn(pc3)(H2O)2]3.H2O).
1 was also
characterized by elemental analysis and XRPD showing the
achievement of a pure phase (see ESI), and adsorption
measurements of H2O, CO2 and NH3 were carried out.
a.MOLTECH-Anjou UMR-CNRS 6200, 2 Bd Lavoisier, 49045 Angers, France. Fax: +33
(2) 41 73 54 05; Tel: +33 (2) 41 73 50 83; E-mail: nicolas.mercier@univ-angers.fr.
b.ICB, UMR-CNRS 6303, Université de Bourgogne-Franche Comté, 9 av A. Savary,
21078 Dijon, France; E-mail: Igor.Bezverkhyy@u-bourgogne.fr.
Electronic Supplementary Information (ESI) available: [details of the synthesis of the
pc3 ligand and 1, table of crystal data and X-ray crystallographic files in CIF format,
XRPD patterns, unit cell determination of dehydrated 1, details of the adsorption
measurement procedure]. See DOI: 10.1039/x0xx00000x
This journal is © The Royal Society of Chemistry 20xx
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-a-
-b-
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DOI: 10.1039/C7DT03541A
-a-
Fig. 1 Details of the structure of 1 showing (a) the dimeric inorganic unit -b-
[Mn2(CO2–carboxylate-)6(H2O)4] of two edge-sharing MnO6 octahedra, and
(b) the environment of one pc32- anionic viologen carboxylate ligand (#1: -
x+2, y-0.5, -z+1.5).
In the structure of 1, the inorganic nodes are centrosymmetrical
dimeric units built from two edge sharing Mn2+ octahedra. Mn2+ Fig. 2 Structure of 1: (a) view of a 2D sheet showing the open square type
aperture and (b) general view along the b axis showing two consecutive 2D
networks (in blue and in red, respectively) and the channels running along this
direction (free water molecules in pores have been omitted for clarity).
ions are surrounded by 4 oxygen of four carboxylate groups and
2 O atoms of water molecules in trans positions (Fig. 1a), while
the whole dimeric unit is connected to 6 ligands through six
carboxylate groups. The surrounding of a pc32- viologen The thermal behaviour of the material has been followed by
carboxylate anion is displayed in Fig. 1b. While three of its four TGA and thermodiffractometry. The desorption of water
carboxylate groups is connected each to a dimeric unit, the last molecules occurs in two consecutive steps up to 140°C (Fig. 3a).
one is free, strongly interacting with two water molecules The weight loss of 15.21 % corresponds to the departure of 5.4
belonging to a neighbouring inorganic node through hydrogen H2O molecules which is close to the expected value determined
bonding (d(O6…H(water) in the 1.83-1.85 Å range, Fig. 1b). The by X-ray analysis (5). This two-step process is in good
resulting neutral network is a 2D coordination polymer which accordance with the two different types of water molecules in
extends along the a and b directions. Rectangle windows of the structure, those binding to Mn2+ ions and strongly
approximately (6 x 4) Å2 are defined when the network is viewed interacting with N+ sites and the free ones in channels of the
along the c direction (Fig. 2a). In the structure, the 2D sheets structure.
stack along the c direction with a shift between two consecutive
sheets in the (a, b) plane, precluding any channel along c.
However, channels inside sheets are clearly defined when the
structure is viewed along the b direction. The estimated section
of these windows is of (6 x 1) Å2. As a consequence, the
structure is porous with channels containing guest water
5.32%
molecules. The porosity has been estimated to 10.4 % according
to squeeze routine of Platon. Interestingly, the bipyridinium
core is interacting through one pyridinium cycle at the N+ site
(N2) with guest water molecules (O11, Fig. 1b) at each side of
the ring, meaning that the viologen could be accessible to guest
molecules if the activation of the compound doesn’t modify its
structure.
9.89%
-a-
-b-
Fig. 3 Thermal behaviour of 1, (a) TGA curve showing the dehydration
in two consecutive steps and the stability of the materials up to 300°C;
(b) thermodiffractometry under nitrogen atmosphere (except the upper
XRPD carried out in air at the end of the experiment) showing the two
phase transitions at 30 °C and 100°C as well as the reversibility of the
process when the dehydrated sample is exposure to air (upper XRPD).
2 | J. Name., 2012, 00, 1-3
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affinity towards H2O, remains intact after exposure to liquid
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DOI: 10.1039/C7DT03541A
water.
Fig. 4 Adsorption isotherm of H2O on 1 at 298K: full symbols – adsorption,
open symbols - desorption. Inset: low-pressure part of the isotherm.
The thermodiffractometry under N2 flux shows two phase
changes, a first one as soon as 30°C and a second one at 80-100
°C, which can be correlated to the departure of guest molecules
in two steps as revealed by TGA. The unit cell of the dehydrated
phase (150 °C) has been tentatively determined (ESI). As clearly
indicated by the shift to the first (1 0 0) line, the a parameter
decreases from 14.5 to 13.5 Å, and it is also proposed that c
doesn’t change, while b decreases from 10.4 to 9.6 Å, finally
showing that no important structural re-organization occurs
during the desorption process. Moreover, the reversibility is
demonstrated as the XRPD of the initial phase is recovered as
soon as the N2 atmosphere is replaced by air (Fig. 3b) through a
fast rehydration process.
Fig. 5 Adsorption isotherm of CO2 on 1 at 298K: full symbols – adsorption,
open symbols – desorption.
The accessibility of coordinatively unsaturated Mn is further
confirmed by the shape of the adsorption isotherm of CO2
recorded at 298 K (Fig. 5). The high uptake of 0.08 g/g observed
at low pressure (< 200 hPa) is indicative of strong interactions
between the molecules and the pore walls. The stoichiometry
of the uptake in this step (1 mol/mol) is different from that of
water due to a larger molecular size of CO2 (3.3 vs 2.64 Å for
H2O) and different molecular shape. We speculate that the high
affinity of 1 towards CO2 can be explained by the interaction of
two Mn atoms with two CO2 molecules. The possibility of such
interaction can be understood if the geometry of Mn dimeric
unit and that of CO2 are taken into account (Fig. S4). The
resulting alignment of two CO2 along one Mn dimer molecules
would explain the observed 1 CO2/1 Mn stoichiometry at low
pressure. The first step in the isotherm is followed by the
second one corresponding to interaction with weaker binding
sites, presumably N+ atoms of viologen units. The total amount
adsorbed at 1000 hPa (0.13 g/g or 2.9 mmol/g) is lower than
that observed for the top MOFs containing CUS sites3,4 or with
pore space partition29. Nevertheless, it is close to the values
As attested by water adsorption isotherm (Fig. 3) the maximum
capacity of
1 is 0.23 g/g at P/P0 = 0.87 which corresponds to 7
H2O molecules/mol of the solid. At lower relative pressure
corresponding to ambient conditions (0.3-0.5) the amount
adsorbed is ca 0.18 g/g or 6 mol/mol which is in quite good
agreement with values determined from the structure analysis
and TGA. The water adsorption isotherm consists of two
different parts. The first one corresponds to a steep increase of
the adsorbed amount up to 0.11 g/g occurring at very low
pressure (P/P°< 0.02, see inset in Fig. 3), the remaining amount
is adsorbed in a gradual fashion. And it is worth noting that the
adsorption of water at very low pressure is of high interest for
applications such as delivery of drinking water.27,28 The shape of
the second part of the isotherm is characteristic of pore filling
by water molecules. In contrast, the steepness of the first step
indicates that it corresponds to strong specific interactions
between water molecules and some Lewis centers present in
the pores. The amount of water adsorbed in the first step (equal
to ~ 3 mol/mol, see inset in Fig. 3) indicates that the role of
Lewis centers can be played by Mn atoms (2 H2O per atom
according to the hydrated structure) and by one accessible N+
of viologen present in the structure. The presence of the first
step in the isotherm allows thus to conclude that the
coordinatively unsaturated Mn atoms formed upon
dehydration are accessible for the molecules adsorbed in the
typically observed for MOFs,30 and in
1 a significant uptake,
0.08 g/g (or 62 % of the total capacity), is attained at pressure
below 200 hPa, i.e. in the range important for post-combustion
capture of CO2.3,4
1 possesses another important property: its
structure is fully preserved after CO2 adsorption-desorption
cycle as follows from XRD and FTIR data (Fig. S5 and S6).
The prepared PCP was also studied in adsorption of another
polar species - NH3 (Fig. 6a and Fig. S7). As in the case of H2O
and CO2 two steps can be distinguished in the isotherm. The first
of them corresponding to uptake of 3 mol/mol (0.1 g/g) can be
attributed to binding of NH3 molecules to Mn atoms and
viologen units. The similarity of kinetic diameters of H2O and
NH3 (2.64 and 2.9 Å) and of their polarities (1.47 and 1.85 D)31
explains the same stoichiometry observed for these two
molecules. As follows from the XRD recorded in situ, the solid
saturated with NH3 remains crystalline and the position of lines
are very close to ones of the initial phase, indicating close unit
cells (Fig. 6b, NH3_in_situ to be compared to the initial
compound, 1_RT). To verify if the sample can be reused, we
pores of
1
. As expected because
1
has been synthesized in water
which exhibits a high
at pH 7, the structure of dehydrated
1
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repeated the adsorption of NH3 three times with intermediate demonstrates stability in liquid water as well as inVtiheweAprtriceleseOnnlcinee
DOI: 10.1039/C7DT03541A
heating under vacuum at 453K (the regeneration is incomplete of 1 bar of NH3.
at 298K). The similar shape of the three successive isotherms
(Fig. 6a) shows that the material keeps its high capacity for NH3
despite the collapse of the structure (Fig.6b, NH3_3c_453).
Notes and references
Given that
1 is stable in the presence of NH3 at 298K, we
‡
Crystal data for 1 (C26H24MnN2O13, M = 627.41, T= 293 K):
monclinic, a = 14.4605(8) Å, b = 10.4594(5) Å, c = 18.7370(10) Å,
β = 111.93(1)°, V = 2629.0(3) Å3, space group P21/c, Z = 4, crystal
size (mm3): 0.15 × 0.09 × 0.04. The refinements of positions and
anisotropic thermal motion parameters of the non-H atoms,
converge to R(F) = 0.066 (4003 reflections (10699 collected (R(int)
= 0.045)), 376 parameters), wR2(F2) = 0.196 (all data), GOF on F2 is
1.04, Δρmax = 1.91 eÅ-3. CCDC 1571877.
supposed that the decomposition occurs during the
regeneration stage done at 453K. To verify this hypothesis we
realized three adsorption cycles with intermediate (incomplete)
regeneration at 298K instead of 453K. It follows from the XRD
pattern (Fig. 6b, NH3_3c_298) that the solid remains crystalline
after such sequence. Moreover, we can observe that while
some lines are common between 1_RT and NH3-3c_298, most
of them are slightly shifted one to each other (see for instance
1
M. P. Suh, H. J. Park, T. K. Prasad and D.-W. Lim, Chem. Rev.,
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the set of three lines in the 9-11 ° and 13-15 ° 2
indicating a close but different unit cell for
adsorption (which still contains an amount of NH3) compared to
. This finding confirms thus that is stable in the presence of

ranges),
2
3
S. Ma and H.-C. Zhou, Chem. Commun., 2010, 46, 44.
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after NH3
1
1
4
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NH3 at 298K and it is the heating of the NH3-containing solid
which provokes the structure collapse. It is worth noting that it
is extremely rare that carboxylate ligand based MOFs are stable
upon NH3 adsorption. For instance MOF-74,32 HKUST-133 and
other viologen-carboxylate MOFs collapse during this step.25,26
In contrast, a recent work shows that an azolate MOF remains
P. Garcia-Garcia, M. Muller and A. Corma, Chem. Sci., 2014,
5
, 2979.
P. M. S. Monk in The Viologens: Physicochemical Properties,
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-a-
-b-
Fig. 6 (a) Three successive adsorption isotherms of NH3 on 1 at 298 K (after
each adsorption the sample was regenerated at 453K under vacuum); (b)
XRPD of 1 (1_RT), 1 saturated with NH3 (NH3_in_situ), 1 after 3 full
adsorption/desorption cycles when the sample is regenerated at 453K
(NH3_3c_453), or at 298K (NH3_3c_298).
In summary, we report here novel PCP [Mn(pc3)(H2O)2].xH2O
(3<x<4) based on assembly of Mn2+ and viologen
tetracarboxylate ligand pc32- (pc3 = 4,4’-bipyridinium,1,1’bis-
(2,4-dicarboxyphenyl)). The structure of this 2D coordination
polymer contains Mn dimeric units held together by pc3 ligands,
and water molecules bound to Mn atoms (two per Mn) and
present in pores. The dehydrated material shows important
adsorption capacity for H2O (0.2 g/g), CO2 (0.13 g/g) and NH3
(0.18 g/g) at room temperature. Moreover, a steep adsorption
in a low pressure range observed for all studied molecules
suggests that the pore walls contain strong binding sites. The
observed adsorption stoichiometry allows to attribute these
sites to open Mn2+ cations and to N+ atoms present in pc3 ligand.
In addition to high affinity and capacity, the prepared material
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A water stable PCP with two kinds of Lewis sites, open Mn2+ cations and viologen, shows
high affinity for H2O, CO2 and NH3.