Expansion of Pore Windows and Interior Spaces of Microporous Porphyrin-based Metal

Carboxylate Frameworks: Synthesis and Crystal Structure of [Cu

2
(ZnBDCBPP)]
Satoshi Matsunaga,* Shigeki Kato, Nanako Endo, and Wasuke Mori*
Department of Chemistry, Faculty of Science, Kanagawa University, Hiratsuka, Kanagawa 259-1293
(Received December 4, 2012; CL-121205; E-mail: matsunaga@kanagawa-u.ac.jp, wmori@kanagawa-u.ac.jp)
We successfully synthesized a novel porphyrin-based
metal carboxylate framework, [Cu
2
(ZnBDCBPP)]5DMF
5H
2
O, with expanded pore windows and interior spaces,
by using a ZnBDCBPP building block. Single-crystal X-ray
analysis revealed that the framework of [Cu
2
(ZnBDCBPP)]
formed a three-dimensional network. The cavity was surrounded
by a total of 16 accessible metal sites with two distinct metals,
and large pore windows were present. These large pore windows
appear to be crucial for an enhanced catalytic performance
because they facilitate the diusion of substrates and products.
Porous metalorganic frameworks (MOFs) have attracted
considerable attention owing to their potential applications in
various elds such as gas storage,
1
gas separation,
2
ion
exchange,
3
and catalysis.
4,5a5d
The incorporation of accessible
metal sites (AMSs) into porous MOFs is important because the
resulting AMS-incorporated MOFs exhibit enhanced gas-ad-
sorption capacities and can be applied to specic catalysis.
6
One
approach to the incorporation of AMSs into MOFs is the use of
AMS-containing building blocks. In this approach, the rational
design of a framework structure is possible through comparison
with the method of formation of AMSs at structural nodes in the
self-assembly process. In addition, because molecules that are
already known to be eective homogeneous catalysts can be
used as building blocks, this approach is useful for the molecular
design of heterogeneous catalytically active MOFs. The use
of AMS-containing building blocks such as metallosalens,
7
N-heterocyclic carbene (NHC) complexes,
8
and metalloporphy-
rins
5a,5e,5f,9
has been reported in many studies.
Metalloporphyrins, in particular, can be found throughout
nature, and they exhibit unique catalytic, electronic, and optical
properties.
10
When metalloporphyrins are used as building
blocks for MOFs, the facile molecular modication of porphy-
rins expands the possibilities of structural design. Because most
of the elements in the periodic table can be inserted into
porphyrins,
10
it is possible to introduce various AMSs into the
pore surface of MOFs without alteration of the framework
topology. In addition, the physical and chemical properties of
metalloporphyrins can be controlled through appropriate func-
tionalization of the porphyrin core using standard modications.
The use of metalloporphyrins as MOF building blocks oers the
potential to tailor the photochemical and redox properties of the
frameworks. Therefore, metalloporphyrins are one of the best
building blocks for the incorporation of AMSs into MOFs.
We have previously reported the synthesis of porphyrin-
based MOFs in which 5,15-bis(dicarboxyphenyl)porphyrin
(BDCPP: Figure 1, left) was linked via a paddle-wheel Cu
2
unit to form [Cu
2
(MBDCPP)] (M= Zn
2+
, Ni
2+
, Pd
2+
,
Mn
3+
(NO
3
), or Ru
2+
(CO)), and have described their crystal
structures and N
2
/H
2
adsorption properties.
5f
These MOFs
exhibited permanent porosity and had an interior space that was
surrounded by two distinct types of AMSs: the metal centers of
the porphyrin moieties and the axial sites of the paddle-wheel
Cu
2
units. In addition, we were able to incorporate various
AMSs (Zn
2+
, Ni
2+
, Pd
2+
, Mn
3+
, or Ru
2+
) into the framework
without altering the structure. Although the BDCPP-based
MOFs contained large interior spaces (ca. 20 in diameter),
the pore window was too small to allow the access of bulky
guest molecules. The small pore window negatively aected the
performance of the catalysts by slowing down substrate and
product diusion through the window, and only small substrates
could be used for catalytic reactions.
To address this issue, we designed an elongated but
geometrically equivalent BDCPP analogue, i.e., 5,15-bis(dicar-
boxybiphenyl)porphyrin (BDCBPP: Figure 1, right), in which
the two 3,5-dicarboxybiphenyl groups are attached to the
porphyrin core via a phenylene group. We report the construc-
tion of a novel porphyrin-based metal carboxylate framework,
[Cu
2
(ZnBDCBPP)]5DMF5H
2
O, with expanded pore win-
dows and interior spaces, achieved through the use of a
ZnBDCBPP building block, and discuss its synthesis, crystal
structure, and gas-adsorption properties.
The synthetic routes to ZnBDCBPP are shown in Scheme 1.
5-Aminoisophthalic acid (1) was iodized by using Sandmeyer
conditions followed by isobutyl esterication to yield
5-iodoisophthalic acid isobutyl ester (2). The porphyrin pre-
cursor aldehyde 3 was synthesized via the SuzukiMiyaura
coupling of 2 with 4-formylphenylboronic acid. The synthesis
of free-base porphyrin tetraisobutyl ester, H
2
BDiBuCBPP, was
achieved through a standard Lindsey method by condensing
17.8 26.2
BDCPP BDCBPP
Figure 1. BDCPP and BDCBPP ligands.
Published on the web March 2, 2013 298
doi:10.1246/cl.2013.298
2013 The Chemical Society of Japan Chem. Lett. 2013, 42, 298300 www.csj.jp/journals/chem-lett/
dipyromethane with aldehyde 3 in CHCl
3
in the presence of
BF
3
OEt
2
as a catalyst.
11
The free-base porphyrin H
2
BDi-
BuCBPP was metalated with Zn(OAc)
2
2H
2
O to provide the
zinc porphyrin tetraisobutyl ester ZnBDiBuCBPP. Basic hydrol-
ysis of the tetraester ZnBDiBuCBPP gave the tetracarboxylic
acid building block ZnBDCBPP. In the steps of the condensation
and metalation reactions, the isobutyl esters were used to
improve the yield and solubility in organic solvents.
5f
The
reaction of ZnBDCBPP with Cu(NO
3
)
2
3H
2
O in DMF/H
2
O
at 60 C for 24 h gave the BDCBPP-based porous complex
[Cu
2
(ZnBDCBPP)]. Large, high-quality crystals of [Cu
2
-
(ZnBDCBPP)] suitable for single-crystal X-ray diraction were
obtained from a mixture of [Cu
2
(ZnBDCBPP)] and Cu(NO
3
)
2

3H
2
O in DMF/H
2
O that was left undisturbed at room temper-
ature for one month. Thermogravimetric analysis (TGA,
Figure S1)
15
of [Cu
2
(ZnBDCBPP)] under atmospheric condi-
tions revealed a weight loss of 30.18% at temperatures of less
than 275 C (calculated 31.76% for a total of ve DMF and ve
water molecules), and the weight loss due to the decomposition
of the framework was observed at approximately 280 C. The
formula for this BDCBPP-based porous complex was deter-
mined on the basis of TGA to be [Cu
2
(ZnBDCBPP)]5DMF
5H
2
O. The composition of this complex was also conrmed by
elemental analysis (see Supporting Information).
15
Single-crystal X-ray analysis revealed that [Cu
2
-
(ZnBDCBPP)] crystallizes in the tetragonal P42/mnm space
group.
12
The carboxylate groups of the ZnBDCBPP building
block form four dierent Cu
2
paddle-wheel units, and the axial
positions of the Cu
2
paddle-wheel units are occupied by
coordinated water molecules (Figure 2). If the paddle-wheel
units are considered to be four-connecting nodes and the two
carboxybiphenyl groups of the ZnBDCBPP ligand are consid-
ered to be three-connecting nodes, the overall structure of
[Cu
2
(ZnBDCBPP)] is three-dimensional and can be symbolized
as a net with (6
2
8
2
10
2
)(6
2
8)
2
, as calculated using the TOPOS
software package. This topological net is recognized as net
sqc3895 (EPINET database).
13
The three-dimensional structure
of [Cu
2
(ZnBDCBPP)] is very similar to that of the BDCPP-
based MOF reported previously
5f
and may also be regarded as
an assembly of cage structures that consist of eight ZnBDCBPP
building blocks and eight Cu
2
paddle-wheel units (Figure 3).
This cage has an ellipsoidal cavity elongated along the c axis
because the ZnBDCBPP building block exhibits a unidirection-
ally elongated molecular structure. The ellipsoidal cage in
[Cu
2
(ZnBDCBPP)] is elongated with a diameter of 19.7 along
the a and b axes (minor axes), which is similar to the elongation
in [Cu
2
(ZnBDCPP)] but with a diameter along the c axis (major
axis) of 27.2 . The void volume, which was calculated from the
single-crystal structures using PLATON/VOID,
14
is 57.4% and
is larger than that of the DDCPP-based MOF (53.5%).
Compared with [Cu
2
(ZnBDCPP)], [Cu
2
(ZnBDCBPP)] contains
larger pore windows when viewed along the a and b axes
because of the elongated molecular size and the dierent
orientation of the BDCBPP units. These large pore windows
appear to be crucial for achieving an enhanced catalytic
performance owing to their facilitation of the diusion of
substrates and products. In fact, unlike [Cu
2
(ZnBDCPP)], the
TGA of the [Cu
2
(ZnBDCBPP)] sample after treatment with THF
showed no weight loss corresponding to the loss of DMF
molecules (Figure S2).
15
This result indicates that the guest
DMF molecules in the cavity can be removed because of the
large pore window, and the elongation of the pore windows can
facilitate the diusion of the guest molecules in the cavity.
To conrm the structural stability of [Cu
2
(ZnBDCBPP)],
we performed X-ray powder diraction studies (PXRD,
N
N N
N
Zn
OH
O
O
OH
OH
O
O
HO
NH
2
OH
O
O
OH
I
O
i
Bu
O
O
i
Bu
O
O
i
Bu
O
O
i
Bu
O
CHO
N
N N
N
Zn
O
i
Bu
O
O
O
i
Bu
O
i
Bu
O
O
i
BuO
N
NH N
HN
O
i
Bu
O
O
O
i
Bu
O
i
Bu
O
O
1) NaNO
2
, HCl / H
2
O
2) KI
3) H
2
SO
4
/
i
BuOH
4-Formylbenzeneboronic acid,
[PdCl
2
(PPh
3
)
2
], K
2
CO
3
/ DMF, H
2
O
1) dipyrrolemethane,
BF
3
OEt
2
/ CHCl
3
2) DDQ, Et
3
N
Zn(OAc)
2
2H
2
O
/ CHCl
3
1) NaOH
/ THF, H
2
O
2) 1M HCl
aq
.
1 2 3
H
2
BD
i
BuCBPP ZnBD
i
BuCBPP ZnBDCBPP
ZnBDCBPP
Cu(NO
3
)
2
3H
2
O
/DMF, H
2
O, HCl
[Cu
2
(ZnBDCBPP)]5DMF5H
2
O
i
BuO
Scheme 1.
19.7
27.2
8.1
(a) (b)
C
N
O
Cu
Zn
Figure 2. (a) ZnBDCBPP moiety of [Cu
2
(ZnBDCBPP)];
(b) cage consisting of eight ZnBDCBPP ligands and eight
paddle-wheel Cu
2
nodes. H atoms are omitted for clarity.
c
a
Figure 3. Extended structure of [Cu
2
(ZnBDCBPP)] viewed
along the crystallographic b axis.
299
2013 The Chemical Society of Japan Chem. Lett. 2013, 42, 298300 www.csj.jp/journals/chem-lett/
Figure S3).
15
The PXRD pattern matched the simulated pattern
based on single-crystal diraction; however, the peaks in the
pattern appeared to be slightly broadened and weakened. This
broadening and weakening suggested that when the sample of
[Cu
2
(ZnBDCBPP)] was removed from the solution, the micro-
porous framework structure gradually collapsed owing to the
desolvation of guest DMF or H
2
O molecules.
Nitrogen gas-adsorption measurements were performed on
[Cu
2
(ZnBDCBPP)] at 77 K (Figure S4).
15
The sample was
immersed in THF for several days to allow exchange of the
included nonvolatile solvates (i.e., DMF and H
2
O), and the
sample was subsequently dried under vacuum at room temper-
ature for 24 h. A limited amount of N
2
(3 cm
3
g
1
) was adsorbed
at ca. 760 mmHg (the BET surface area was 3.90 m
2
g
1
, and the
Langmuir surface area was 5.81 m
2
g
1
). The void volume
calculated from the N
2
isotherm was 0.00170 cm
3
g
1
and
0.127% at a relative pressure of 0.200, which is signicantly
smaller than that calculated from the single-crystal structures
using PLATON/VOID (57.4%). These facts suggest that N
2
molecules may be adsorbed only on the external surface of
[Cu
2
(ZnBDCBPP)] because of the collapse of the microporous
framework structure.
The PXRD and N
2
adsorption measurements indicated that
the microporous framework structure of [Cu
2
(ZnBDCBPP)] was
unstable with respect to the removal of the guest molecules in
the cavity. This structural weakness of the [Cu
2
(ZnBDCBPP)]
framework may be related to the elongation of the ZnBDCBPP
building block. Therefore, the BDCBPP-based framework of
[Cu
2
(ZnBDCBPP)] may not be suitable for gas-phase heteroge-
neous catalysis. However, the persistence of permanent porosity
after solvent evacuation is not required for a heterogeneous
catalyst in a solution;
7b
therefore, the interior space that is
surrounded by two distinct types of AMSs and the large pore
windows are useful for solution-based heterogeneous catalysis
applications.
In conclusion, we have succeeded in the construction of a
novel porphyrin-based metal carboxylate framework, [Cu
2
-
(ZnBDCBPP)]5DMF5H
2
O, with expanded interior spaces
and pore windows, by using a ZnBDCBPP building block. The
complex has a three-dimensional porous structure with an
internal ellipsoidal cavity, which is surrounded by a total of 16
AMSs of two types. This porous complex is isostructural with
previously reported BDCPP-based frameworks; it therefore has
the potential for systematic incorporation of a wide variety of
AMSs into the framework without alteration of the framework
topology. Compared with BDCPP-based frameworks, [Cu
2
-
(ZnBDCBPP)]5DMF5H
2
O contains large pore windows,
which appear to be crucial for achieving an enhanced catalytic
performance because they facilitate the diusion of substrates
and products. We are currently working on the synthesis of
BDCBPP-based MOFs containing other metals, and eorts are
underway to evaluate the catalytic activities of these MOFs.
This work was supported by the Ministry of Education,
Culture, Sports, Science and Technology, Japan, through a
Grant-in-Aid for Young Scientists (B) No. 24750138. The
authors would like to thank Enago (www.enago.jp) for the
English language review.
References and Notes
1 a) W. Mori, F. Inoue, K. Yoshida, H. Nakayama, S. Takamizawa,
M. Kishita, Chem. Lett. 1997, 1219. b) H. Li, M. Eddaoudi, T. L.
Groy, O. M. Yaghi, J. Am. Chem. Soc. 1998, 120, 8571. c) K. Seki,
S. Takamizawa, W. Mori, Chem. Lett. 2001, 122. d) M. Kondo, T.
Yoshitomi, H. Matsuzaka, S. Kitagawa, K. Seki, Angew. Chem.,
Int. Ed. Engl. 1997, 36, 1725. e) J. L. C. Rowsell, O. M. Yaghi,
Angew. Chem., Int. Ed. 2005, 44, 4670. f) S. Kitagawa, R. Kitaura,
S.-i. Noro, Angew. Chem., Int. Ed. 2004, 43, 2334.
2 J.-R. Li, R. J. Kuppler, H.-C. Zhou, Chem. Soc. Rev. 2009, 38,
1477.
3 K. S. Min, M. P. Suh, J. Am. Chem. Soc. 2000, 122, 6834.
4 a) M. Fujita, Y. J. Kwon, S. Washizu, K. Ogura, J. Am. Chem. Soc.
1994, 116, 1151. b) S. Naito, T. Tanibe, E. Saito, T. Miyao, W.
Mori, Chem. Lett. 2001, 1178. c) C.-D. Wu, A. Hu, L. Zhang, W.
Lin, J. Am. Chem. Soc. 2005, 127, 8940.
5 a) T. Sato, W. Mori, C. N. Kato, E. Yanaoka, T. Kuribayashi, R.
Ohtera, Y. Shiraishi, J. Catal. 2005, 232, 186. b) W. Mori, T. Sato,
T. Ohmura, C. N. Kato, T. Takei, J. Solid State Chem. 2005, 178,
2555. c) W. Mori, T. Sato, C. N. Kato, T. Takei, T. Ohmura, Chem.
Rec. 2005, 5, 336. d) W. Mori, S. Takamizawa, C. N. Kato, T.
Ohmura, T. Sato, Microporous Mesoporous Mater. 2004, 73, 31.
e) S. Matsunaga, N. Endo, W. Mori, Eur. J. Inorg. Chem. 2011,
4550. f) S. Matsunaga, N. Endo, W. Mori, Eur. J. Inorg. Chem.
2012, 4885.
6 M. Dinc, J. R. Long, Angew. Chem., Int. Ed. 2008, 47, 6766.
7 a) R. Kitaura, G. Onoyama, H. Sakamoto, R. Matsuda, S.-i. Noro,
S. Kitagawa, Angew. Chem., Int. Ed. 2004, 43, 2684. b) F. Song,
C. Wang, J. M. Falkowski, L. Ma, W. Lin, J. Am. Chem. Soc.
2010, 132, 15390.
8 K. Oisaki, Q. Li, H. Furukawa, A. U. Czaja, O. M. Yaghi, J. Am.
Chem. Soc. 2010, 132, 9262.
9 a) M. E. Kosal, J.-H. Chou, S. R. Wilson, K. S. Suslick, Nat.
Mater. 2002, 1, 118. b) D. W. Smithenry, S. R. Wilson, K. S.
Suslick, Inorg. Chem. 2003, 42, 7719. c) T. Ohmura, A. Usuki, K.
Fukumori, T. Ohta, M. Ito, K. Tatsumi, Inorg. Chem. 2006, 45,
7988. d) A. M. Shultz, O. K. Farha, J. T. Hupp, S. T. Nguyen, J.
Am. Chem. Soc. 2009, 131, 4204. e) I. Goldberg, CrystEngComm
2008, 10, 637. f) E.-Y. Choi, C. A. Wray, C. Hu, W. Choe,
CrystEngComm 2009, 11, 553. g) B. J. Burnett, P. M. Barron, C.
Hu, W. Choe, J. Am. Chem. Soc. 2011, 133, 9984. h) O. K. Farha,
A. M. Shultz, A. A. Sarjeant, S. T. Nguyen, J. T. Hupp, J. Am.
Chem. Soc. 2011, 133, 5652. i) X.-S. Wang, L. Meng, Q. Cheng,
C. Kim, L. Wojtas, M. Chrzanowski, Y.-S. Chen, X. P. Zhang, S.
Ma, J. Am. Chem. Soc. 2011, 133, 16322.
10 The Porphyrin Handbook, ed. by K. M. Kadish, K. M. Smith, R.
Guilard, Academic Press, San Diego, CA, 2000.
11 J. S. Lindsey, R. W. Wagner, J. Org. Chem. 1989, 54, 828.
12 A deep-purple plate crystal of [Cu
2
(ZnBDCBPP)] (0.15
0.15 0.01 mm
3
) was surrounded with liquid paran (Paratone-
N) and analyzed at 90(2) K. Data: tetragonal, space group P42/
mnm; a = 18.5837(7) , c = 53.135(3) , V = 18350.5(14)
3
,
Z = 8, d
calcd
= 0.747 g cm
3
; (Mo K) = 0.751 mm
1
. Solvent
molecules in the structure were highly disordered and impossible
to rene using conventional discrete-atom models. To resolve
these issues, the contribution of the solvent electron density was
removed using the SQUEEZE routine in PLATON. CCDC-
910789 contains the supplementary crystallographic data for this
paper. These data can be obtained free of charge from The
Cambridge Crystallographic Data Centre via http://www.ccdc.
cam.ac.uk/data_request/cif.
13 S. Ramsden, V. Robins, S. T. Hyde, S. Hungerford, EPINET:
Euclidean Patterns in Non-Euclidean Tilings, 2006, http://epinet.
anu.edu.au.
14 A. L. Spek, J. Appl. Crystallogr. 2003, 36, 7.
15 Supporting Information is available electronically on the CSJ-
Journal Web site, http://www.csj.jp/journals/chem-lett/index.html.
300
2013 The Chemical Society of Japan Chem. Lett. 2013, 42, 298300 www.csj.jp/journals/chem-lett/