A new metal carboxylate framework based on porphyrin with extended π-conjugation

Article abstract of DOI:10.1002/ejic.201100660

We have designed a new tetracarboxylporphyrin building block, ZnTCPEP-H₄, and used it in the construction of a novel porphyrin-based metal carboxylate framework, [Zn₄(μ₃- OH)₂(H₂O)₂(ZnTCPEP

Full text of DOI:10.1002/ejic.201100660

FULL PAPER
DOI: 10.1002/ejic.201100660
A New Metal Carboxylate Framework Based on Porphyrin with Extended π-
Conjugation
Satoshi Matsunaga,*[a] Nanako Endo,[a] and Wasuke Mori*[a]
Keywords: Microporous materials / Zinc / Metal–organic frameworks / Porphyrinoids / Carboxylate ligands
We have designed a new tetracarboxylporphyrin building
block, ZnTCPEP-H4, and used it in the construction of a
novel porphyrin-based metal carboxylate framework, [Zn4-
(μ3-OH)2(H2O)2(ZnTCPEP-H)2(DABCO)]·2DMF·10.5H2O
(Zn4·ZnTCPEP·DABCO). The framework forms a 3D network
linked by tetranuclear Zn cluster nodes {Zn4(μ3-OH)2(H2O)2},
ZnTCPEP-H4, and DABCO. The ZnTCPEP-H4 building block
exhibits extended π-conjugation from the porphyrin core to
the terminal carboxyl groups via ethynyl linkers attached to
the porphyrin core. The Zn4·ZnTCPEP·DABCO framework
gives rise to a 3D porous structure containing open channels
with cross sections of approximately 10ϫ10 and 7ϫ7 Å. It
has a BET surface area of 461 m2/g and a Langmuir surface
area of 581 m2/g. A hydrogen adsorption capacity of 0.86wt.-
% was determined for Zn4·ZnTCPEP·DABCO at 77 K and
0.1 MPa.
carboxylate microporous MOF containing H2TCPP,
[Rh2(H2TCPP)]n, and reported on its gas adsorption ability
and catalytic activity for the hydrogenation of ethylene and
propylene.[2a] In 2005, we also reported that rhodium carb-
oxylate microporous MOFs incorporating various metallo-
TCPPs, that is, [Rh2(MTCPP)] (M = H2, Cu2+, Ni2+, Pd2+),
showed high turnover frequencies for the hydrogenation of
olefins, and the catalytic activities depended on the type of
metal center coordinated to the porphyrin ring, which
means that the metallo-TCPPs exhibit a bimetallic effect.[2b]
Recently, Choe and co-workers reported on the crystal
structure and hydrogen adsorption capacity of a similar
compound, [Zn2(ZnTCPP)], in which Zn2+ was used as the
node metal.[7h] Furthermore, many other supramolecular
structures constructed by self-assembly of TCPP derivatives
have been reported; especially well known are the signifi-
cant works by Goldberg and co-workers.[11] Most recently,
Farha and co-workers reported on robust porphyrinic mate-
rials (RPMs).[7k]
However, the multicarboxylporphyrin derivatives that
have been used as MOF building blocks are limited to
meso-aryl-substituted porphyrins. In meso-aryl-substituted
porphyrins, the aryl groups are twisted out of the porphyrin
plane due to steric hindrance between protons at the β posi-
tion of the porphyrin core and protons at the ortho posi-
tions of the aryl groups. Therefore, the porphyrin plane is
not coplanar with the carboxyl planes, which results in the
interruption of the π-conjugation (Figure 1a). To solve this
problem, we have designed a novel porphyrin derivative,
TCPEP (Figure 1b), in which the four carboxyphenyl
groups are attached to the porphyrin core via ethynyl link-
ers. The carboxyl planes of TCPEP are almost coplanar
with the porphyrin plane due to a lack of steric hindrance.
By using TCPEP as MOF building blocks, it is possible to
Introduction
Porous metal–organic frameworks (MOFs) have at-
tracted much attention because of their potential applica-
tions in various fields, including gas storage,[1,2d–2f] gas sep-
aration,[3] ion exchange,[4] and catalysis.[2,5] In order to fur-
ther functionalize MOFs, it is important to incorporate
functional ligands as the MOF building blocks. The use of
functional building blocks provides a unique opportunity to
add desirable ligand-intrinsic properties to the frameworks.
Many studies have been reported, in which functional
building blocks, such as metallosalens,[6] metalloporphyr-
ins,[7] carboranes,[8] and polyoxometalates,[9] were used.
Metalloporphyrins in particular can be found throughout
nature and have unique catalytic, electronic, and optical
properties.[10] The physical and chemical properties of
metalloporphyrins can be controlled by proper functionali-
zation of the porphyrin core through standard modifica-
tions. Using metalloporphyrins as MOF building blocks of-
fers the potential to tailor the photochemical and redox
properties of the frameworks. Additionally, by incorporat-
ing accessible metal sites (AMSs) into MOFs, their catalytic
activity and gas adsorption capacity can be enhanced.
Metalloporphyrins are also one of the best building blocks
for incorporation of AMSs into MOFs.
We have studied porphyrin-based microporous MOFs
and a multicarboxylporphyrin derivative in particular, tet-
rakis(4-carboxyphenyl)porphyrin (TCPP), as a potential
building block.[2] In 2003, we synthesized a rhodium
[a] Department of Chemistry, Faculty of Science, Kanagawa
University, Hiratsuka,
Kanagawa 259–1293, Japan
E-mail: matsunaga@kanagawa-u.ac.jp
Supporting information for this article is available on the
WWW under http://dx.doi.org/10.1002/ejic.201100660.
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A New Porphyrin-Based Metal Carboxylate Framework
Figure 1. TCPP and the designed TCPEP porphyrin ligand.
construct new structural MOFs with properties derived ZnTCPEP-H4 with Zn(NO3)2·6H2O and DABCO (1,4-di-
from a large π-conjugated system. In this paper we report azabicyclo[2.2.2]octane) in DMF/EtOH at 80 °C for 24 h
on the construction of novel porphyrin-based metal carb- afforded dark green single crystals of Zn4·ZnTCPEP·
oxylate frameworks [Zn4(μ3-OH)2(H2O)2(ZnTCPEP-H)2- DABCO. According to elemental and thermogravimetric/
(DABCO)]·2DMF·10.5H2O (Zn4·ZnTCPEP·DABCO) with differential thermal analyses (TG/DTA), the single crystals
3D network topology synthesized by using a ZnTCPEP of Zn4·ZnTCPEP·DABCO contain two DMF molecules,
linker and discuss their detailed synthesis, crystal structure, 10.5 water molecules, and two coordinating water molecules
and gas adsorption properties.
and have the formula [Zn4(μ3-OH)2(H2O)2(ZnTCPEP-H)2-
(DABCO)]·2DMF·10.5H2O (Figure S1).
Results and Discussion
Absorption Spectra of the ZnTCPEP-H4 Building Block
Synthesis
The UV/Vis absorption spectra of the ZnTCPEP-H4
The syntheses of the ZnTCPEP-H4 building blocks and building block and ZnTCPP as a reference compound are
Zn4·ZnTCPEP·DABCO are summarized in Scheme 1. shown in Figure 2. The absorption spectrum of ZnTCPEP-
Compounds 2–4 were prepared according to literature pro- H4 in DMF shows a Soret band at 485 nm, together with
cedures.[12] Lithiation of TIPS-acetylene (1) followed by smaller Q-bands at 633 and 687 nm. All bands are red-
acylation with 4-formylmorpholine afforded TIPS-propiolic shifted relative to ZnTCPP (Soret band: 428 nm, Q-bands:
aldehyde (2). The tetra-TIPS-ethynyl-substituted zinc por- 560, 600 nm). The large redshifts of both the Soret band
phyrin 4 was prepared by condensation of pyrrole with 2 and the Q-bands indicate a decreased energy gap between
and subsequent heating of the resultant porphyrin 3 with the HOMO and LUMO orbitals, a consequence of the ex-
Zn(OAc)2·2H2O in CHCl3. Deprotection of the tetra-TIPS- panded π-conjugation. In the meso-aryl-substituted por-
ethynyl-substituted porphyrin 4 with tetrabutylammonium phyrins, the aryl groups are twisted out of the porphyrin
fluoride (TBAF) yielded the deprotected ethynylporphyrin, plane due to steric hindrance between the protons at the β
which was then coupled to methyl-4-iodobenzene under position of the porphyrin core and protons at the ortho po-
copper-free Sonogashira coupling conditions[13] to give the sitions of the aryl groups, resulting in interruption of the π-
tetraester porphyrin ZnTCPEP-Me4. Basic hydrolysis of the conjugation. In contrast, the carboxyphenyl plane of
tetraester ZnTCPEP-Me4 gave the tetracarboxylic acid ZnTCPEP-H4 is coplanar with the porphyrin plane, be-
building block ZnTCPEP-H4. Subsequent reaction of cause the porphyrin core and aryl groups at the meso-posi-
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S. Matsunaga, N. Endo, W. Mori
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Scheme 1. Syntheses of the ZnTCPEP-H4 building block and Zn4·ZnTCPEP·DABCO.
tion are linked via an ethynyl spacer. Therefore, ZnTCPEP- in the visible region indicates that ZnTCPEP-H4 can be a
H4 exhibits extended π-conjugation from the porphyrin building block for visible-light-sensitive functionalized
core to the terminal carboxyl groups. The large absorption MOFs.
Figure 2. UV/VIS absorption spectra of ZnTCPEP-H4 and ZnTCPP in DMF. Inset shows enlarged view.
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A New Porphyrin-Based Metal Carboxylate Framework
Structural Characterization of Zn4·ZnTCPEP·DABCO
shows different coordination modes: two oxygen atoms
[O(1) and O(2)] linking two zinc atoms [Zn(2) and Zn(3)],
Single-crystal X-ray analysis revealed that Zn4· two oxygen atoms [O(3) and O(4)] coordinating one zinc
ZnTCPEP·DABCO crystallizes in the orthorhombic Ccca atom [Zn(3)], and one oxygen atom [O(7)] coordinating one
space group. The ZnTCPEP-H4 units are linked by a tetra- zinc atom [Zn(2)]. The C–O distances for the noncoordina-
nuclear zinc cluster, that is, {Zn4(μ3-OH)(H2O)2}, and ting carboxylic acid are 1.224 Å [C(47)–O(5)] and 1.340 Å
DABCO units, resulting in the formation of a 3D frame- [C(47)–O(6)], in agreement with typical values for carbox-
work. In the cluster unit, two crystallographically indepen- ylic acids. The noncoordinating carboxyl group forms a hy-
dent Zn atoms exist: (i) Zn(2) is tetrahedrally coordinated, drogen bond with a hydrated water molecule [O(11)]. The
binding to two O atoms from two carboxylate groups, one molecular length of the ZnTCPEP unit (ca. 24 Å) is 125%
O atom from a μ3-OH, and one nitrogen atom of a DABCO the length of the ZnTCPP unit (ca. 19 Å) due to the inser-
unit connected to Zn(1) of ZnTCPEP; (ii) Zn(3) is octahe- tion of ethynyl spacers. Every ZnTCPEP unit links three
drally coordinated, binding to three O atoms from two [Zn4(μ3-OH)2(H2O)2] cluster units, and every cluster unit
carboxylate groups, two O atoms from two μ3-OH, and one connects eight ZnTCPEP units via the carboxylate groups
O atom from a H2O (Figure 3a). The bond valence sums and DABCO. This results in a 3D framework with open
(BVSs),[14] calculated from the observed bond lengths, are channels along the diagonal line of the ab plane and the c
1.365 for the O(9) atom and 0.351 for the O(10) atom, axis, which have cross sections of approximately 10ϫ10 and
which reasonably correspond to those of OH– and H2O, 7ϫ7 Å, respectively (Figure 4). Although the open chan-
respectively. A tetranuclear zinc cluster node similar to that nels include some DMF and H2O molecules, it was not pos-
observed in Zn4·ZnTCPEP·DABCO has been reported for sible to locate the guest solvent molecules without taking
Zn4(OH)2(H2O)2(py)2(TCBPB)2·3DMF·py·3H2O (TCBPB into consideration the hydrogen bonding between H2O and
=
1,3,5-tris[4Ј-carboxy(1,1Ј-biphenyl4-yl)]benzene, py
=
a free carboxylic acid, because of their high disorder. There-
pyridine).[15] In the present case, X-ray analysis revealed a fore, the SQUEEZE routine of PLATON was used to re-
high coplanarity of the porphyrin core, the phenyl groups, move the diffraction contribution from these solvents to
and the carboxylate groups within the ZnTCPEP moiety produce a set of solvent-free diffraction intensities.[16]
(average torsion angle between the phenyl ring and the por- Three-dimensional porphyrin-based paddle-wheel frame-
phyrin core: 5.98° in ZnTCPEP compared to 80.14° in works have previously been reported by Choe et al.[17]
ZnTCPP[7h]). Three of the four carboxylate groups of These frameworks were assembled by connecting the inter-
ZnTCPEP are coordinated to the Zn4 cluster, while the re- secting 2D porphyrin paddle-wheel grids through a pyridyl-
maining group is present as a free carboxylic acid (Fig- based organic pillar (e.g., 4,4Ј-bipyridine), which resulted in
ure 3b). Each of the three coordinating carboxylate groups a 3D pillared-layer coordination polymer. In contrast, the
Figure 3. (a) Tetranuclear Zn cluster; (b) ZnTCPEP moiety in Zn4·ZnTCPEP·DABCO. H atoms are omitted for clarity.
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S. Matsunaga, N. Endo, W. Mori
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Figure 4. Extended structure of Zn4·ZnTCPEP·DABCO viewed along (a, b) the diagonal line of the ab plane and (c) the crystallographic
c axis. H atoms are omitted for clarity.
structure of Zn4·ZnTCPEP·DABCO appears to be a more (TCBPB)2·3DMF·py·3H2O, which has a similar tetra-
complicated 3D nonpillared-layer structure. The void vol- nuclear zinc cluster node, showed no permanent porosity,
ume, calculated from single-crystal structures with PLA- possibly, because of a collapse of the framework upon re-
TON/VOID, is 56%.[16]
moval of coordinated water and pyridine.[15] The void vol-
ume calculated from the N2 isotherm is 16.5%, which is
smaller than that calculated from the single-crystal struc-
tures with PLATON/VOID (56%).[16] The pore diameter
distribution of Zn4·ZnTCPEP·DABCO, calculated accord-
Adsorption Properties
Gas adsorption measurements for N2 and H2 at 77 K
were performed on Zn4·ZnTCPEP·DABCO (Figures 5 and
6). The sample was immersed in acetone for several days,
to exchange all of the included nonvolatile solvates (DMF,
H2O), and subsequently dried under vacuum at room
temp. for 24 h. The nitrogen adsorption isotherm of
Zn4·ZnTCPEP·DABCO (Figure 5) shows type-I behavior,
as expected for a microporous compound, indicating the
retention of the microporous structure of the framework
after removal of the solvent molecules in the channels. The
BET surface area is 461 m2/g, the Langmuir surface area is
581 m2/g, and the specific micropore volume is 0.2006 cm3/
g. The hydrogen uptake of Zn4·ZnTCPEP·DABCO was
0.86wt.-% at 0.1 MPa (Figure 6). A sample evacuated at
100 °C for 24 h showed a lower hydrogen uptake of 0.52wt.-
% under the same conditions. Both the specific surface area
and the H2 uptake of Zn4·ZnTCPEP·DABCO are lower
than the corresponding values of TCPP-based microporous
MOFs.[7h] These results may indicate that the desolvation of
coordinated H2O causes partial collapse of the microporous
framework structure in Zn4·ZnTCPEP·DABCO. In fact,
Figure 5. Nitrogen adsorption isotherm at 77 K. Inset: the pore
gas adsorption measurements on Zn4(OH)2(H2O)2(py)2- diameter distribution calculated by the Saito–Foley model.
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A New Porphyrin-Based Metal Carboxylate Framework
ing to the Saito–Foley model[18] from the adsorption iso-
therms by using N2 at 77 K, showed a narrow peak at ap-
proximately 10 Å (inset of Figure 5). This pore diameter is
consistent with the pore size estimated from the crystal
structure and larger than that of the TCPP-based micro-
porous MOFs (ca. 7 Å).
(DTA) were acquired with a Rigaku Thermo Plus 2 series TG/DTA
TG 8120 instrument. Adsorption isotherm measurements were per-
formed with an automatic volumetric adsorption apparatus
(ASAP2010). The as-synthesized sample was immersed in acetone
for several days to exchange all of the included nonvolatile solvates
(DMF, H2O). The adsorbate was placed in a sample tube, which
was then evacuated by using the degas function of the analyzer at
room temp. for 24 h prior to measurement. The change in the pres-
sure was monitored, and the degree of adsorption was determined
by the decrease in pressure at the equilibrium state. The specific
surface area was obtained by the Langmuir and Brunauer–Em-
mett–Teller (BET) methods. The total pore volume was computed
from the amount of gas adsorbed at p/p0 = 0.200, and the micro-
pore volume was calculated by using the Saito–Foley model.
X-ray Crystallography: A green block crystal of [Zn4(μ3-OH)2-
(H2O)2(ZnTCPEP-H)2(DABCO)2] (0.08ϫ0.05ϫ 0.03 mm3) was
surrounded by liquid paraffin (Paratone-N) and analyzed at 90 K.
Data: orthorhombic, space group Ccca; a = 27.5447(18) Å, b =
32.731(2) Å, c = 44.208(3) Å, V = 39857(4) Å3, Z = 8, dcalcd.
=
1.637 g/cm3; μ(Mo-Kα) = 1.824 mm–1. Data collection was per-
formed with a Bruker SMART APEX CCD diffractometer at 90 K
in the range of 1.84° Ͻ 2θ Ͻ 55.00°. The intensity data were auto-
matically corrected for Lorentz and polarization effects during inte-
gration. The structure was solved by direct methods (SIR2004),[19]
followed by difference Fourier calculation and refinement by a full-
matrix least-squares procedure on F2 (program SHELXL-97).[20a]
An absorption correction was performed with the SADABS pro-
gram (empirical absorption correction).[20b] Solvent molecules in
the structure were highly disordered and impossible to refine by
using conventional discrete-atom models. To resolve these issues,
the contribution of the solvent electron density was removed by
using the SQUEEZE routine in PLATON.[16] CCDC-831533 con-
tains the supplementary crystallographic data for this paper. These
data can be obtained free of charge from The Cambridge Crystallo-
graphic Data Centre via www.ccdc.ac.uk/data_request/cif.
Figure 6. Hydrogen adsorption isotherms at 77 K.
Conclusions
In summary, we have designed a porphyrin-based build-
ing block, ZnTCPEP-H4, in which the porphyrin core, the
phenyl groups, and the carboxyl groups are almost copla-
nar, and used it to synthesize a porphyrin-based MOF,
Zn4·ZnTCPEP·DABCO. This MOF has a 3D porous struc-
ture with open channels, which have cross sections of ap-
proximately 10ϫ10 and 7ϫ7 Å. In contrast to the conven-
tional multicarboxylate meso-aryl-substituted porphyrins
such as ZnTCPP, ZnTCPEP-H4 exhibits extended π-conju-
gation from the porphyrin core to the terminal carboxyl
groups. Therefore, the Soret and Q-bands are redshifted rel-
ative to those of ZnTCPP. The pore diameter of
Zn4·ZnTCPEP·DABCO is also larger than that of the
TCPP-based MOFs due to elongation of the building
block. The strong absorption in the visible region and large
pore diameter of Zn4·ZnTCPEP·DABCO suggest its use as
a visible-light-sensitive functionalized MOF for photocatal-
ysis.
Syntheses
[5,10,15,20-tetrakis(4-Carboxymethylphenyl)ethynylporphyrinato]-
zinc(II) (ZnTCPEP-Me4): To a solution of 5,10,15,20-tetrakis-
(TIPS-ethynyl)porphyrin (4) (286 mg, 0.261 mmol) in a mixture of
CH2Cl2 (10 mL) and THF (30 mL) was added TBAF (1.57 mL,
1 m in THF). After the mixture was stirred at room temperature
for 1 h under ambient conditions, water (50 mL) was added. The
solution was concentrated under reduced pressure, filtered, and
washed with water. The obtained green solid was dried under vac-
uum to give the deprotected ethynylporphyrin. To a degassed solu-
tion of the deprotected ethynylporphyrin, methyl 4-iodobenzoate
(547 mg, 2.09 mmol), and AsPh3 (128 mg, 0.42 mmol) in a mixture
of THF (100 mL) and Et3N (10 mL) was added Pd2(dba)3 (15 mg,
0.0261 mmol). The mixture was stirred at 50 °C for 18 h. Upon
cooling to room temperature, the resultant precipitate was filtered
and washed with CH2Cl2. After drying under vacuum, ZnTCPEP-
Me4 was obtained as a purple solid (217 mg, 0.216 mmol, 82.6%
1
yield). H NMR (400 MHz, CDCl3): δ = 9.25 (s, 8 H, β), 8.17 (d,
Experimental Section
J = 8.1 Hz, 8 H, Ph-ortho), 8.02 (d, J = 8.1 Hz, 8 H, Ph-meta), 4.05
(s, 6 H, -OCH3 ) ppm. MS (MALDI-TOF+ ): calcd. for
C60H36N4O8Zn [M+] 1004.18; found 1004.11.
General Methods: 1H NMR (400 MHz) spectroscopic data were re-
corded for samples in 5 mm tubes (outer diameter) with a JEOL
JNM-EX 400 FTNMR spectrometer and a JEOL EX-400 NMR
spectroscopic data-processing system. Elemental analyses were car-
ried out with a Perkin–Elmer 2400 CHNS Elemental Analyzer II
(Kanagawa University). Infrared spectra were recorded with a Ja-
sco 4100 FTIR spectrometer by using KBr disks at room tempera-
ture. Thermogravimetric (TG) and differential thermal analyses
[5,10,15,20-tetrakis(4-Carboxyphenyl)ethynylporphyrinato]zinc(II)
(ZnTCPEP-H4): To a THF solution of ZnTCPEP-Me4 (50 mg,
0.0497 mmol, 20 mL) was added aqueous NaOH solution (2 m,
0.25 mL, 0.500 mmol). The mixture was stirred at room tempera-
ture overnight. Then aqueous HCl solution (1 m, 20 mL) was added
to neutralize the reaction mixture. The resultant precipitate was
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[4]
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filtered and washed with H2O. After drying under vacuum, the por-
phyrin complex ZnTCPEP-H4 was obtained in quantitative yield
as a greenish-purple solid. H NMR (400 MHz, CDCl3): δ = 9.37
(s, 8 H, β), 8.18 (dd, J = 20.4 and 8.18 Hz, 16 H, Ph-ortho and
-meta) ppm. MS (MALDI-TOF+): calcd. for C56H28N4O8Zn [M+]
948.12; found 947.59.
1
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(Zn4·ZnTCPEP·DABCO): A mixture of Zn(NO3)·6H2O (157 mg,
0.526 mmol), ZnTCPEP-H4 (100 mg, 0.105 mmol), and DABCO
(24 mg, 0.210 mmol) was dissolved in DMF/EtOH/H2O (70:4:1)
(75 mL) in a Teflon-lined stainless steel vessel. One drop of HCl
(1 m) was added, and the solution was heated to 80 °C for 48 h.
The resultant green block crystals were filtered, washed with DMF,
and dried under vacuum to give [Zn4(μ3-OH)2(H2O)2(ZnTCPEP-
H)2 (DABCO)2 ]·2DMF·10.5H2 O (146 mg, 99.8 % yield).
C130H115N14O32.5Zn6 (2785.84): calcd. C 56.05, H 4.16, N 7.04;
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found C 55.92, H 3.80, N 7.20. IR: ν = 1654 (s), 1601 (s), 1538 (m),
˜
1498 (w), 1386 (s) cm–1. TG/DTA under atmospheric conditions: a
weight loss of 15.7% was observed below 200 °C; calcd. 12.0% for
2DMF and 10.5H2O.
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Received: June 29, 2011
Published Online: September 8, 2011
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© 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
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