Supramolecular ionic networks with superior thermal and transport properties based on novel delocalized di-anionic compounds

Article abstract of DOI:10.1039/c4ta05792a

Supramolecular ionic networks based on highly delocalized dianions having (trifluoromethane-sulfonyl)imide, (propylsulfonyl)methanide and (cyano-propylsulfonyl)imide groups were developed and their physical properties were examined in detail. Most of the synthesized compounds were semi-crystalline possessing T_m values close to 100°C; however, amorphous networks were also obtained using aromatic asymmetric dianions. Rheological measurements in temperature sweep tests at a constant frequency confirmed two different behaviors: a fast melting close to the T_m for semi-crystalline materials and a thermoreversible network for liquid transition for the amorphous supramolecular ionic networks. It was found that the amorphous ionic networks showed significantly higher ionic conductivity (10^-3 S cm^-1 at 100°C) than the crystalline ionic networks (10^-6 S cm^-1) and previously reported amorphous citrate ionic networks (10^-5 S cm^-1). The supramolecular ionic networks containing hydrophobic (trifluoromethanesulfonyl)imide groups demonstrated improved water stability and higher thermal stability than the previously synthesized carboxylate ones. Noticeably, the obtained amorphous supramolecular ionic networks combine not only high ionic conductivity and thermal stability, but also self-healing properties into the same material.

Full text of DOI:10.1039/c4ta05792a

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DOI: 10.1039/C4TA05792A
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ARTICLE TYPE
Supramolecular ionic networks with superior thermal and transport
properties based on novel delocalized di-anionic compounds
a
b*
a
b,c
b
M. Ali Aboudzadeh, Alexander S. Shaplov, Guiomar Hernandez, Petr S. Vlasov, Elena I. Lozinskaya,
d
d
b
a*
Cristina Pozo-Gonzalo, Maria Forsyth, Yakov S. Vygodskii , David Mecerreyes
5
Received (in XXX, XXX) Xth XXXXXXXXX 20XX, Accepted Xth XXXXXXXXX 20XX
DOI: 10.1039/b000000x
Supramolecular ionic networks based on highly delocalized dianions having (trifluoromethaneꢀsulfonyl)imide,
propylsulfonyl)methanide and (cyanoꢀpropylsulfonyl)imide groups were developed and their physical properties were examined in
(
detail. Most of the synthesized compounds were semicrystalline possessing Tm values close to 100 ºC; however, amorphous networks
were also obtained using aromatic asymmetric dianions. Rheological measurements in temperature sweep tests at a constant frequency
1
0
confirmed two different behaviors: a fast melting close to the T for semicrystalline materials and a thermoreversible network to liquid
m
transition for the amorphous supramolecular ionic networks. It was found the amorphous ionic networks showed significantly higher
ꢀ
3
ꢀ6
ionic conductivity (10 S/cm at 100 ºC) than the crystalline ionic networks (10 S/cm) and previously reported amorphous citrate ionic
ꢀ
5
networks (10 S/cm). The supramolecular ionic networks containing hydrophobic (trifluoromethanesulfonyl)imide groups demonstrated
improved water stability and higher thermal stability than previously synthesized carboxylate ones. Noticeably, the obtained amorphous
supramolecular ionic networks combine not only high ionic conductivity and thermal stability, but also selfꢀhealing properties into the
same material.
1
5
(
T ) was revealed which facilitated the use of such
nl
9
ꢀ11
Introduction
supramolecular ionic networks in selfꢀhealing applications.
5
5
6
6
7
7
0
5
0
5
0
5
However, supramolecular ionic networks reported thus far
possessed some intrinsic issues, related to the constituent
carboxylate compounds, such as water sensitivity, poor thermal
stability temperature and low ionic conductivity. Therefore the
primary advantage of supramolecular ionic networks, which is
the fact that they can combine selfꢀhealing and ionic conductive
properties in one material, has not attained yet. Therefor the main
goal of this work is to report the synthesis of a new family of
supramolecular ionic networks having highly delocalized
dianions which may overcome these limitations.
2
2
3
3
4
4
0
5
0
5
0
5
The introduction of new cations and anions coming from ionic
liquids (ILs) chemistry is extending the properties and classical
applications of ionic polymers.
combined with supramolecular chemistry can also be translated to
the development of supramolecular polymers based on ionic
interactions. In comparison to other nonꢀcovalent counterparts,
ionic interactions have unique properties as follows. Firstly, they
1
ꢀ4
This emerging ionic chemistry
5
are stronger and lessꢀdirectional; secondly, they may form larger
aggregated structures depending on the steric environment of the
6,7
ion pair; thirdly, coulombic interactions are asymmetric and
Our strategy to develop supramolecular ionic networks with
superior properties first involves the development of novel
8
sensitive to the local constant of the medium they are in; and
fourthly, ionic interactions are easily tunable through the
combination of various anion (e.g. sulfonate vs. carboxylate) and
cation structures (e.g. primary or secondary amine, quaternary
ammonium), that are accessible through straightforward
delocalized dianionic compounds (Scheme 1). Although, ionic
17,18
liquids of dicationic type are well known,
dianionic systems
having typical anions such as sulfonamides have not been
19
20
synthesized yet. Recently, Shaplov et al. and Armand et al.
9
ꢀ12
chemistry.
have shown the synthetic pathway for the preparation of
methacrylate and 4ꢀvinylbenzene ionic liquid like monomers with
highly delocalized attached trifluoromethaneꢀsulfonyl)imide,
(propylsulfonyl)methanide and (cyanoꢀpropylsulfonyl)imide
anions. This approach was taken into consideration and allows us
to design and synthesize a series of highly delocalized dianionic
compounds. These novel dianions were combined with geminal
diꢀimidazolium dications as the building blocks for the
preparation of supramolecular ionic materials. In this paper we
also present the superior thermal and transport properties of these
materials that make them promising candidates as electrolytes for
electrochemical devices with intrinsic selfꢀhealing properties that
may offer advantageous in terms of safety.
Only six years ago, Grinstaff et al. reported the preparation of
organic supramolecular ionic networks by mixing multiꢀcationic
and multiꢀanionic compounds.
molecules such as alkyl phosphonium dications were employed.
More recently, we developed more simple pathways for the
synthesis of supramolecular ionic networks by using multiꢀ
1
3ꢀ16
In this case; complex
9ꢀ12
carboxylate anions and simple proton transfer reactions.
Among the investigated molecules citric acid showed great
potential leading to supramolecular ionic networks with unique
rheological properties when combined with a variety of dicationic
compounds. Thus, a rapid soft solid network to liquid transition
This journal is © The Royal Society of Chemistry [year]
[journal], [year], [vol], 00–00 | 1

Journal of Materials Chemistry A
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DOI: 10.1039/C4TA05792A
Results and Discussions
Synthesis and characterization of novel delocalized dianionic
compounds
5
0
5
0
5
0
5
0
5
0
5
The design of novel dianionic monomers involves the chemical
modification of the sulfonate group to highly delocalized anions
having
propylsulfonyl)methanide
(trifluoromethaneꢀsulfonyl)imide,
or (cyanoꢀpropylsulfonyl)imide
(
groups. For this purpose, two different disulfonate sodium salts
were chosen (Scheme 1, compounds 1 and 5). While 1 is
representative of aliphatic compounds, 5 belongs to the 1,3ꢀ
substituted aromatics. The choice of the latter was driven by the
desire to reduce the asymmetry and subsequent melting point of
the final ionic monomers. The two steps synthetic route of 3, 4, 7
and 8 was similar to the procedure published by some of us
1
1
2
2
3
3
4
4
5
5
19
previously in the case of methacrylic anionic monomers. On the
first stage 1,4ꢀbutanedisulfonic acid disodium salt or benzeneꢀ 60 Scheme 1 Synthetic route for the preparation of ionic monomers
o
1
,3ꢀdisulfonic acid disodium salt were converted into their
Reagents and conditions: (i) SOCl
2
, THF/DMF, 0 C
RT; (iib) CH (CN) , THF, NEt
RT; (iii) Brꢀ(CH ) ꢀ
2 3
→
RT; (iia)
o
respective sulfonyl chloride derivatives by reaction with thionyl
chloride in the presence of DMF as a catalyst. Both bisꢀsulfonyl
chlorides (Scheme 1, 2 and 6) were obtained as solid crystalline
products. It was noticeable that aromatic compound 6 undergoes 65 materials in comparison with previous supramolecular ionic
vacuum sublimation at low temperature and can thus be further
NH
0 C
2
SO
RT; (iic) NH
Br or Brꢀ(CH ꢀBr, MeOH, 0
2
CF
3
, THF, NEt
3
, 0 C
→
2
2
,
3
o
o
→
CN, THF, NEt
, 0 C
→
2
3
o
)
→
55 C.
2
5
networks based on the carboxylate anion, which were water
9ꢀ12
purified. The second stage consisted of the reaction of 2 or 6
soluble in most cases.
with trifluoromethanesulfonamide (Scheme 1,
malononitrile (Scheme 1, 4) or cyanamide (Scheme 1, 8) in the
presence of a 2.2 molar excess of triethylamine in anhydrous 70 based
THF. Unexpectedly, in contrast to respective charged
3 and 7),
In contrast, supramolecular ionic networks iNet-4 and iNet-5,
on diꢀanionic compounds having
(propylsulfonyl)methanide and (cyanoꢀpropylsulfonyl)imide
groups, were soluble in water. As a result, an alternative synthesis
route was developed in this case (Scheme 2b). This route
consisted of two reaction steps. Thus, in the first stage the diꢀ
1
9
20
methacrylate or styrene derivatives, all dianionic monomers 3,
4, 7 and 8 along with reaction byproduct (triethylammonium
hydrochloride) precipitated during synthesis. Taking into account
the nature of the cations, the separation process of the main 75 silver salts of the respective monomers 4 and 8 were obtained and
reaction and its byproducts represented quite a difficult task. An
elegant solution was found in the difference in solubility of 3, 4,
7, 8 and triethylammonium hydrochloride. The insolubility of the
latter in anhydrous DMF allowed its nearly quantitative
separation from the main reaction products.
quantitatively isolated, whereas in the second stage they were
allowed to react with aqueous solution of 10 or 11 providing
iNet-4 and iNet-5 in a pure form, after the removal of
precipitated AgBr. Aliphatic chains between imidazolium rings in
80 compounds 10 o 11 was chosen to provide a direct comparison
with our previous supramolecular network with same type of
1
12
The structure and purity of 3, 4, 7 and 8 were determined by H,
dicationic molecules.
1
3
19
C and F NMR, IR spectroscopy and elemental analysis. Three
dianionic monomers represented solid crystalline or wax like
The structure and purity of the supramolecular ionic network
o
1
13
products with a melting point equal to 40ꢀ43, 73ꢀ74 and >150 C 85 products were confirmed by H and
C NMR and IR
for 7, 3 and 4 respectively. Only compound 8 was an ionic liquid
at room temperature.
spectroscopy. Except for iNet-3 that was obtained as a
transparent amorphous material, all other products represented
crystalline solids at room temperature as confirmed by powder Xꢀ
Ray diffraction (PXRD) experiments. According to XꢀRay
90 analysis a crystallinty degree of > 90 % for iNet-1, iNet-2, iNet-4
and iNet-5 was revealed. Thus most of the synthesized
supramolecular ionic networks (four among five) with highly
delocalized dianions were found to be highly crystalline. This
was not the case for ionic networks based on citrate, which were
Synthesis of supramolecular ionic networks using delocalized
dianionic and dicationic compounds
In the second step, supramolecular ionic networks were prepared
via two synthetic pathways as illustrated in Scheme 2. In all the
cases, reactants were mixed in equimolar amounts at room
temperature in water as
a
solvent. The synthesis of 95 mostly amorphous. Whereas using other types of carboxylates,
supramolecular ionic networks based on diꢀanionic compounds
having (trifluoromethaneꢀsulfonyl)imide group, was simple. By
mixing with dicationic compounds (10 or 11), the resultant ionic
networks iNet-1, iNet-2 and iNet-3 precipitated in water which
allowed for their easy separation and purification. This fact was a 100
good indication of the diminished aqueous sensitivity of these
having very rigid and regular structures, such as malonate and
terephthalate dicarboxylates, will lead to crystallization, avoiding
9
the formation of 3D ionic networks.
2
| Journal Name, [year], [vol], 00–00
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Journal of Materials Chemistry A
View Article Online
DOI: 10.1039/C4TA05792A
O
S
O
S
O
S
O
S
F3C
N
(CH2)4
N
CF3
N
N
(CH2)5
N
N
iNet-1
CH3
CH3
n
O
O
O
O
25
5
O
S
O
S
O
S
O
S
O
O
N
N
(CH2)3
N
N
(
ii)
CH3
CH3
iNet-2
O
S
S
O
(
C2H5)3 NH3F3C
N
R1
N
CF3 HN (C2H5)3
N
N
S
S
O
O
S
O
O
O
O
F3C
CF3
O
O
n
3
R1 = -(CH2)4-
7
R1 = -1,3-(C6H4)-
O
O
N
N
(CH2)5
N
N
iNet-
3
0
3
O
S
S
O
CH3
CH3
N
N
O
O
S
1
1
2
4
5
5
6
6
7
7
0
5
0
5
0
5
0
5
0
5
F3C
CF3
O
O
n
O
O
O
S
O
S
O
O
S
NC
NC
CN
(i)
NC
NC
CN
(ii)
NC
NC
CN
(
C2H5)3 NH
C
O
S
(CH2)4
S
C
HN (C2H5)3
Ag
C
(CH2)4
C
Ag
C
S
(CH2)4
C
N
N
(CH2)3
N
N
CN
CN
CN CH3
CH3
O
O
O
O
O
O
4
35
n
n
iNet-4
O
(
i)
O
O
(ii)
O
O
N
N
(CH2)3
N
N
(
C2H5)3 NH
S
S
HN (C2H5)3
CH3
CN
CH3
N
N
Ag
NC
S
S
Ag
CN
S
S
NC
O
O
CN
N
O
N
N
N
O
NC
O
O
8
iNet-5
40
Scheme 2 Synthetic route for the supramolecular ionic networks preparation. Reagents and conditions: (i) AgNO , H O, RT; (ii) 10 or
3
2
1
1, H O, RT.
2
Thermal and rheological properties
80
The thermal properties of supramolecular ionic networks were
investigated by differential scanning calorimetry (DSC) and
thermal gravimetric analysis (TGA). By DSC it was observed that
stability of iNet-2 and iNet-3 is higher than of iNet-5 (Table 1,
entries 2, 3 and 5), while Td of iNet-1 exceeds the onset
decomposition temperature of iNet-4 (Table 1, entries 1 and 4).
all the crystalline networks showed a melting point in the first 85 Thermal behavior of our previously synthesized supramolecular
12
heating cycle at 101, 94, 116 and 109 ºC for iNet-1, iNet-2, iNet-
and iNet-5, respectively (Table 1). While, in the second heating
cycle only a glass transition temperature in the range of T = ꢀ1 ÷
network based on the carboxylate anion was also included in
Fig. 2 (Table 1, entry 6). As can be clearly observed, these new
supramolecular ionic networks based on delocalized anions
showed an improved thermal stability of between 60 to 160 ºC.
4
g
ꢀ
22 ºC (Table 1, entries 1ꢀ2 and 4ꢀ5) was observed. In contrast,
amorphous iNet-3 demonstrated only a glass transition at ꢀ20 ºC
in both heating cycles. DSC curves of iNet-3 along with
crystalline iNet-1 are shown in Fig. 1 for comparison. It can be
concluded that a change of the aliphatic dianion into its aromatic
analogue leads to a more amorphous behavior (Table 1, entries 1
and 3). When the same dianion monomers are used, an increase
of the spacer between two imidazolium cations also appears to
avoid crystallinity (Table 1, entries 2 and 3).
90
Thermal stability of novel supramolecular ionic networks was
estimated by TGA. It was revealed that their onset decomposition
temperatures in air vary from 200 to 295°С (Table 1, Fig. 2). In
terms of thermal stability, the obtained products could be
arranged in the following order: iNet-2 ≈ iNet-3 > iNet-1 > iNet-
> iNet-4. Thus, iNet-2 and iNet-3 based on aromatic 7 with
bis(trifluoromethylsulfonyl)amide anions demonstrated the
highest T among the investigated networks (Table 1, entries 2
and 3). The transfer from an aromatic spacer (7) to an aliphatic
5
d
o
one (3) results in a decrease of thermal stability by ~ 40 C (Table
1
,
entries
1
and 3). It is known that, the
bis(trifluoromethylsulfonyl)amide anion usually imparts higher
thermal stability to the ILs in comparison with dicyanamide
based salts (Td = 390 ÷ 420 C
respectively). Following the same general tendency, the thermal
95
Fig. 1 DSC profiles of iNet-1 (1) and iNet-3 (2), first heating
cycle (black color) and second heating cycle (red color), the
figure in the inset shows magnified glass transition temperature
for both materials.
o
22
o
23
and 290 ÷ 335 C
,
100
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Page 4 of 7
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DOI: 10.1039/C4TA05792A
4
5
5
6
5
0
5
0
heating cycle again similar to iNet-1, however, during the cooling
cycle after the melt transition, this material remained amorphous
within the timescale of the measurement and a transition from
liquid state to a network state was observed at T = 8 ºC.
ln
It is worth to mention that the amorphous supramolecular ionic
network iNet-3 shows the typical rheological properties
associated with selfꢀhealing behavior. This was observed before
in other supramolecular ionic systems where this rheological
behavior was translated into selfꢀhealing by a slight temperature
change before and after the Tnl transition. Bellow the Tnl the
material shows a solid film like properties, when a crack is
provoked the material healed itself in some minutes even without
the need of applying a heat and recovers its initial shape/aspect.
Table 1 Thermal Characterization of supramolecular ionic
Fig. 2 Thermal gravimetric analysis (TGA) curves of iNet-1,
iNet-2 and iNet-3 as well as the supramolecular ionic network
based on citrate anion and 10
networks
a
b
c
d
d
5
Supramolecular
ionic network
T
g
T
m
T
d
T
nl
T
ln
(˚C) (˚C) (˚C) (˚C) (˚C)
Rheological analysis of the ionic networks was carried out using
temperature sweeps in smallꢀamplitude oscillatory flow
measurements. The temperature dependences of storage (elastic)
G′ and loss (viscous) G″ moduli at constant frequency of 1 Hz are
shown in Fig. 3. As can be seen from Fig. 3, at temperatures
below ꢀ10 ºC the ionic interactions in amorphous iNet-3 brought
about a soft solid characterized by a high elastic modulus with a
iNet-1
iNet-2
iNet-3
iNet-4
ꢀ19
ꢀ1
101
94
ꢀ
260
290
295
200
ꢀ
ꢀ
ꢀ
8
1
1
2
0
5
0
ꢀ20
ꢀ17
ꢀ12
ꢀ
ꢀ13
ꢀ
116
6
constant value of Ge = 7.2×10 which became a viscoelastic liquid
iNet-5
Citrate + 10
b
ꢀ22
ꢀ14
109
ꢀ
240
135
ꢀ
ꢀ
20
d
with G″> G′ values as the temperature increased. G reflects the
e
equilibrium elasticity of the network. This transition from
network to liquid state is characteristic for the majority of
21
9
ꢀ12
a
c
supramolecular ionic networks developed previously.
As an
By DSC. By DSC. Onset loss temperature by TGA. The
transition temperatures from the network to the liquid state, Tnl,
indicator of this transition, the crossover temperature at which G′
= G″, or the temperature for the maximum in G″, can be taken.
The thermoreversible character of this supramolecular network is
also analyzed in this measurement. Approximately the same G′
and G″ values were obtained on a continuous cooling cycle,
without any significant hysteresis being observed. The latter can
indicate the rapid thermal reversibility of the network that can be
explained by the nonꢀcovalent nature of the involved interactions,
and the rapid dissocation and subsequent recovery of these
interactions.
and from the liquid to the network state, T , obtained from
temperature scans at ω= 6.28 rad/s.
ln
25
3
0
On the other hand in rheological experiments iNet-1
demonstrated an almost constant elastic modulus G′ (Fig. 3). It is
noticeable that in the temperature range of 40 to 100 ºC, i.e.
below iNet-1 melting point, its G′ was always higher than the
associated loss modulus G″. Such behavior is typical for a soft
solid material and additionally confirms the crystalline nature of
the network. Upon melting, both moduli decreased dramatically,
indicating flow of the sample. This drastic decrease in modulus
represents the melting transition. Although the cooling cycle was
performed with the same temperature ramp rate, the rapid thermal
reversibility was not observed, possibly due to the longer times
needed for solidification. iNet-4 and iNet-5 showed the same
behavior as for iNet-1 in the rheological experiments except that
the sharp drop in both moduli occurred at their corresponding
melting points. iNet-2 exhibited crystalline behavior during the
35
65
Fig. 3 Temperature dependence of dynamic storage modulus G´
40
(heating ■ & cooling+) and loss modulus G´´ (heating ■ &
coolingꢀ) for iNet-3 (left) and iNet-1 (right) Arrows in the
figure indicate the melting point (T ) and network to liquid
m
transition (Tnl).
4
| Journal Name, [year], [vol], 00–00
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Journal of Materials Chemistry A
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DOI: 10.1039/C4TA05792A
Ionic conductivity
60
The ionic conductivity of supramolecular ionic networks was
measured by AC impedance spectroscopy. It was revealed, that
depending on the monomer’s combination the ionic conductivity
5
ꢀ
12
ꢀ7
ꢀ1
of networks varies in the range of 7.7×10 and 7.3×10 S cm at
0ºC. The increase of spacer between two imidazolium cations
3
65
results in an increase in respective network’s conductivity. The
change of aliphatic dianion to its aromatic analogue leads to an
increase in conductivity of nearly three orders of magnitude. The
comparison of ionic conductivity for networks based on
1
1
2
2
3
3
4
4
5
5
0
5
0
5
0
5
0
5
0
5
monomers
propylsulfonyl)methanide and (cyanoꢀpropylsulfonyl)imide does
not show a clear effect.
having
trifluoromethaneꢀsulfonyl)imide,
70
(
The temperature dependence of conductivity was also
investigated. Fig. 4 shows representative results for a crystalline
supramolecular ionic network (iNet-1), a citrate based amorphous
9
supramolecular ionic network and an amorphous supramolecular
ionic network based on delocalized anions (iNet-3). At
temperatures below 70 ºC crystalline iNet-1 demonstrate nearly
linear behavior (Arrhenius behavior) with the conductivity
75
ꢀ
10
ꢀ9
ꢀ1
Fig. 4 Temperature dependence of the ionic conductivity for
iNetꢀ1, iNetꢀ3, iNetꢀ3+10% LiTFSI and supramolecular ionic
network based on citrate
increasing from 1.3×10
to 4.4×10 S cm . However, at
temperatures close to the melting transition, T , a more rapid
m
increase in ionic conductivity, equal to three orders of magnitude,
was observed (Fig. 4). The temperature dependence of ionic
conductivity for amorphous iNet-3 was different (Fig. 4) to the
two crystalline materials. The behavior for iNet-3 appears
predominantly linear and shows the highest values of ionic
80
Conclusions
We have demonstrated a new synthetic route to supramolecular
ionic networks based on highly delocalized diꢀanions. In
particular, supramolecular ionic networks containing hydrophobic
(trifluoromethaneꢀsulfonyl)imide groups showed improved water
stability and higher thermal stability than previously synthesized
carboxylate ones. Although, most of the synthesized compounds
were semicrystalline, amorphous networks were also obtained
using aromatic asymmetric dianions. In this case rheological
measurements in temperature sweep tests at a constant frequency
confirmed a reversible network to liquid transition behavior
associated with selfꢀhealing properties. Amorphous ionic
networks showed high ionic conductivity, showing values close
ꢀ
6
ꢀ3
ꢀ1
conductivity (between 10 and 10 S cm ) for the entire
temperature range (30ꢀ100 °C) in comparison with crystalline
iNet-1. Furthermore, the effect of lithium doping was
investigated by adding 10 % LiTFSI to the amorphous iNetꢀ3.
The doped materials showed very similar values of ionic
conductivity than the original iNet. In fact, the doped material
showed a slightly higher ionic conductivity value at low
temperatures which is the typical behavior of polymer
electrolytes (Fig. 4). However at high temperatures where the
viscosity drops, the ionic conductivity is lower in the case of the
doped sample. This behavior is actually the typical one of ionic
liquids where addition of a lithium salt decreases the overall ionic
conductivity value.
8
9
9
5
0
5
ꢀ
3
to 10 S/cm (at 100 ºC). iꢀNets reported here combine properties
such as ionic conductivity and selfꢀhealing properties. This can
be very interesting for applications like batteries for electric
vehicles where security of the battery is a must and further
optimization of the ionic conductivity of our materials could lead
to an electrolyte for a battery that repairs itself.
Fig. 4 also compares the new supramolecular ionic networks
based on delocalized anions with the conventional
supramolecular ionic network materials based on carboxylates
such as the citrate + diamine system. It is worth to remark that the
new supramolecular ionic networks (iNet) showed a two to three
order of magnitude improvement of its ionic conductivity with
respect to previous amorphous supramolecular ionic networks
1
00 Acknowledgements
DM acknowledges the European Research Council for grant iPES
ERCꢀStgꢀ 2012ꢀ306250. MF acknowledges the ARC for her
Laureate Fellowship. This work was also supported by the
Russian Foundation for Basic Research (projects no. 13ꢀ03ꢀ
ꢀ
3
based on citrate. The ionic conductivity value of 10 S/cm (at
00 ºC) makes them of potential interest for real application in
electrochemical devices such as batteries. However, the value of
1
ionic conductivity at room temperature may not be enough for 105 00343ꢀa and 14ꢀ29ꢀ0403914_ofi_m) and by European
real applications. Further investigations are being carried out to
Commission through the International Research Staff Exchange
Scheme (FP7ꢀPEOPLEꢀ2012ꢀIRSES, project no. 318873
replace the aliphatic groups by ethylene oxide units to improve
21
the ionic conductivity of the supramolecular ionic networks.
«IONRUN»). Authors would like to thank Dr. E.G. Kononova for
IR spectroscopy.
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Journal Name, [year], [vol], 00–00 | 5

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DOI: 10.1039/C4TA05792A
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| Journal Name, [year], [vol], 00–00
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Journal of Materials Chemistry A
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DOI: 10.1039/C4TA05792A
Table of Contents
Supramolecular ionic networks with superior thermal and
transport properties based on novel delocalized di-anionic
compounds
a
b
a
b,c
M. Ali Aboudzadeh, Alexander S. Shaplov, Guiomar Hernandez, Petr S. Vlasov,
b
d
d
b
Elena I. Lozinskaya, Cristina Pozo-Gonzalo, Maria Forsyth, Yakov S. Vygodski and
a*
David Mecerreyes
ꢀ