Crystalline and permanently porous porphyrin-based metal tetraphosphonates

Article abstract of DOI:10.1039/c7cc07766a

The new porphyrin-based tetraphosphonic acid (Ni-H₈TPPP) was employed in the synthesis of four isostructural MOFs of composition [M(Ni-H₆TPPP)(H₂O)], denoted CAU-29 (M = Mn, Co, Ni, Cd). Ni-CAU-29 was thoroughly characterized regarding its thermal and chemical stability as well as for proton conductivity.

Full text of DOI:10.1039/c7cc07766a

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Crystalline and permanently porous porphyrin-based metal
tetraphosphonates
Received 00th January 20xx,
Accepted 00th January 20xx
a
b
c
c
Timo Rhauderwiek, Konrad Wolkersdörfer, Sigurd Øien-Ødegaard, Karl-Petter Lillerud, Michael
b
a,c
Wark and Norbert Stock
DOI: 10.1039/x0xx00000x
www.rsc.org/
The new porphyrine-based tetraphosphonic acid (Ni-H
8
TPPP) was reported. These molecular compounds were characterized
1
2, 13, 16
13, 16,
employed in the synthesis of four isostructural MOFs of regarding their electrochemical
1
and photochemical
7
14, 15
18-20
composition [M(Ni-H
6
TPPP)(H
2
O)], denoted CAU-29 (M= Mn, Co,
properties as well as in catalytic
processes.
and self assembling
2
1
Ni, Cd). Ni-CAU-29 was thoroughly characterized regarding its
thermal and chemical stability as well as on its proton Here we present the synthesis of a new planar porphyrin-
conductivity.
based tetraphosphonic acid (Ni-H
synthesis of MOFs. The linker with a Ni ion coordinated in the
centre of the porphyrin ring (Ni-H TPPP) was obtained in a
three step synthesis (Fig. S1) starting from 4-
8
TPPP) and its use in the
2
+
Metal phosphonates are often highly stable which can be
explained by the higher charge and the larger number of donor
8
2
-
-
1
2
2, 23
atoms of the –PO3 in comparison to the –CO2 group. They
are therefore promising candidates for applications in gas
2, 3
brombenzaldheyd.
In the second step the resulting
TBrPP) was phosphorylated using
With a yield of 75 % this approach is
by far more efficient compared to the Pd-catalysed reaction
4
-bromophenylporphyrin (H
2
2
4, 25
separation and catalysis.
Metal phosphonates containing
2
NiCl as the catalyst.
-
PO H groups are also studied for their proton conductivity.
2
–
3
2
6, 27
Only a relatively small number of porous metal phosphonates
has been reported to date due to the higher coordination
leading to H10TPPP (yield: 28 %)
Acid catalyzed (conc. HCl)
hydrolysis leads in the last step to the metalated linker
Ni-H TPPP. The resulting product was obtained in high purity
3
, 4
flexibility of the phosphonate groups.
Taddei et al. have
8
recently demonstrated that the use of non-linear large and
rigid tritopic phosphonic acids leads to the formation of porous
with an overall yield of 23 %.
High-throughput methods were employed in the screening of
synthesis parameters such as molar ratio of metal to linker, pH
and reaction temperature (details see SI). The use of the
5
metal phosphonates. Accordingly tetratopic ligands with
tetrahedral geometry like adamantan or methane based
tetraphosphonic acids resulted in four porous metal
2
+
2+
2+
2+
divalent metal ions Mn , Co , Ni and Cd in hydrothermal
syntheses resulted in the formation of a series of four
isostructural, highly crystalline and porous MOFs (Fig. 1) of
composition [M(Ni-H TPPP)(H O)] (M = Mn, Co, Ni, Cd), which
6
,7
phosphonates.
In recent years numerous metal organic frameworks (MOFs)
were obtained using tetra(4-carboxyphenyl)porphyrin
6
2
8
, 9
(
H TCPP) as the organic building unit.
6
Especially Zr-MOFs
8, 10
was denoted as M-CAU-29. The use of molar metal to linker
ratios of 1 to 1 resulted in CAU-29 with low crystallinity, while
higher ratios up to 5 to 1 of metal and the 3-fold concentration
of metal and linker led to highly crystalline CAU-29 (Fig. S5).
4
containing the H TCPP ion are highly porous and stable.
-
2
The presence of the porphyrin moiety leads to selective redox
9
properties. The analogous linker containing –PO H instead of
3
2
–
COOH groups, i.e. tetra(4-phosphonophenyl)porphyrin
1
H TPPP) has been already reported in 1992, but it has not
1
(
10
been employed for the synthesis of MOFs yet. In addition to
1
2, 13
the free-base linker H TPPP, its esterified form
1
as well as
have been
0
1
4, 15
the Mn-metalated linker (Mn-H TPPP)
8
Figure 1. Scheme of the high-throughput investigation of M-CAU-29 (M= Mn, Co,
8 2 2
Ni, Mn) using Ni-H TPPP (left) and MCl salts in H O as solvent.
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3
2
30
32
30
to 1.491(6) Å and 1.529(3) to 1.581(6) Å ,
Despite the harsh reaction conditions of 180 °C and a reaction 1.486(3)
2
+
time of 48 h, no leaching of Ni ions form the porphyrin center respectively.
was observed, as proven by UV/vis spectroscopy (Fig. S28) as
well as TG and elemental analysis (see SI).
Mn-, Co- and Cd-CAU-29 were obtained as microcrystalline
powders while Ni-CAU-29 consists also of very small single
crystals (Fig. S6). The crystal structure of CAU-29 was
elucidated by single crystal X-ray diffraction using a crystal
3
28
(
5x10x20 µm ) of Ni-CAU-29 (Tab. S1). High resolution PXRD
measurements of M-CAU-29 (M= Mn, Co, Ni, Cd) were
performed (Fig. 3) and Rietveld-refinements (Co-, Ni-CAU-29)
and Pawley-fits (Mn-, Cd-CAU-29, Fig. S8-S11, Tab. S2) were
carried out using the single crystal X-ray diffraction data of Ni-
CAU-29 as a starting model. Thus, phase purity was proven and
lattice parameters of the isostructural compounds were
determined. Ni-CAU-29 crystallizes in a triclinic crystal system
ꢀ
in the space group P1 (a=9.561(5), b=15.086(9), c=16.722(9) Å
and α=94.723(9), β=97.602(9), γ=7.880(9) °, Tab. S1). The
Figure 3. High resolution PXRD pattern of M-CAU-29 (M= Mn, Co, Ni, Cd).
inorganic building unit of Ni-CAU-29, [Ni(Ni-H TPPP)(H O)] ∙ 11
2
6
The sorption properties of M-CAU-29 were studied employing
N (Fig. 4) and H O (Fig. S12) at 77 and 298 K, respectively.
H O, consists of two isolated edge-sharing NiO polyhedra,
2
6
2
which are bridged by the linker Ni-H TPPP to a three
-
2
2
6
Prior to the measurements the samples were activated at 170
dimensional porous network (Fig. 2). Thus two kinds of 1D
pores with the dimensions 2.8 x 5.0 Å and 3.8 x 3.8 Å are
formed, taking the van-der-Waals radii into account. The
coordination modes [2,002] and [1,001] of the (di)hydrogen
-
2
°
C under reduced pressure of 10 kPa for 16 h. Ni-CAU-29
shows no uptake of N at 77 K but the highest water uptake of
81 mg g . Mn-, Co- and Cd-CAU-29 exhibit N uptakes of 90,
145 and 180 m g and H O uptakes of 140, 166 and 116
2
-1
1
2
2
-1
2
9
2
phosphonate groups in Ni-CAU-29 are shown in Figure S7.
-1
mg g , respectively. These differences in adsorption properties
are probably due to the presence of the small micropores in
combination with slight metal-dependent structural changes
upon thermal activation (dehydration) as confirmed by
variable temperature PXRD as well as differences in the kinetic
The bond lengths found in Ni-CAU-29 are in good agreement
with literature values (selected bond lengths are shown in Tab.
S1a). Ni-O distances between 2.04(2) and 2.14(2) Å were
3
0, 31
observed (lit.: 2.008(15)-2.114(16) Å).
The P-O bond
lengths vary between 1.48(2) and 1.57(2) Å, which agrees well
-
with the presence of P=O, P-OH and P-O groups. In literature
-
P=O and P-OH/ P-O distances are reported in ranges of
3
3
2 2
diameters of N and H O (3.64 and 2.65 Å) and the different
temperatures during sorption measurements (77 vs. 298 K).
2
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Such differences are not unusual and have been reported for UV/vis spectroscopy was employed to prove the metalation of
3
4
example for STA-12. Similar The pore volumina were the porphyrin moiety after the solvothermal reaction. The
determined at p/p = 0.5 for Mn-, Co- and Cd-CAU-29 as 0.05, pure linker Ni-H TPPP as well as the MOFs exhibited nearly
.08 and 0.09 cm g . PXRD measurements after the sorption identical positions for the Soret- and Q1- band at 412/413 and
0
8
3
-1
0
experiments prove the stability of CAU-29 after activation and 526/527 nm, respectively (Fig. S28).
the sorption experiment (Fig. S13). Due to the strong The proton conductivity of Ni-CAU-29 was tested due to the
-
H groups protruding into the pores. The
hysteresis observed in all samples, which is probably due to presence of –PO
3
kinetic effects, well known for samples containing impedance spectroscopic measurements were carried out at
ultramicropores (< 0.7 nm), the desorption measurement was 50, 75, 90 % relative humidity (%rh) and temperatures in the
3
5
aborted at p/p
0
=0.1.
range of 80 to 140 °C. The ionic resistance ꢁꢂꢃꢄꢂꢅ was extracted
from Bode plots (Fig. S25). The ionic conductance ꢆꢂꢃꢄꢂꢅ was
then calculated according to:ꢇꢇꢆꢂꢃꢄꢂꢅ ꢈ ꢉ ⁄ ꢊꢋ ꢌ ꢁꢂꢃꢄꢂꢅꢍ, with ꢉ
being the sample thickness and A the electrode surface,
respectively.
The relative humidity controls the proton conductivity of Ni-
CAU-29. At 80 °C a change in relative humidity from 50 to 90
-
7
-6
%
rh increases the proton conductivity from 2.4∙10 to 5.6∙10
-1
-
S∙cm (Table 1). The –PO H groups pointing into the pores of
3
the CAU-29 could facilitate the formation of an H-bond
network which is in line with a strong influence of humidity on
the proton conduction. The activation energy of the ionic
conductance can be extracted from the slope of the straight
3
6
line of an Arrhenius plot. An increase in humidity induces a
decrease in the activation energy (Figure 5). The values of the
activation energy range from 0.1 to 0.4 eV. Accordingly, these
2
Figure 4. Results of the N -sorption experiments of M-CAU-29 (M= Mn, Ni, Co, Cd) at 77
-1
K (activated prior the measurement at 170 °C, overnight at reduced pressure of 10
kPa).
3
6
values support that Grotthus mechanism is the dominant
pathway for proton conductivity in Ni-CAU-29.
The thermal stability of all title compounds was proven by
thermogravimetric (TG, Fig. S14-S18, Tab. S3) and variable
temperature- (VT-) PXRD measurements (Fig. S20-S23). In the
TG curves of all compounds two broad steps of weight loss are
observed at nearly identical temperatures. The first step up to
a temperature of 300 °C indicates the loss of crystal water and
the second step; the collapse of the frameworks is observed
above 350 °C. An increase in weight just before the collapse of
the framework is only observed in an air atmosphere. Since
2
this increase has not been observed in N (Fig. S17), we
assume the formation of e.g. NiO before the collapse of the
framework. The results of the VT-PXRD measurements are in
good agreement with those of the TG measurements. The
complete loss of crystallinity due to the collapse of the
framework is observed around 350 °C. Prior to the complete
loss of crystallinity in case of Ni- and Cd-CAU-29 a small
decrease of crystallinity is observed above 250 °C. In case of
Mn- and Co-CAU-29 a phase transformation above 200 °C
followed by the complete loss of crystallinity is observed. PXRD
pattern of the remaining products of the TG measurements
Figure 5. Arrhenius plot of the ionic conductance of Ni-CAU-29.
Table 1. Proton conductivity at different temperatures between 80 and 140 °C and
A
Arrhenius activation energies E of Ni-CAU-29 at different relative humidities (rh) of 50,
7
5 and 90 %.
(
Fig. S19) reveal the formation of different Ni-M- pyro- and
relative humidity [rh%]
50
75
90
-
1
-7
-6
-6
-6
-6
-6
-6
-6
-6
metaphosphates (M= Mn, Co, Cd).
conductivity [S cm ] 80 °C
2.41∙10
1.35∙10
1.78∙10
2.60∙10
3.42∙10
0.23
5.62∙10
5.80∙10
6.85∙10
7.82∙10
0.10
-
7
7
6
The chemical stability of Ni-CAU-29 was proven for Ni-CAU-29
by stirring the compound in different solvents for 24 h and
subsequent PXRD anaylsis (Fig. S24). Ni-CAU-29 is stable in a
pH range (HCl or NaOH) between 1 and 11 as well as in all
tested organic solvents (DCM, EtOH, DMF, acetone) and in 100
100 °C
3.46∙10
-
1
1
20 °C
40 °C
6.02∙10
-
1.04∙10
0.34
A
E [eV]
Moreover, the structure is unaffected by the humidified
atmosphere at elevated temperature during the proton
%
acetic acid. At pH 0 a loss of crystallinity is observed and
above pH 11 and in phosphate buffer (0.1 M, pH7) the
complete decomposition of the framework takes place.
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In summary, we have demonstrated the successful synthesis
and characterization of a series of isostructural MOFs
containing a new Ni-metalated porphyrin-based phosphonic
acid as linker molecule. To the best of our knowledge to date
only four other porous and crystalline metal phosphonates
1
2
+
2+
,
2+
with the in this work discussed cations Mn , Co
Ni and
M-CAU-29 [M(Ni-
O)] (M= Mn, Co, Ni, Cd) exhibit different sorption
properties towards N and H O at 77 and 298 K, respectively.
2
+
2, 31, 34, 37, 38
1
1
1
Cd have been reported.
TPPP)(H
H
6
2
2
2
The thermal and chemical stability of M-CAU-29 was tested
and reveals a thermal stability up to 400 °C and chemical
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conductivity by electrochemical impedance spectroscopy; at
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8
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1
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We appreciate support from
8
TPPP as the linker.
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| J. Name., 2012, 00, 1-3
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DOI: 10.1039/C7CC07766A
Synopsis
The first porous MOF containing a porphyrin-based phosphonic acid was synthesized and
characterized regarding its sorption properties and proton conductivity.
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