Guest molecule-responsive functional calcium phosphonate frameworks for tuned proton conductivity

Article abstract of DOI:10.1021/ja500356z

We report the synthesis, structural characterization, and functionality (framework interconversions together with proton conductivity) of an open-framework hybrid that combines Ca²⁺ ions and the rigid polyfunctional ligand 5-(dihydroxyphosphory

Full text of DOI:10.1021/ja500356z

Article
pubs.acs.org/JACS
Guest Molecule-Responsive Functional Calcium Phosphonate
Frameworks for Tuned Proton Conductivity
Montse Bazaga-García,† Rosario M. P. Colodrero,† Maria Papadaki,‡ Piotr Garczarek,§ Jerzy Zon,∥
́
Pascual Olivera-Pastor,† Enrique R. Losilla,† Laura Leon-Reina,⊥ Miguel A. G. Aranda,†,#
́
Duane Choquesillo-Lazarte,∇ Konstantinos D. Demadis,*,‡ and Aurelio Cabeza*,†
†Departamento de Química Inorgan
́ ́ ́
ica, Universidad de Malaga, Campus Teatinos s/n, Malaga 29071, Spain
‡Crystal Engineering, Growth and Design Laboratory, Department of Chemistry, University of Crete, Voutes Campus, Crete, GR-71003, Greece
∥
§Department of Medicinal Chemistry and Microbiology, Faculty of Chemistry and Department of Thermodynamics, Institute
of Heat Engineering and Mechanics, Faculty of Mechanical and Power Engineering, Wrocław University of Technology,
27 Wybrzeze Wyspian
́
̇
́
́ ́
aga, Campus Teatinos s/n, 29071-Malaga, Spain
́
S
* Supporting Information
ABSTRACT: We report the synthesis, structural characterization, and functionality (framework interconversions together
with proton conductivity) of an open-framework hybrid that combines Ca2+ ions and the rigid polyfunctional ligand
5-(dihydroxyphosphoryl)isophthalic acid (PiPhtA). Ca2[(HO3PC6H3COOH)2]2[(HO3PC6H3(COO)2H)(H2O)2]·5H2O (Ca-PiPh-
tA-I) is obtained by slow crystallization at ambient conditions from acidic (pH ≈ 3) aqueous solutions. It possesses a high water content
(both Ca coordinated and in the lattice), and importantly, it exhibits water-filled 1D channels. At 75 °C, Ca-PiPhtA-I is partially
dehydrated and exhibits a crystalline diffraction pattern that can be indexed in a monoclinic cell with parameters close to the pristine
phase. Rietveld refinement was carried out for the sample heated at 75 °C, Ca-PiPhtA-II, using synchrotron powder X-ray diffraction
data, which revealed the molecular formula Ca2[(HO3PC6H3COOH)2]2[(HO3PC6H3(COO)2H)(H2O)2]. All connectivity modes of
the “parent” Ca-PiPhtA-I framework are retained in Ca-PiPhtA-II. Upon Ca-PiPhtA-I exposure to ammonia vapors (28% aqueous
NH3) a new derivative is obtained (Ca-PiPhtA-NH3) containing 7 NH3 and 16 H2O molecules according to elemental and thermal
analyses. Ca-PiPhtA-NH3 exhibits a complex X-ray diffraction pattern with peaks at 15.3 and 13.0 Å that suggest partial breaking and
transformation of the parent pillared structure. Although detailed structural identification of Ca-PiPhtA-NH3 was not possible, due in
part to nonequilibrium adsorption conditions and the lack of crystallinity, FT-IR spectra and DTA-TG analysis indicate profound
structural changes compared to the pristine Ca-PiPhtA-I. At 98% RH and T = 24 °C, proton conductivity, σ, for Ca-PiPhtA-I is 5.7 ×
10−4 S·cm−1. It increases to 1.3 × 10−3 S·cm−1 upon activation by preheating the sample at 40 °C for 2 h followed by water equilibration
at room temperature under controlled conditions. Ca-PiPhtA-NH3 exhibits the highest proton conductivity, 6.6 × 10−3 S·cm−1,
measured at 98% RH and T = 24 °C. Activation energies (Ea) for proton transfer in the above-mentioned frameworks range between
0.23 and 0.4 eV, typical of a Grothuss mechanism of proton conduction. These results underline the importance of internal H-bonding
networks that, in turn, determine conductivity properties of hybrid materials. It is highlighted that new proton transfer pathways may be
created by means of cavity “derivatization” with selected guest molecules resulting in improved proton conductivity.
Received: January 13, 2014
© XXXX American Chemical Society
A
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Article
EXPERIMENTAL SECTION
INTRODUCTION
■
■
Materials and Common Instrumentation. The starting
salt CaCl2·2H2O was from EM Science Merck and used as received.
Deionized (DI) water from an in-house laboratory cation-exchange
column was used for all syntheses. Stock solutions of HCl and NaOH
were used for pH adjustments. The pH meter used was a wTw pH315i
setup, equipped with a SeTix 41 electrode. Elemental analyses (C, H, N)
were measured on a Perkin-Elmer 240 analyzer. Infrared spectra were
collected in a FTIR Nicolet 5DXC spectrometer. All spectra were
recorded in the 4000−400 cm−1 range at 4 cm−1 resolution, and 50 scans
Metal−organic framework (MOF) materials are now at the
epicenter of research efforts of many groups around the globe.
An obvious exegesis for the “explosion” in the field is two-fold:
(a) new structural motifs are constantly being sought,1a and (b)
functionality in these materials becomes increasingly impor-
tant.1b−d More specifically, potential applications are inves-
tigated in fields such as gas adsorption, storage and separation,2
magnetism,3 catalysis,4 photoluminescence, sensors,5 con-
trolled release of pharmaceuticals, medicinal and dental
materials,6 chiral separations,7 and ion exchange,8 just to
mention a few.
A plethora of organic linkers/ligands have been widely utilized
to construct these hybrid MOF materials, with the majority being
carboxylate, imidazolate, or polypyridyl based. On the other
hand, multichelating phosphonate ligands are “alternative”
organic linkers (to the widespread polycarboxylates, imidazoles,
and various derivatives) and provide synthetic access to a number
of thermally and chemically stable MOFs.9
1
were accumulated. The H, 13C{1H}, and 31P{1H} NMR (see below;
operating frequency, solvent) spectra in solution were recorded on a
Bruker Avance DRX300 instrument. Chemical shifts (δ) are given in ppm.
Syntheses. The ligand 5-(dihydroxyphosphoryl)isophthalic acid
[5-(H2O3P)C6H3-1,3-(COOH)2] (PiPhtA, 1) was synthesized through
a number of intermediates, shown in Figure 1, as follows.
Recently, phosphonates,10 phosphocarboxylates,11 and phos-
phonosulfonates12 that possess an aromatic entity (usually one
or more phenyl rings) have been exploited in synthetic efforts,
yielding multidimensional (mostly 2D and 3D) platforms.
Proton conductivity has long been investigated as a desirable
property in a variety of diverse materials, whether organic,13
inorganic,14 or hybrid.15 The field of MOFs and more specifically
metal phosphonates has provided an opportune arena for
elegant efforts for accessing suitable and highly conducting
materials.15f,16 Furthermore, postsynthetic modification1d of the
internal surfaces of MOFs offers opportunities for enhancing
desired properties of crystalline solids.16c The main requirement
for a MOF material to be proton conductive is the presence of
acidic protons within an appropriately structured metal−organic
framework that facilitates charge transport. In the case of
metal phosphonate materials the phosphonic acid group (or
partially protonated phosphonate) assumes the role of the acidic
group. Such well-ordered structural motifs, with highly ordered
phosphonate groups located in close proximity to lattice water
molecules, often present appropriate platforms that are
candidates for high proton conductivity.12 For instance, proton
conductivity higher than 10−2 S cm−1 has been reported
for PCMOF21/2,15f a mixed sulfonate−phosphonate MOF,
and for derivatized MIL-101 with H2SO4 and/or H3PO4.15g
Other notable examples are metal derivatives containing the
N,N-amino-bis(methylenephosphonate) moiety, such as
ZrChDTMP,17 MgH6ODTMP,18 and LaH5DTMP,19 phases,
which exhibit conductivity values from 1 × 10−4 to 8 × 10−3
S cm−1. The high flexibility imparted by the ligand is considered
to exert a key role in determining internal proton transfer
pathways.
Figure 1. Protocol for the synthesis of 5-(dihydroxyphosphoryl)-
isophthalic acid (PiPhtA, 1): (i) NaNO3, HCl, KI; (ii) SOCl2, CH3OH;
(iii) HP(O)(OR)2, (i-C3H7)2NC2H5, Pd(OOCCH3)2, dppf, CH3CN;
(iv) aqueous HCl, H2O; (R = C2H5).
5-Iodoisophthalic Acid (2). This compound was prepared from
commercially available 5-aminoisophthalic acid according to a literature
procedure.20 Specifically, 5-aminoisophthalic acid (5.00 g, 0.0276 mol)
was dissolved in a mixture of concentrated hydrochloric acid (49 cm3)
and water (49 cm3). This solution was cooled in an ice−water bath, and
a solution of sodium nitrite (2.05 g, 0.0295 mol) in water (9.6 cm3) was
added with such a rate that the temperature of the mixture did not
exceed 4 °C. Next, a solution of potassium iodide (15.0 g, 0.0903 mol) in
water (38 cm3) was slowly added. Evolution of nitrogen was observed,
and the mixture turned a yellow-reddish color. Afterwards the mixture
was refluxed for 1 h. After cooling the precipitate was filtered off and air
dried to yield 5-iodoisophthalic acid: 5.76 g (72%), mp 284−285 °C
(lit. 288−289 °C20).
Dimethyl 5-Iodoisophthalate (3). 5-Iodoisophatlic acid (2, 14.83 g,
0.050 mol) was heated under reflux with thionyl chloride (65 cm3,
0.89 mol) for 3.5 h. Next, the excess of thionyl chloride was distilled off.
Methanol (50 cm3) was added to the residue carefully due to an
exothermic effect and evolution of hydrogen chloride, and the mixture
was heated to reflux for a few hours. A precipitate formed during the
heating process and was filtered off and recrystallized from methanol to
obtain dimethyl 5-iodoisophthalate (3): 13.32 g (82%), mp 103−105 °C
(lit. 104 °C21).
Dimethyl 5-(Diisopropyloxyphosphoryl)isophthalate (4a). A
50 cm3 round-bottom flask was charged with dimethyl 5-iodoisophthalate
(3, 2.00 g, 6.25 mmol), acetonitrile (20 mL), diisopropyl phosphite (1.246 g,
7.5 mmol), and diisopropylethylamine (1.05 g, 8.125 mmol). The
flask was flushed with argon for 15 min, after which palladium acetate
(0.014 g, 0.0625 mmol) and 1,1′-bis(diphenylphosphine)ferrocene
(dppf, 0.038 g, 0.0687 mmol) were added. The reaction mixture was
stirred and heated in an oil bath at 90 °C for 24 h under constant flow of
argon. After cooling to room temperature the mixture was evaporated to
dryness in vacuo, and the remaining residue was purified by column
In the present work, we report the synthesis, structural
characterization, and proton conductivity of an open-framework
hybrid that combines Ca2+ ions and the rigid polyfunctional
ligand 5-(dihydroxyphosphoryl)isophthalic acid (PiPhtA). This
material was obtained by slow crystallization at ambient
conditions from acidic (pH ≈ 3) aqueous solutions. It possesses
a high water content (both Ca coordinated and in the lattice),
and importantly, it exhibits water-filled 1D channels. Both
characteristics are, in principle, considered to be remarkable
attributes to evaluate the proton conductivity of this hybrid
compound. The effects of the guest species (water and NH3) on
the conductivity properties will be highlighted.
B
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chromatography on silica gel using ethyl acetate as eluent to yield
dimethyl 5-(diisopropyloxyphosphoryl)isophthalate (4a): 1.434 g
(64%), Rf = 0.40 (silica gel on TLC-PET foil, ethyl acetate, UV light
254 nm). 1H NMR (300 MHz, CDCl3) δ: 8.82 (m, 1H, CH arom.), 8.63
(dd, JHH = 1.68 Hz, JHP = 16.35 Hz, 2H, CH arom.), 4.74 (m, 2H, CH),
3.96 (s, 3H, CH3), 1.39 (d, JHH = 6.18 Hz, CH3), 1.24 (d, JHH = 6.18 Hz).
13C NMR (75 MHz, CDCl3) δ: 165.43, 136.64 (J = 10.94 Hz), 133.88,
131.88 (J = 192.01 Hz), 130.97 (J = 14.94 Hz), 71.51 (J = 5.59 Hz),
52.60, 24.02 (J = 3.81 Hz), 23.86 (J = 4.58 Hz). 31P{1H} NMR (121
MHz, CDCl3) δ: 14.16 (s).
Dimethyl 5-(Diethoxyphosphoryl)isophthalate (4b). Compound
4b was synthesized using the same procedure as 4a, starting from 1.173 g
of dimethyl 5-iodoisophthalate, although diethyl phosphite was used.
Yield of the ester 4b: 42%, Rf = 0.30 (silica gel on TLC-PET foil, ethyl
acetate, UV light 254 nm). 1H NMR (300 MHz, CDCl3) δ: 8.83 (m, 1H,
CH arom.), 8.63 (dd, JHH = 1.68 Hz, JHP = 13.32 Hz, 2H CH arom.), 4.16
(m, 4H, CH2), 3.96 (s, 6H, CH3), 1.34 (t, J = 7.06 Hz, 6H, CH3).
31P{1H} NMR (121 MHz, CDCl3) δ: 16.33 (s).
delay time of 5 min to ensure thermal stabilization. Data acquisition was
carried out between 4° and 40° (2θ) due to “less-than-ideal” crystallinity
of the samples. A step size of 0.017° and an equivalent counting time of
150 s step−1 were used.
Crystal Structure Determination. Suitable-size crystals of
Ca-PiPhtA-I were kept under inert conditions and immersed in
perfluoropolyether as protecting oil for manipulation. A suitable crystal
was mounted on MiTeGen Micromounts, and this sample was used for
data collection. Data were collected with a Bruker SMART APEX
diffractometer. Data were processed with APEX222 suite and corrected
for absorption using SADABS.23 The structure was solved by direct
methods,24 which revealed the position of all non-hydrogen atoms.
These atoms were refined on F2 by a full-matrix least-squares procedure
using anisotropic displacement parameters.24 All hydrogen atoms were
located in difference Fourier maps, except those corresponding to C−H
groups, which were placed geometrically and included as fixed con-
tributions riding on attached atoms with isotropic thermal displacement
parameters 1.2 (C−H) or 1.5 (O−H) times those of the respective
bonded atom.
Synchrotron X-ray powder diffraction data (SXRDP) for Ca-PiPhtA-
II were collected in Debye−Scherrer (transmission) mode using the
X-ray powder diffraction station of ALBA, the Spanish Synchrotron
Radiation Facility (Barcelona, Spain).25 The wavelength, 0.62020(1) Å,
was selected with a double-crystal Si (111) monochromator and
determined from a Si640d NIST standard (a = 5.43123 Å) mea-
surement. The capillary was rotated during data collection to improve
diffracting particle statistics. The detector system used was the
MYTHEN, which allows fast collection of good-resolution patterns.
The data acquisition time was ∼20 min per pattern to attain very good
signal-to-noise ratio over the angular range 1−41° (2θ).
5-(Dihydroxyphosphoryl)isophthalic Acid (PiPhtA, 1). A 25 cm3
round-bottom flask was charged with dimethyl 5-(diisopropyloxyphosphoryl)-
isophthalate (4a, 1.072 g, 3.00 mmol), water (4 cm3), and concentrated
hydrochloric acid (4 cm3). The mixture was refluxed for 20 h. After
cooling down to room temperature it was evaporated to dryness in
vacuo to yield the product 1 as a white solid: 0.734 g (99%). 1H NMR
(300 MHz, D2O) δ: 8.29 (d, J = 3.82 Hz, 1H, CH arom.), 8.21 (dd, JHP
=
13.36 Hz, JHH = 2.62 Hz, 2H, CH arom.);. 31P{1H} NMR (121 MHz,
D2O) δ: 12.63 (s).
Ca2[(HO3P−C6H3−COOH)2]2[(HO3P−C6H3−(COO)2H)−(H2O)2])·
5H2O (Ca-PiPhtA-I). A quantity of the ligand 5-(dihydroxyphosphoryl)-
isophthalic acid (1, 0.061 g, 0.250 mmol) was dissolved in 10 cm3 of
DI water. A small quantity of a 0.1 M NaOH stock solution was added
dropwise until the ligand dissolved completely and a clear, colorless
solution was obtained. A quantity of CaCl2·2H2O (0.037 g, 0.250 mmol)
was separately dissolved in 5 cm3 of DI water. The two solutions were
subsequently mixed, and the final solution pH was adjusted to 3.00 using
the 0.1 M NaOH stock solution. The transparent colorless solution
was left undisturbed for 1 week, after which the product appeared as a
white crystalline material. It was isolated by filtration, washed with DI
water, and air dried. Yield: 92%. Anal. Calcd for Ca2[(HO3P−C6H3−
COOH)2]2[(HO3P−C6H3−(COO)2H)(H2O)2]·5H2O, fw 940.56,
C24H31Ca2O28P3: C, 30.81; H, 2.80. Found: C, 29.27; H, 3.36.
Ca2[(HO3P−C6H3−COOH)2]2[(HO3P−C6H3−(COO)2H)−(H2O)2]
(Ca-PiPhtA-II). This compound was obtained by thermal treatment of
solid Ca-PiPhtA-I at 75 °C for 2 h.
Absorption of NH3 Vapors (Aqueous Solution). A 150 mg
amount of Ca-PiPhtA-I was placed in contact with vapors from a
commercial solution of 28 wt % of NH3 in water for 2 h in a closed
container. Subsequently, the product was air dried for 15 min and kept at
98% relative humidity at 10 °C for 18 h following the same procedure
described below to measure the proton conductivity. The obtained solid,
Ca2[(HO3P−C6H3−COOH)2]2[(HO3P−C6H3−(COO)2H)]-
(NH3)7(H2O)16 (Ca-PiPhtA-NH3), has the following elemental
analysis. Anal. Calcd: C, 23.69; H, 5.38; N, 8.06. Found: C, 23.86; H,
4.75; N, 7.65. TG -analysis: weight loss up to 400 °C, found 32.67%,
calcd 33.36%.
Thermal Analysis. Differential thermal analysis (DTA) and
thermogravimetric analysis (TGA) data were recorded on an SDT-
Q600 analyzer from TA Instruments. The temperature varied from
room temperature to 900 °C at a heating rate of 10 °C·min−1. Mea-
surements were carried out on samples in open platinum crucibles under
a flow of air.
X-ray Crystallography. Laboratory X-ray powder diffraction
(XRPD) patterns were collected on a PANanalytical X’Pert Pro
automated diffractometer. Powder patterns were recorded in Bragg−
Brentano reflection configuration using a Ge(111) primary mono-
chromator (Cu Kα1) and the X’Celerator detector. Thermodiffracto-
metric studies for Ca-PiPhtA-I and Ca-PiPhtA-NH3 were carried out
on samples loaded in an Anton Paar HTK 1200N chamber under static
air. Data were collected between room temperature and 240 °C. All
measurements were performed with a heating rate of 10 °C·min−1 and a
The X-ray powder pattern was autoindexed using the DICVOL06
program.26 The crystal structure of Ca-PiPhtA-II compound was
determined by the Rietveld method27 using the structure of Ca-PiPhtA-
I available from single-crystal data as starting model. Rietveld refinement
was carried out using the GSAS package28 with soft constraints to
maintain chemically reasonable geometries for the phosphonate,
aromatic ring, and carboxylic groups. The soft constraints were as
follows: /PO3C tetrahedron/P−O, 1.53(1) Å; P−C, 1.80(1) Å; O···O,
2.55(2) Å; O···C, 2.73(2) Å; /aryl/aromatic ring/C−C [1.40(1) Å],
Cring···Cring [2.40(1) Å], Cring···Cring [2.78(1) Å], /COO group/, Caryl
-
Ccarb [1.50(1) Å], C−Ocarb [1.23(1) Å], Ocarb···Ocarb, 2.21(2) Å; Caryl···
Ocarb, 2.36(2) Å. Two isotropic atomic displacement parameters were
refined, one for calcium and phosphorus atom and a second one for
carbon and oxygen atoms. Hydrogen atoms were not included in the
refinements. Crystallographic data and CCDC reference codes are given
in Table 1.
Proton Conductivity Studies. Impedance data were collected
on cylindrical pellets (∼10 mm diameter; ∼0.9−1.1 mm thickness)
obtained by pressing ∼0.15 g of sample at 500 MPa for 2 min between
porous C electrodes (Sigracet, GDL 10 BB, no Pt). Impedance data were
collected using a HP4284A impedance analyzer over the frequency
range from 20 Hz to 1 MHz with an applied voltage of 1 V. All mea-
surements were electronically controlled by the winDETA package of
programs.29
Electrical measurements were taken in a double-walled, temperature-
controlled glass chamber with a gas inlet and outlet. The temperature of
the chamber was controlled by a Julabo F32-MA refrigerated/heating
circulator from 10 to 24 °C every 2 °C with a heating rate of
0.4 °C·min−1 using EasyTEMP software. Samples were equilibrated for
15 min after each step in temperature, measured in closest vicinity to the
sample. The relative humidity (RH) was obtained by a continuous flow of
water-saturated nitrogen at different temperatures through the cell. Pellets
were equilibrated at 98% RH for 18 h to ensure a fixed water content of
the sample and stable conductivity values. RH is approximately constant
in the measured temperature range from 10 to 24 °C.
RESULTS AND DISCUSSION
■
Synthesis. The product Ca-PiPhtA-I is formed at a relatively
low reaction pH (∼3.0). At this pH the carboxylic acid groups are
C
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Table 1. Crystallographic Data for Ca-PiPhtA-I and
Ca-PiPhtA-II
Ca-PiPhtA-I
Ca2C24H31O28P3
Ca-PiPhtA-II
chemical formula
formula mass
cryst syst
Ca2C24H21O23P3
850.49
940.56
orthorhombic
monoclinic
cryst size (mm) color/
shape
0.10 × 0.09 × 0.08 colorless/
block
Figure 2. Three deprotonation states of the ligand PiPhtA in the
structure of Ca-PiPhtA-I.
λ/Å
0.71073
23.112(4)
6.9534(13)
22.638(4)
90.0
0.62020(1)
23.0652(7)
6.9731(1)
22.4165(7)
90
a/Å
b/Å
c/Å
α/deg
β/deg
90.0
91.540(4)
90
γ/deg
unit cell volume/Å3
90.0
3638.1(12)
−173
3604.1(2)
25
temp/°C
space group
Pca21
Pa
Z
4
4
Rint
0.0832
no. of independent reflns 4603
3455
data (reflns)/restraints/
6716/1/522
5500/299/357
params
a
a
R factor [I > 2σ(I)]
R factor (all data)
RWP
R1 = 0.0715; wR2 = 0.1610
a
a
R1 = 0.1075; wR2 = 0.1834
0.0654
0.0464
0.075
RP
GoF/RF
1.032
CCDC number
968321
968322
a
2
R1(F) = Σ∥Fo| − |Fc∥/Σ|Fo|; wR2(F2) = [Σw(Fo − Fc2)2/ΣF4]1/2
.
expected to be deprotonated, whereas the phosphonic acid group
is monodeprotonated. This would render the ligand trianionic,
and a possible 1:1 adduct with Ca2+ would be anionic. However,
based on elemental analyses and the structure solved, a solid
with a Ca:ligand ratio of 2:3 is instead obtained, indicating that
the protonation state of the ligand is complex. As suggested by
the empirical formula, the ligand is found in different protonation
states, which are adjusted depending on the various modes of
coordinating to Ca2+ (Figure 2).
Structural Study. Ca-PiPhtA-I shows a complex pillared
layered structure with a unit cell containing two calcium atoms,
three PiPhtA ligands, and seven water molecules (two are Ca
coordinated and the remaining five are situated within the
lattice). The coordination geometry of both calcium centers is
pentagonal bipyramidal (see Figure 3).
In this geometry, four of the equatorial positions are occupied
by oxygen atoms of three different phosphonate groups, one of
them chelating the metal ion in a bidentate fashion. The fifth
equatorial coordination position is occupied by an oxygen atom
of a carboxylate group. All of these equatorial oxygen atoms
belong to two ligands, P2 and P3, which configure edge-sharing
calcium polyhedral chains and connect them into the layers,
while leaving alternately arranged free carboxylic groups inside
the interlayer space (Figure 4). The axial positions of the calcium
polyhedron are occupied by a water molecule and a phosphonate
or carboxylate oxygen of the third organic ligand, P1, which is
pillaring adjacent layers.
Within the layers, each phosphonate moiety uses only two
oxygen atoms to coordinate calcium in such a way that one
oxygen atom is bridging two metal centers, thus leaving a free
POH pointing to the interlayer space. One of the carboxylate
moieties of both dicarboxyphosphonate ligands, P2 and P3, is
Figure 3. Coordination environment of the two Ca centers in the
structure of Ca-PiPhtA-I.
coordinated to calcium atoms through one of the oxygens, while
the other one is protonated. Besides, the second carboxylic group
of each these ligands is pointing toward the interlayer space
and faced up to each other interacting strongly by a H-bond. This
disposition creates H-bond rings contributing to the stabilization
of the pillared layered structure. The third dicarboxyphosphonate
ligand, P1, is linking adjacent layers only by one phosphonate
oxygen, by one side, and one carboxylate oxygen atom, from the
other side. This connectivity mode leaves a POH and a free
carboxylic group inside the interlayer space (see Figure 4).
The overall structure architecture reveals interlayer hydro-
philic 1-D channels running parallel to the b axis, filled with five
lattice waters per unit cell forming zigzag chains inside the
cavities (Figure 5).
The parallel zigzag chains acquire a left-handed helix and a
right-handed helix along the c axis. The water-to-water interac-
tions between these lattice waters create an extended network of
H bonds along the 1-D channels and therefore a potential proton
transfer pathway, which may play an important role in the proton
conductivity exhibited by the Ca-PiPhtA materials (see Table S1,
Supporting Information).
The title compound shares some similarities with compounds
Ca2(H2O)[H(OOC)2C6H3PO3H]2 and [Sm2(H2O)4(H-
(OOC)2C6H3PO3)2]·2H2O obtained by hydrothermal treat-
ment.30 In the former, each ligand is 2-fold deprotonated resulting
D
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differently, Sm3+ is nine coordinated and, additionally, side arms
of edge-sharing polyhedra of Sm3+ are attached to the main
chain. Thus, the chains are interconnected by phosphonate and
carboxylate groups coordinated to Sm3+ ions, giving hybrid layers
interconnected by hydrogen bonding between two carboxylic
acid groups.
FT-IR Spectroscopy. Comparison of the FT-IR spectrum of
the “free” ligand PiPhtA with that of Ca-PiPhtA-I is revealing.
The ligand shows antisymmetric ν(CO) stretches at 1705,
1665, and 1599 cm−1 and symmetric ν(C−O) stretches at 1454,
1437, and 1395 cm−1. These are shifted in the spectrum of Ca-
PiPhtA-I, with the antisymmetric ν(CO) stretches appearing
at 1692, 1605, and 1572 cm−1 and the symmetric ν(C−O)
stretches located at 1434, 1406, and 1381 cm−1. Such shifts upon
ligand coordination in bands associated with the carboxylate
group are well established in the literature.31 There are also
notable shifts in the vibrations related to the phosphonate group.
There is a set of three strong intensity bands in the ligand
spectrum at 1109, 1135, and 1242 cm−1, which are appropriately
shifted to 1132, 1255, and 1278 cm−1 in the compound spectrum.
These are assigned to the −PO3 antisymmetric stretch. Lastly,
a band at 932 cm−1 in the ligand spectrum assigned to the
P−O stretch shows up at 913 cm−1 in the compound spectrum
(Figure S1, Supporting Information). All phosphonate-related
bands appear in the same region as that reported for several other
metal phosphonate materials.
Figure 4. (Top) 3D structure of Ca-PiPhtA-I along the b axis, showing
the relative arrangement of the water-filled 1D channels and the moieties
protruding from the channel wall to the interior. (Bottom) Longitudinal
view (b-axis horizontal) of the 1D water columns within the pillared
scaffold.
Thermal Behavior. The thermal stability of Ca-PiPhtA-I
compound was studied by TG-DTA analysis and X-ray
thermodiffraction. The TG and heat flow curves, Figure 6,
Figure 6. TGA (green) and DTA (blue) curves for Ca-PiPhtA-I
(dashed line) and after adsorption of NH3, Ca-PiPhtA-NH3 (solid
lines).
Figure 5. (Top) Two neighboring water channels. Upper channel
(in blue) represents a left-handed helix, whereas the lower (in red)
represents a right-handed helix. (Bottom) Close contacts between the O
atoms within a water channel.
show that dehydration of the solid takes place in three over-
lapping steps between 50 and 220 °C. The two first steps are
centered at 75 and 130 °C and correspond to removal of five
lattice waters (observed weight loss 9.63%, calculated 9.62%).
The third step, centered at 180 °C, is due to elimination of the
Ca-bound water. The dehydration process ends at 220 °C with an
associated weight loss of 13.24%, which is consistent with the loss of
seven water molecules (calculated 13.5%) and the results from the
crystallographic study. Above this temperature, a small but
progressive mass loss is observed that suggests partial decomposition
of the solid before combustion of the organic moieties at 380 °C.
Dehydration of Ca-PiPhtA-I was also followed by thermodif-
fraction (Figure 7). Although no water is lost between room
temperature and 50 °C, a slight change in the symmetry of the
in three distinctive coordinating groups, one carboxylate, one
carboxylic, and one hydrogen phosphonate group. Ca2+ ions
are also coordinated by seven oxygen atoms, and Ca polyhedrons
are found sharing edges. However, only discrete Ca2O12 dimers are
present in the structure of the reported Ca derivative instead of
lineal chains. In addition, the connectivity of the three groups is
also modified, the title compound showing a higher connectivity
of the hydrogen phosphonate groups relative to the carboxylate/
carboxylic groups. Regarding the samarium derivative, the main
structural feature common with the title compound is the
presence of edge-sharing Sm polyhedron chains. However,
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Figure 8. b-axis view (a-axis horizontal) of the crystal structures for Ca-
PiPhtA-I (left) and Ca-PiPhtA-II (right) showing the slightly different
conformation of the 1D channels along the c axis.
Figure 7. Thermodiffractometric study for Ca-PiPhtA-I at selected
temperatures.
changes in the interlayer region of the monoclinic cell is the
appearance of asymmetric H-bond rings between facing-up
carboxylic groups, with interaction distances −COO−H···O−
C−OH− of 2.1 and 2.8 Å. The existence of different 1-D
channels may affect the H-bond strength in the monoclinic cell
upon rehydration.
compound is already apparent in this temperature range, as
indicated by the splitting of some of the diffraction peaks. At
75 °C, the sample is partially dehydrated and exhibits a diffraction
pattern that can be indexed in a monoclinic cell with parameters
very close to the “as-synthesized sample”. This framework re-
mains stable upon heating up to 135 °C, as confirmed by the
corresponding LeBail fits. The appearance of additional
diffraction peaks in the range 135−220 °C, which cannot be
indexed in the monoclinic cell, is indicative of further structural
changes taking place concurrently with removal of the
coordinated water and a progressive loss of crystallinity.
However, the crystallinity is restored when the sample preheated
at 220 °C is exposed to air or put in contact with a controlled
humidity atmosphere (saturated K2SO4 solution) at room tem-
perature for 4 days (Figure 7). The resulting diffraction pattern
agrees well with a mixture of the orthorhombic and monoclinic
phases. Thermogravimetric analysis also reveals that this sample
is fully rehydrated (13.39% of weight loss at 250 °C).
Rietveld refinement was carried out for the sample heated at
75 °C, Ca-PiPhtA-II, in order to gain better insight on the structural
identity of the monoclinic phase. For refinement, the crystal
structure of Ca-PiPhtA-I was used as a starting model after
reducing symmetry to the monoclinic space subgroup Pa. A
total of 104 atoms in the asymmetric unit were refined using
synchrotron powder X-ray diffraction data. The final Rietveld
plot is given as Supporting Information (Figure S2). The water
content for this sample was determined to be 9.70% by
thermogravimetric analysis, at a time scale similar to that of the
thermodiffractometric study. The weight loss agrees well with
complete removal of the lattice water.
Absorption of NH3 Vapors. Ca-PiPhtA-I was exposed to
vapors from a concentrated aqueous ammonia solution (28%). A
new derivative was obtained (Ca-PiPhtA-NH3) containing 7
NH3 and 16 H2O molecules according to elemental and thermal
analyses. This material exhibits a complex X-ray diffraction
pattern with peaks at 15.3 and 13.0 Å that suggest partial breaking
of the pillared structure (Figure S3, Supporting Information).
This hypothesis is strongly supported by the inability of the
original narrow 1-D channels to accommodate the high number
(23) of intercalated guest species. Although a detailed structural
analysis of Ca-PiPhtA-NH3 has not yet been possible, due in part
to the lack of crystallinity, inspection of the IR spectra and DTA-
TG analysis indicate profound structural changes compared to
the pristine Ca-PiPhtA-I. Hence, in addition to the characteristic
IR bands corresponding to metal carboxyphosphonates observed
for Ca-PiPhtA-I and in agreement with the crystallographic
data,32 the IR spectrum of Ca-PiPhtA-NH3 (Figure S1,
Supporting Information) shows a shift to lower wave numbers
in the water stretching vibrations region, which is indicative of
the existence of strong hydrogen bonds between intercalated
water and ammonia guest molecules. In addition, the character-
istic bands corresponding to the carboxylic31 (∼1700 cm−1) and
hydrogen phosphonate33 (915−930 cm−1) groups are practically
absent in the vibrational spectrum of Ca-PiPhtA-NH3 as a
consequence of the reaction of these acidic groups with NH3. In
addition, the DTA-TG curves of the ammonia derivative
Ca-PiPhtA-NH3 (Figure 6) show a higher guest molecule
content between room temperature and 400 °C. Importantly, a
different weight loss profile is noted, revealing a new
endothermic peak at 210 °C, indicative of strongly retained
guest species. Thermodiffraction of Ca-PiPhtA-NH3 shows a
progressive amorphization of the sample with removal of the
guest species, although the peak at 15.3 Å (corresponding to the
new intercalated phase) persists up to 125 °C. This is a good
indication of the high stability of this phase.
Removal of lattice waters provokes small structural changes,
according to the refined unit cell parameters (see Table 1), which
are more significant along the pillaring direction (c axis). The
resulting monoclinic phase, Ca-PiPhtA-II, has 4 Ca atoms, 6
ligands, and 4 water molecules in the asymmetric unit. All
connectivity modes of the “parent” Ca-PiPhtA-I framework are
retained in Ca-PiPhtA-II. However, the higher complexity of the
unit cell results in higher distortion of the calcium polyhedra and
hence formation of an alternate interlayer region with slightly
different cavity dimensions (see Figure 8), the alteration of the
axial angles O−Ca−O along the c axis being the most significant
In the absence of precise structural data, we speculate that
Ca-PiPhtA-NH3 is a multiphase compound with peaks at 15.3
and 13 Å representing the d(oo2) basal spacing of two new layered
phases originated by rupture of the interlayer phosphonate/
Ca2+ or carboxylate/Ca2+ bonds (see Figure 9). The similar
bond lengths for the distances Ca−Ocarboxylate [2.378(9) Å] and
structural change in the monoclinic cell. Hence, new O5b−Ca1b
−
Ow6b = 153(3)° and O1b−Ca2−Ow76 = 153(3)° angles are ob-
served, together with Oax−Ca−Oax angles close to 180°
characteristic of the orthorhombic cell. A consequence of these
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Figure 9. Schematic representation for the rupture of the 3D framework
to give new 2D intercalated derivatives.
Figure 10. Plot of the complex impedance plane for Ca-PiPhtA
compounds at 24 °C and 98% RH.
Ca−Ophosphonate [2.394(9) Å] may support both breaking
mechanisms. Other phases at lower d spacing, if existing, are
more difficult to distinguish due to overlapping with other
reflections of the crystal. The reactivity of Ca-PiPhtA-I toward a
concentrated solution of ammonia is in clear contrast to the
almost inexistent adsorption by running a typical NH3-TPD
experiment on a sample previously dehydrated at 200 °C. This
suggests that ammonia and water adsorption occurs through a
cooperative mechanism of hydrogen-bond interaction.
materials is higher than those reported for other Ca-based
MOFs, the latter exhibiting values in the range from 10−5 to
4 × 10−4 S·cm−1 under similar experimental conditions.34,35
As observed in Figure 11, the proton conductivity of
Ca-PiPhtA-III remains practically constant up to ∼40 °C,
Proton Conductivity Study. The Ca-PiPhtA-I framework
possesses 1D channels hosting zigzag chains of water molecules
that simultaneously interact with the pendant−POH and
−COOH groups. These structural features prompted us to
undertake a study of its proton conductivity. Effective pathways
for proton transfer could be created through the H-bond
interactions among the acidic groups and both lattice and
Ca-bound water molecules. Thermogravimetric analysis revealed
that the starting samples exposed to 98% RH were fully hydrated,
as the measured weight losses were very close to the observed
value of 13% at 250 °C for the as-synthesized material
Ca-PiPhtA-I. All conductivity measurements were carried out
after equilibration for 18 h to ensure that the samples exhibit stable
conductivity values and were fully reproducible after several cycles
of measurements (Figure S4, Supporting Information).
The impedance plots, Figure 10, show similar features with
spikes inclined to the Z′ axis by ∼70°, indicating a partial-
blocking electrode response that allows limited diffusion and,
therefore, confirms the conducting species must be ionic, i.e.,
H+ ions. The total pellet resistances, RT, were obtained from the
intercept of the spikes and/or the arcs (low frequency end) on
the Z′ axis. At 98% RH and T = 24 °C, the conductivity values,
σ, are 5.7 × 10−4 and 3.6 × 10−4 S·cm−1 for Ca-PiPhtA-I and
Ca-PiPhtA-II, respectively. These conductivities rise up to 1.3 ×
10−3 S·cm−1 upon preheating the sample at 40 °C for 2 h and
subsequently water-equilibrated (Ca-PiPhtA-III). The X-ray
diffraction pattern for Ca-PiPhtA-III is similar to that of
Ca-PiPhtA-I, and its water content remains unchanged as
confirmed by thermal analysis. We attribute the increase in
conductivity to a thermal activation mechanism implying small
but effective structural and/or textural changes (surface effect)
leading to an enhancement of the proton conduction properties.
The conductivity value obtained for the Ca-PiPhtA-I sample
after thermal activation is of the same magnitude as for other
functionalized metal phosphonates (from 1.6 × 10−3 to 8 × 10−3
S·cm−1)18,19 and other MOF materials, some of them reaching
10−2 S·cm−1.15g,f However, the proton conductivity of Ca-PiPhtA
Figure 11. Plot of log σ vs 1000/T for Ca-PiPhtA-III from 24 to 75 °C.
notwithstanding the relative humidity is progressively decreas-
ing. Higher temperatures cause a profound drop in conductivity,
most likely due to dehydration, according to the TG curve. This
behavior is characteristic of water-mediated proton conductors
when a drastic reduction in proton carrier number occurs.15d
As the nature and size of the internal cavities may strongly
influence the proton conductivity behavior, it was decided to
measure the conductivity of the NH3 derivative, which can host
a considerably high number of proton carriers and thus possesses
impressive swelling properties. As shown in Figure 10, Ca-
PiPhtA-NH3 exhibits the highest proton conductivity in the
selected temperature range. The maximum conductivity value
measured at 98% RH and T = 24 °C was 6.6 × 10−3 S·cm−1.
These results underline the importance of internal H-bonding
networks that, in turn, determine conductivity properties of
hybrid materials. Additionally, post-synthetic cavity “derivatization”
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with selected guest molecules may enhance these properties by
creating new proton transfer pathways.
be an important mechanism to create new proton transfer
pathways that improve the proton conductivity.
The activation energies (Ea) for the proton transfer in
Ca-PiPhtA-I, Ca-PiPhtA-III, and Ca-PiPhtA-NH3 range
between 0.23 and 0.4 eV (Figure 12). Preheating the sample at
ASSOCIATED CONTENT
* Supporting Information
■
S
ATR-IR spectra for Ca-PiPhtA-I and Ca-PiPhtA-NH3; Rietveld
refinement powder XRD profile of Ca-PiPhtA-II; powder X-ray
diffraction patterns for (a) Ca-PiPhtA-I and (b) Ca-PiPhtA-
NH3; plot of log σ vs time for Ca-PiPhtA-I and Ca-PiPhtA-III
for two cycles; table of bond lengths and H-bond distances for
Ca-PiPhtA-I; CIF files for Ca-PiPhtA-I and Ca-PiPhtA-II. This
material is available free of charge via the Internet at http://pubs.
acs.org.
AUTHOR INFORMATION
Corresponding Authors
demadis@chemistry.uoc.gr. (K.D.D.)
aurelio@uma.es (A.C.)
■
Author Contributions
The manuscript was written through contributions of all authors.
All authors have given approval to the final version of the
manuscript.
Notes
The authors declare no competing financial interest.
Figure 12. Arrhenius plots vs T−1 from 10 to 24 °C.
ACKNOWLEDGMENTS
ALBA synchrotron is thanked for providing synchrotron
beamtime at BL04-MSPD beamline. The project “Factoria de
■
40 °C seems to induce small structural distortions favorable for
proton transfer through a pathway of sites separated by a smaller
energy barrier.15f,16 The activation energy of Ca-PiPhtA-NH3
although increased with respect to the two other Ca-PiPhtA
compounds is still within the range of values consistent with the
Grotthuss H+ transfer mechanism.36
́
́
Cristalizacion, CONSOLIDER INGENIO-2010” provided X-
ray diffraction facilities for this work. The work at UMA was
funded by a MAT2010-15175 research grant (Spain) which is
cofunded by FEDER. The work at the UoC was supported by
grants from the Research Committee of the University of Crete,
ELKE (KA 3517 and KA 3806). The work at Wrocław University
of Technology was founded by The Faculty of Chemistry and the
Faculty of Mechanical and Power Engineering.
CONCLUSION
■
We reported the synthesis, structural characterization, and some
important properties (framework interconversions and proton
conductivity) of an open-framework hybrid material containing
1D channels filled with hydrogen-bonded water molecules,
namely, Ca2[(HO3PC6H3COOH)2]2[(HO3PC6H3(COO)2H)-
(H2O)2]·5H2O (Ca-PiPhtA-I). Its partial dehydration at 75 °C
produces Ca-PiPhtA-II, which exhibits lower water content
but otherwise retains the framework structural features of its
parent Ca-PiPhtA-I. Structure solution using synchrotron
powder X-ray diffraction data revealed its molecular formula
Ca2[(HO3PC6H3COOH)2]2[(HO3PC6H3(COO)2H)(H2O)2].
Upon Ca-PiPhtA-I exposure to ammonia vapors (28% aqueous
NH3) a new derivative is obtained (Ca-PiPhtA-NH3) containing
7 NH3 and 16 H2O molecules. The above-mentioned materials
were studied for proton conductivity. At 98% RH and T = 24 °C,
proton conductivity for Ca-PiPhtA-I is 5.7 × 10−4 S·cm−1. The
proton conductivity properties of this phase can be enhanced up
to 1.3 × 10−3 S·cm−1 by activation upon preheating the sample at
40 °C for 2 h followed by water equilibration. Ca-PiPhtA-NH3
exhibits the highest proton conductivity, 6.6 × 10−3 S·cm−1,
measured at 98% RH and T = 24 °C. Activation energies (Ea) for
proton transfer in the above-mentioned frameworks range
between 0.23 and 0.4 eV, typical of a Grothuss mechanism of
proton conduction. These results emphasize the significance of
internal H-bonding networks and their profound effect on
conductivity properties, at least in the case of Ca-PiPhtA-I.
Finally, cavity “derivatization” with selected guest molecules may
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