Formation of a metalloporphyrin-based nanoreactor by postsynthetic metal-ion exchange of a polyhedral-cage containing a metal-metalloporphyrin framework

Article abstract of DOI:10.1002/chem.201204358

A change for the better: Exchange of Cd^II in the catalytically inactive framework MMPF-5 (see scheme) with Co^II afforded a metalloporphyrin-based nanoreactor, MMPF-5(Co). This framework, consisting of small cubicuboctahedral cages, d

Full text of DOI:10.1002/chem.201204358

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DOI: 10.1002/chem.201204358
Formation of a Metalloporphyrin-Based Nanoreactor by Postsynthetic
Metal–Ion Exchange of a Polyhedral-Cage Containing a Metal–
Metalloporphyrin Framework
Xi-Sen Wang,[a] Matthew Chrzanowski,[a] Lukasz Wojtas,[a] Yu-Sheng Chen,[b] and
Shengqian Ma*[a]
Metal–organic frameworks (MOFs),[1] which are typically
comprised of metal ions or metal clusters (also known as
secondary building units, SBUs) that are linked by multitop-
ic organic ligands into two-or three-dimensional networks,[2]
have been a significant topic of research in recent decade. A
major driving force behind their rapid development lies in
their amenability to design: a desired structure can thus be
targeted by judicious selection of the organic linker and the
SBU.[3] Furthermore, their modular nature means that the
properties (for example, pore size and surface area) of pro-
totypal MOFs can be tuned by custom-designing the func-
tional organic ligands under the concept of “reticular syn-
thesis”.[4] Such features not only make them stand out over
traditional porous materials in terms of potential applica-
tions for gas storage/separation,[5] but also offer them an op-
portunity to be developed as a new type of heterogeneous
catalysts.[6]
In the context of developing MOFs for catalysis applica-
tion, current efforts have been mainly dedicated to three as-
pects, namely the utilization of their pore systems to encap-
sulate catalytically active guest species,[6a,7] post-synthetic
modification to graft catalytically active moieties,[8] and
direct incorporation of active centers into the frame-
works.[6,9] An appealing approach to achieve highly efficient
MOF-based catalytic systems is decorating vertexes, and/or
edges, and/or faces of polyhedral cages in MOFs[10] with cat-
alytically active centers to afford MOF-based nanoreactors.
This kind of nanoreactor features a high density of active
sites within the confined nanospace, which could lead to co-
operative interactions between the active sites and sub-
strates, thus resulting in high catalytic activities.[11] To create
polyhedral cage-containing MOFs as nanoreactors, catalyti-
cally active metallo-ligands[12] can be employed as linkers
that could reside on the vertexes, or edges or faces of the
polyhedron. In this regard, metalloporphyrin ligands[13]
which can be readily custom-designed to meet the geometry
requirements for the formation of polyhedral cages,[14] are
most promising. The porphyrin macrocycles of custom-de-
signed porphyrin ligands could be pre-metalated[15] or meta-
lated in situ[11,16] with active metal centers to afford metallo-
porphyrin-based nanoreactors. However, the premetalation
approach usually requires tedious synthetic procedures,
whereas the approach of metalation in situ inevitably leads
to the same metal centers in both the porphyrin rings and
SBUs, thus making the systems complicated for study.
Herein, we report a facile route to create a metalloporphyr-
in-based nanoreactor by post-synthetic metal-ion exchange
with active metal cations of a catalytically inactive metal-
metalloporphyrin framework (MMPF) that consists of nano-
scopic polyhedral cages. The local coordination environment
of the active metal center within the porphyrin macrocycle
after metal-ion exchange was crystallographically identified,
and the resulted metalloporphyrin-based nanoreactor was
proved to be catalytically active and demonstrated interest-
ing performance in catalytic epoxidation of trans-stilbene.
Using a crystal engineering strategy of vertex-directed
self-assembly, we recently constructed a porphyrin-based
MOF, MMPF-5, that is based upon small cubicuboctahedral
cages.[17] Each small cubicuboctahedral cage is composed of
the faces of six CdII-metalated tetrakis(3,5-dicarboxyphe-
nyl)porphine (tdcpp(Cd)) moieties that are linked by eight
triangular CdACTHUNTRGNE(UNG CO2)3 moieties and that exhibits window di-
mensions of 8.004 ꢀ ꢁ 8.574 ꢀ and internal cage diameter
of 22.521 ꢀ (atom to atom distance) (Figure 1a). In the
crystal structure of MMPF-5, it is observed that the CdII
cation residing within the porphyrin ring of the tdcpp ligand
lies far out of the porphyrin plane: DCb, the average devia-
tion of b-carbon atoms from the porphyrin plane, is 0.86 ꢀ,
[a] Dr. X.-S. Wang, M. Chrzanowski, Dr. L. Wojtas, Prof. Dr. S. Ma
Department of Chemistry, University of South Florida
4202 E. Fowler Avenue, Tampa, FL 33620 (USA)
Fax : (+1)813-974-3203
ꢀ
and the Cd N bond distances are 2.327(3) ꢀ (Figure 1b).
This indicates weak bonding of CdII cation within the por-
phyrin macrocycle and prompted us to exchange the large
CdII cation with smaller divalent metal cations.[18]
E-mail: sqma@usf.edu
[b] Dr. Y.-S. Chen
ChemMatCARS, Center for Advanced Radiation Sources
The University of Chicago, 9700 S. Cass Avenue
Argonne, IL 60439 (USA)
Immersing the crystals of MMPF-5 in the DMSO solution
of CoACHTNUGRTNEUNG
(NO3)2 at 858C for two days afforded the CoII-ex-
Supporting information for this article is available on the WWW
under http://dx.doi.org/10.1002/chem.201204358.
changed MMPF-5 (hereafter denoted MMPF-5(Co)). UV/
Chem. Eur. J. 2013, 19, 3297 – 3301
ꢂ 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
3297

Table 1. Crystal data and structure refinements of MMPF-5 and MMPF-
5(Co).
MMPF-5[b]
MMPF-5(Co)[c]
formula
Fw
C156H60Cd11N12O51
4154.56
C156H60Cd8Co3N12O54
4042.15
l [ꢀ]
1.54178
0.41328
crystal system
space group
a [ꢀ]
b [ꢀ]
c [ꢀ]
cubic
Pm3m
22.521(15)
22.521(15)
22.521(15)
90.00
cubic
Pm3m
22.260(11)
22.260(11)
22.260(11)
90.00
¯
¯
a [8]
b [8]
90.00
90.00
g [8]
90.00
11423(13)
1
0.10ꢁ0.10ꢁ0.10
1.037
0.0816, 0.2483
90.00
11029(9)
1
0.11ꢁ0.11ꢁ0.11
1.006
0.1087, 0.2524
Figure 1. a) Representation of the crystal structure of the small cubicu-
boctahedron in MMPF-5 formed by 6 square tdcpp(Cd) moieties and 8
triangular CdACHTUNGTRENNUNG(CO2)3 moieties. Internal diameter 22.521 ꢀ, window di-
mensions 8.004 ꢀ ꢁ 8.574 ꢀ. b) The metalloporphyrin macrocycle in
MMPF-5, showing that the CdII cation lies far out of the porphyrin plane
with DCb =0.86 ꢀ.
V [ꢀ3]
Z
crystal size [mm]
GOF
R1, wR2
[a]
2
2
[a] R1 =Sj jFo jꢀjFc j j/SjFo j and wR2 ={[Sw
G
ACHTUNGTRENNUNG .
(Fo )2]}C1/2
[b] CCDC 862932. [c] CCDC 895641.
Figure 3. a) The metalloporphyrin macrocycle in MMPF-5(Co), showing
that CoII cation is located within the plane of the porphyrin with DCb =0.
b) The small cubicuboctahedron in MMPF-5(Co) formed by 6 square
Figure 2. Solution-state UV/Vis spectra of MMPF-5(Co), MMPF-5, and
MMPF-2[16e] digested by hydrochloric acid in water.
tdcpp(Co) moieties and 8 triangular CdACTHNUTRGNEUNG(CO2)3 moieties. Internal diame-
ter 22.260 ꢀ, window dimensions 7.929 ꢀ ꢁ 8.440 ꢀ.
Vis spectroscopy studies (Figure 2) on the hydrochloric acid
digested samples in water revealed that the Soret band at
435 nm and Q band[19] at 645 nm for MMPF-5 shifted to
430 nm and 540 nm, respectively, for MMPF-5(Co), which is
consistent with the Soret band and Q band for MMPF-2
as the nodes in the framework remain intact, which is possi-
bly due to their strong chelation with six oxygen atoms from
three carboxylate groups. Therefore the small cubicubocta-
hedral cage in MMPF-5(Co) features the faces of six CoII-
metalated tdcpp moieties that are linked by eight triangular
that is based upon tdcppACHTNUTGRNEUNG
(CoII).[16e] These results therefore in-
dicated the successful and complete exchange of CdII cations
with CoII cations within the porphyrin rings of tdcpp ligands.
MMPF-5 retained its single-crystalline nature after metal-
ion exchange with CoII. Single-crystal X-ray crystallographic
studies conducted using synchrotron radiation at the Ad-
vanced Photon Source, Argonne National Laboratory re-
vealed that MMPF-5(Co) also crystallized in the space
CdACHTNGUTERNUN(G CO2)3 moieties with an internal diameter of 22.260 ꢀ
and window dimensions of 7.929 ꢀ ꢁ 8.440 ꢀ (atom-to-atom
distance) (Figure 3b). The exclusive substitution of CdII cati-
ons within the porphyrin rings of tdcpp ligands by CoII cati-
ons was further confirmed by inductively coupled plasma
mass spectrometry (ICP-MS) studies, which revealed a Cd/
Co ratio of 2.69:1 consistent with the stoichoimetric ratio of
2.67:1 derived from crystal data. These results thus distin-
guished MMPF-5(Co) from other post-synthetic metal-ion
exchange behavior in MOFs in which the metal cations in
the SBUs[20] or in both metalloligands and SBUs[21] are in-
volved in the exchange processes. MMPF-5(Co) is also a
rare example of a structure of metal-ion exchanged crystal
that has been determined by single crystal X-ray diffraction
¯
group Pm3m with a=22.260(11) ꢀ, which is in good agree-
ment with the unit cell parameters of MMPF-5 (Table 1). In
the crystal structure of MMPF-5(Co), all of the CdII cations
within the porphyrin macrocycles of tdcpp ligands are re-
placed by CoII cations, and the CoII cations are located
ꢀ
within the porphyrin plane with DCb =0 and Co N=
2.028(3) ꢀ (Figure 3a). Interestingly, the CdII cations serving
3298
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Chem. Eur. J. 2013, 19, 3297 – 3301

Metalloporphyrin-Based Nanoreactors
COMMUNICATION
analysis.[20a,21b] The retention of framework integrity and
phase purity for bulk MMPF-5(Co) was confirmed by
powder X-ray diffraction studies (Supporting Information,
Figure S1). MMPF-5(Co) also preserved its permanent po-
rosity, as seen by CO2 adsorption isotherms at 273 K, which
revealed a NLDFT (non-local density functional theory)[22]
surface area of about 600 m2gꢀ1. (Supporting Information,
Figure S2). The decrease in surface area compared to pris-
tine MMPF-5 (ca. 740 m2gꢀ1) could be presumably to be due
to partial decomposition during either metal-ion exchange
process or activation procedure.
Table 2. Summary of catalytic data for epoxidation of trans-stilbene cata-
lyzed by MMPF-5(Co) and related catalysts.[a]
Catalyst
Conversion [%]
Epoxide [%]
MMPF-5(Co)
tdcmpp(Co)[b]
MMPF-5
87.0
28.1
9.2
9.0
9.1
81.5
64.4
55.1
55.8
55.9
80.2
blank
filtrate[c]
MMPF-5(Co)[d]
80.1
[a] trans-Stilbene (1 mmol), tBuOOH (3.0 mmol), catalyst (0.001 mmol),
acetonitrile (5.0 mL) were stirred at 608C for 24 h. [b] 0.003 mmol cata-
lyst. [c] After catalytic assay for MMPF-5(Co). [d] The fifth cycle.
To show that MMPF-5(Co) is catalytically active, we eval-
uated the performance of MMPF-5(Co) as metalloporphyr-
in-based nanoreactor in the context of epoxidation of trans-
stilbene.[23] Catalytic assays for the epoxidation of trans-stil-
bene were carried out using tert-butyl hydroperoxide as oxi-
dant in acetonitrile at 608C. Control experiments were con-
ducted for MMPF-5, homogeneous cobalt(II) metalated tet-
rakis(3,5-dicarboxymethylesterphenyl)porphine (tdcmpp(Co)),
and a blank under the same conditions. As revealed in
Figure 4 and Table 1, MMPF-5(Co) showed much more effi-
cient catalytic activity for epoxidation of trans-stilbene in
trans-stilbene under similar conditions,[11] thus highlighting
the high efficiency of metalloporphyrin-based nanoractor in
MMPF-5(Co). No detectable leaching of the active site or
cobalt metal in the reaction solution was observed after re-
moval of MMPF-5(Co) by filtration, as shown by the fact
that the filtrate exhibited virtually the same activity (9.1%
yield, 55.9% epoxide) as the blank (Table 2). MMPF-5(Co)
could be reused for five cycles without significant drop in its
catalytic activity (Table 2; Supporting Information, Fig-
ure S3), and its structure remained intact after catalysis as
evidenced by PXRD studies (Supporting Information, Fig-
ure S1).
It should be noted that several factors, such as amount of
catalyst, oxidant, solvent, reaction temperature, and time,
can profoundly influence performance (for example, conver-
sion, epoxide selectivity) in catalytic epoxidation of trans-
stilbene.[25] We are currently studying these factors in the
context of MMPF-5(Co) and are also investigating epoxida-
tion of different olefin substrates of various molecular sizes
and shapes to assess whether or not size- and shape-selectiv-
ity can be effected. Additionally, we noticed that CoII-based
metalloporphyrins have recently been widely investigated as
homogeneous catalysts[26] for reactions of cyclopropana-
[28]
tion,[27] C H amination,
and aziridination of alkenes;[29]
ꢀ
the exploration MMPF-5(Co) as metalloporphyrin-based
nanoreactor for these types of reactions is underway as well.
These studies will be reported separately in the near future.
Apart from post-synthetic metal-ion exchange with CoII
for MMPF-5, our preliminary results indicated that MMPF-
5 can also be exchanged with CuII, MnIII, NiII, and ZnII (Sup-
porting Information, Figure S4). Results along this line will
be reported as a full article in due course.
Figure 4. Kinetic traces of of trans-stilbene epoxidation catalyzed by
MMPF-5(Co) and MMPF-5 (mol ratio of trans-stilbene/tBuOOH/cata-
lyst=1000:3000:1 was used for the catalytic assays), tdcmpp(Co) (ratio
trans-stilbene/tBuOOH/catalyst=1000:3000:1), and the blank.
terms of both yield (87.0% over 24 h) and selectivity
(81.5% epoxide product) compared to MMPF-5 (9.2%
yield, 55.1% epoxide), which is basically as inactive as the
blank (9.0% yield, 55.8% epoxide). The low activity
(28.1% yield, 64.4% epoxide; Table 2) observed for homo-
geneous tdcmpp(Co) could be attributed to catalyst deacti-
vation as a result of the oxo-bridged dimer formation,[24]
which on the other hand indicates the stabilization of active
CoII center within porphyrin ring through the MOF frame-
work. MMPF-5(Co) also outperformed 3D channeled
MMPF-2[16e] (67.2% yield, 58.0% epoxide) and 2D layered
PPF-1Co[16c] (23.7% yield, 30.1% epoxide) in epoxidation of
In summary, a metalloporphyrin-based nanoreactor was
created in MMPF-5(Co) by post-synthetic metal-ion ex-
change with CoII cations for the catalytically inactive CdII-
based MMPF-5 that consists of small cubicuboctahedral
cages. The structure of MMPF-5(Co) was determined by
single-crystal X-ray diffraction analysis, which together with
UV/Vis and ICP-MS studies confirmed the successful and
complete replacement of CdII by CoII occurring exclusively
within the porpyrin macrocycles. MMPF-5(Co) preserved
permanent microporosity and demonstrated interesting per-
formances in catalytic epoxidation of trans-stilbene. The
facile and exclusively exchange of metal ions within por-
Chem. Eur. J. 2013, 19, 3297 – 3301
ꢂ 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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an easy and versatile route to create porphyrin-based MOFs
of different active centers with the same framework struc-
ture for heterogeneous catalysis.
Experimental Section
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Preparation of MMPF-5(Co): MMPF-5(Co) was obtained by placing
crystals of MMPF-5, which were synthesized according to the procedures
in Ref. [17], into
ACHTUNGTRENNUNG
a dimethylsulfoxide (DMSO) solution of Co-
(NO3)2·6H2O (20 mgmLꢀ1), followed by heating at 858C for 48 h. The
crystals were washed with DMSO and methanol several times to afford
pure MMPF-5(Co).
Full experimental details, PXRD patterns, gas sorption isotherms, and
UV/Vis spectra are presented in the Supporting Information.
CCDC 862932 (MMPF-5) and CCDC 895641 (MMPF-5(Co)) contain the
supplementary crystallographic data for this paper. These data can be ob-
tained free of charge from The Cambridge Crystallographic Data Centre
via www.ccdc.cam.ac.uk/data_request/cif.
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Acknowledgements
S. Ma acknowledges the University of South Florida for financial support
of this work. The crystal diffraction of MMPF-5(Co) was carried out at
the Advanced Photon Source on beamline 15ID-B of ChemMatCARS
Sector 15, which is principally supported by the National Science Foun-
dation / Department of Energy under grant number NSF/CHE-0822838.
Use of the Advanced Photon Source was supported by the U. S. Depart-
ment of Energy, Office of Science, Office of Basic Energy Sciences,
under Contract No. DE-AC02–06CH11357.
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Keywords: catalysis
frameworks · metalloporphyrins · nanoreactors
·
ion exchange
·
metal–organic
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Published online: February 5, 2013
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