Tailor-Made Pyrazolide-Based Metal-Organic Frameworks for Selective Catalysis

Article abstract of DOI:10.1021/jacs.8b02710

The predesignable porous structures in metal-organic frameworks (MOFs) render them quite attractive as a host-guest platform to address a variety of important issues at the frontiers of science. In this work, a perfluorophenylene functionalized metalloporphyrinic MOF, namely, PCN-624, has been rationally designed, synthesized, and structurally characterized. PCN-624 is constructed by 12-connected [Ni₈(OH)₄(H₂O)₂Pz₁₂] (Pz = pyrazolide) nodes and fluorinated 5,10,15,20-tetrakis(2,3,5,6-tetrafluoro-4-(1H-pyrazol-4-yl)phenyl)-porphyrin (TTFPPP) linker with an ftw-a topological net. Notably, PCN-624 exhibits extinguished robustness under different conditions, including organic solvents, strong acid, and base aqueous solutions. The pore surface of PCN-624 is decorated with pendant perfluorophenylene groups. These moieties fabricate densely fluorinated nanocages resulting in the selective guest capture of the material. More importantly, PCN-624 can be employed as an efficient heterogeneous catalyst for the selective synthesis of fullerene-anthracene bisadduct. Owing to the high chemical robustness of PCN-624, it can be recycled over five times without significant loss of its catalytic activity. All of these results demonstrate that MOFs can serve as a powerful platform with great flexibility for functional design to solve various synthetic problems.

Full text of DOI:10.1021/jacs.8b02710

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Article
Tailor-Made Pyrazolide-Based Metal-
Organic Frameworks for Selective Catalysis
Ning Huang, Kecheng Wang, Hannah Drake, Peiyu Cai, Jiandong
Pang, Jialuo Li, Sai Che, Lan Huang, Qi Wang, and Hong-Cai Zhou
J. Am. Chem. Soc., Just Accepted Manuscript • DOI: 10.1021/jacs.8b02710 • Publication Date (Web): 02 May 2018
Downloaded from http://pubs.acs.org on May 3, 2018
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Tailor-Made Pyrazolide-Based Metal-Organic Frameworks for
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Ning Huang, Kecheng Wang, Hannah Drake, Peiyu Cai, Jiandong Pang, Jialuo Li, Sai Che,
§
†
†,
Lan Huang, Qi Wang, and Hong-Cai Zhou *
†
Department of Chemistry, Texas A&M University, College Station, Texas 77842-3012, United States
§
Department of Materials Science and Engineering, Texas A&M University, College Station, Texas 77843-3003, Unit-
ed States
ABSTRACT: The pre-designable porous structures in metal-organic frameworks (MOFs) render them quite attractive as a
host-guest platform to address a variety of important issues at the frontiers of science. In this work, a perfluorophenylene
functionalized metalloporphyrinic MOF, namely PCN-624, which has been rationally designed, synthesized and structur-
ally characterized. PCN-624 is constructed by 12-connected [Ni (OH) (H O) Pz ] (Pz = pyrazolide) nodes and fluorinated
8
4
2
2
12
5
,10,15,20-tetrakis(2,3,5,6-tetrafluoro-4-(1H-pyrazol-4-yl)phenyl)-porphyrin (TTFPPP) linker with an ftw-a topological net.
Notably, PCN-624 exhibits extinguished robustness in different conditions, including organic solvents, strong acid and
base aqueous solutions. The pore surface of PCN-624 is decorated with pendant perfluorophenylene groups. These moie-
ties fabricate densely fluorinated nanocages resulting in the selective guest capture of the material. More importantly,
PCN-624 can be employed as an efficient heterogeneous catalyst for the selective synthesis of fullerene-anthracene
bisadduct. Owing to the high chemical robustness of PCN-624, it can be recycled over five times without significant loss
of its catalytic activity. All of these results demonstrate that MOFs can serve as a powerful platform with great flexibility
for
functional
design
to
solve
various
synthetic
problems.
INTRODUCTION
have been designed and successfully developed, giving
rise to a series of new strategies to encapsulate macro-
molecules, such as proteins, nucleic acid, and fullerene
derivatives. In addition, it’s been reported that electron-
poor hosts tend to bind even electron-poor guests with
Metal−organic frameworks (MOFs) are a big family of
crystalline porous materials, consisting of inorganic metal
clusters and organic linkers. Owing to their designable
structures and huge potentials in many applications,
MOFs have aroused considerable interest of scientists in
1
11
the high affinity and selectivity. For example, Nitschke
2
3
and coworkers have successfully developed an electron-
various fields, such as gas adsorption, sensing, proton
II
4
5
6
deficient cubic Fe L cage, wherein the incorporation of
conduction, heterogeneous catalysis, light emitting,
8 6
7
perfluorophenylene units greatly enhanced its binding
ability to specific functionalized fullerenes. Based on Re-
and biochemical systems. In principle, MOFs are capable
of satisfying a great variety of requirements based on the
synthetic and reticular chemistry. The high tunability of
II
8
bek’s rule, the Fe L cage can selectively encapsulate C -
8
6
60
indene and C -anthracene bisadducts instead of unfunc-
surface chemistry environment and pore textural proper-
ties, such as surface area, pore size, and pore shape, ena-
bles the generation of a great many of MOFs and the abil-
ity to tailor their characteristic properties for various ap-
plications. MOFs can be predesigned to incorporate vari-
ous ligands that not only act as inert scaffolds, but also
contain functional groups that have certain interactions
with particular guest molecules. This strategy has been
successfully employed to design MOFs that can bind spe-
cific molecules and further transform the reactivity of
60
tionalized fullerenes and monoadducts. Inspired by this
work, we attempted to apply this concept to MOFs. The
great structural similarity may trigger selective binding of
fullerene derivatives in MOFs. Considering the high sta-
bility and insolubility of pyrazolide-based MOFs, it’s quite
promising to develop MOFs as recyclable heterogeneous
catalysts for the synthesis of fullerene adducts. In particu-
lar, the fluorine atom has the highest electronegativity
and exceptionally poor polarizability, polyfluorinated ma-
terials usually exhibit unique physicochemical proper-
9
these guests under certain conditions.
1
2
ties. The distinct electron deficiency of fluorinated com-
pounds endow them with specific fluorophilicity that
In supramolecular systems, the molecular recognition
through encapsulation processes is primarily determined
by the volumes of host and guest molecules. According to
Rebek’s rule, the strong binding usually occurs when the
volume ratio of guest/host molecules is in the range of
13
promotes electro-poor self-aggregation/segregation.
Fullerenes are well known as a class of carbon allo-
tropes consisting of molecules composed totally of carbon
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4
1
0
atoms in the forms of hollow spheres or ellipsoids. Due
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to their remarkable electronic properties and solution
processability, many derivatives of fullerenes have been
widely utilized in material synthesis, electronics, bio-
tive sites, it remains a big challenge to selectively synthe-
size fullerenes with a certain number of functional units.
Although several synthetic strategies have been devel-
oped to implement their functionalization, such as cyclo-
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medical systems, nanotechnologies, and solar energy
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20a
20b
conversion . However, owing to the high symmetry of its
spherical structures and the existence of multifold reac-
propanations, 1,3-dipolar cycloadditions,
and Diels-
Alder
a
Scheme 1. Synthetic routes of TTFPPP
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a
Reaction conditions: (a) i. CH Cl , CF COOH, r.t., 48 h; ii. DDQ, r.t., overnight, 22%; iii. Ni(OAc) , DMF, reflux, overnight,
2
2
3
2
8
7%. (b) Trityl chloride, Et N, CH Cl , reflux, 48 h, 82%. (c) i. Pd(PPh ) , t-BuLi, CuCl, DMF, 100 °C, 72 h, 75%. (d) i. CF COOH,
3
2
2
3 4
3
CHCl , 24 h, 56%; ii. Boc O, Et N, CH Cl , 72 h, 80%; iii. DMF, MeOH, 80 °C, 48 h, 85%.
3
2
3
2
2
20c
cycloadditions, these reactions generally produce a mix-
ture of many fullerene derivatives, which are very difficult
washed with anhydrous N,N-dimethylformamide (DMF)
three times and acetone twice.
21
to be separated from each other. In response to the chal-
lenges for selective synthesis of fullerene derivatives, we
rationally designed and synthesized a MOF, namely PCN-
Instrumentation. Powder X-ray diffraction (PXRD)
experiments were carried out on a BRUKER D -Focus
8
Bragg−Brentano X-ray powder. Diffractometer equipped
with a Cu sealed tube (λ = 1.54178 Å) at 40 kV and 40 mA.
Nuclear magnetic resonance (NMR) data were collected
on a Mercury 400 NMR spectrometer. The simulated
PXRD spectra were obtained by the diffraction-crystal
module of the Mercury program based on the single-
crystal data. The program is available free of charge via
the Internet at http:/www.iucr.org. FT-IR spectra were
recorded on an IR Affinity-1 instrument. Thermogravi-
metric analysis (TGA) data were obtained on a TGA-50
6
24, which is isostructural to PCN-602 with an ftw-a to-
22
pology (Figure 1a, b). Firstly, the incorporation of elec-
tron-deficient perfluorophenylene units into MOFs could
selectively enhance its binding ability to electron-poor
fullerenes. Secondly, unique combination of the favorable
pore size, pore shape and pore volume provides addition-
al driving force for the encapsulation of fullerene deriva-
tives in MOFs. Finally, the network of PCN-624 con-
structed by [Ni ] cluster and pyrazolide-based porphyrin
8
ligands were proven to have high chemical stability,
which endows PCN-624 with long-term recycling stability.
The feasible PCN-624 nanoreactor could realize the con-
trol over the reactivity of fullerenes and selective for-
mation of desired fullerene adducts.
(
SHIMADZU) thermogravimetric analyzer with a heating
−1
rate of 10 °C min under air atmosphere. N2 adsorp-
tion−desorption isotherms were measured using a Mi-
crometritics ASAP 2020 system at 77 K. The samples were
activated by supercritical carbon dioxide using MADRIDE
prior to gas adsorption. The UV−vis absorption spectra
were recorded on a Shimadzu UV-2450 spectrophotome-
ter with a wavelength of 350 nm. The product was identi-
fied with Shimadzu/Kratos Axima CFR MALDI-TOF PSD
instrument of moderate resolution and mass accuracy.
The conversions of the reactants and the yields of prod-
ucts were measured by Shimadzu LC-2030C system
equipped with a UV/Vis detector.
EXPERIMENTAL SECTION
Materials. The commercial chemicals are purchased
unless mentioned otherwise. 1,4-Dioxane, pyrrole, tri-
fluoroacetic acid (TFA), 2,3-dichloro-5,6-dicyano-1,4-
benzoquinone (DDQ), potassium carbonate (K CO ),
2
3
pentafluorobenzaldehyde, lithium bromide, and triphe-
nylmethyl chloride were purchased from Sigma-Aldrich
Synthesis of 5,10,15,20-tetrakis(2,3,5,6-tetrafluoro-4-
Corporation. Nickel(II) acetylacetonate (Ni(acac) ), nick-
2
(1H-pyrazol-4-yl)phenyl)-porphyrin (TTFPPP). The
el(II) acetate tetrahydrate (Ni(OAc) ), fullerene (C ), an-
2
60
synthesis route and details are described in Scheme 1 and
Supporting Information Section 2.
thracene and tetrakis(triphenylphosphine)palladium
(
Pd(PPh ) ) were purchased from Tokyo Kasai Co. (TCI).
3 4
4
-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-
Synthesis of PCN-624. Ni(AcO) ·4H O (8 mg, 32.3
2
2
pyrazole was purchased from Ark Pharm Incorporation.
The precipitate was collected by centrifugation and
mmol), TTFPPP(10 mg, 17.4 mmol), and deionized (DI)
water (1.2 mL) in 2 mL of N,N-dimethylformamide were
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mixed and ultrasonically dissolved in a 5 mL high-
tile solvates (DMF). After the removal of acetone by de-
canting, the samples were activated by drying under vac-
uum, then dried again by using the “outgas” function of
the adsorption instrument for 6 h at 100 °C prior to gas
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pressure vessel. The resulting mixture was sealed and
heated at 120 °C for 24 h. After the vial cooled down to
room temperature, purple crystalline powder of PCN-624
was collected by filtration (9 mg).
adsorption/desorption measurement. Then, their N up-
2
take was measured at 77 K.
Gas Adsorption of PCN-624. Before the gas sorption
experiment, as-synthesized PCN-624 (∼100 mg) was
washed twice with DMF and acetone once, respectively.
Fresh acetone was subsequently added, and the sample
was soaked for 24 h to exchange and remove the nonvola-
PXRD Measurement for Stability Test of PCN-624.
After being washed with DMF and acetone, as-obtained
PCN-624 sample (100 mg for each batch) were immersed
in about 10 mL aqueous
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Figure 1. (a) Assembly of O and D4h nodes into the ftw-a topological network. (b) Reticular design and construction of PCN-602
h
using [Ni ] (as [Ni ] cluster = [Ni (OH) (H O) Pz ], Pz = pyrazolide) cluster and H TPPP (H TPPP = 5,10,15,20-tetrakis(4-(1H-
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4
2
2
12
4
4
pyrazol-4-yl)-phenyl)porphyrin) ligand. (c) Synthesis of PCN-624 based on the assembly of ligand TTFPPP and nickel (II) acetate.
d) The crystal structure of PCN-624 is depicted with the space-filling view (Ni, yellow; N, blue; C, gray; O, red; F, green; H,
(
white).
solutions of HCl (1 M) aqueous solution, Na CO (3 M)
The adsorption of fullerenes was then recorded and
used to calculate the amount of fullerene derivatives
that were adsorbed by PCN-624 according to Lambert-
Beer’s Law.
2
3
aqueous solution, and K PO (3 M) aqueous solution at
3
4
room temperature for 24 h, respectively. The treated
samples were collected and washed successively with DI
water (3×5 mL) and acetone (3 ×5 mL). The obtained
powders were dried in an oven at 100 °C before PXRD
measurements.
Heterogeneous Catalysis. Anthracene (9.9 mg, 55.5
µmol) and C60 (20 mg, 27.7 µmol) were added into 5 ml
acetonitrile in a 20 mL pressure tube. PCN-624 (100 mg)
was dispersed into the mixture and heated at 50 °C for 24
N Adsorption for Stability Test of PCN-624. Five
2
batches of PCN-624 samples (about 100 mg for each) were
immersed in 10 mL of HCl (1 M), Na CO (3 M), and K PO
4
h under N atmosphere. After the completion of the reac-
2
tion, the precipitate was collected by filtration and
washed with toluene (2×5 mL) and CS (3×5 mL). The re-
maining solid was dried under vacuum and then soaked
2
3
3
(3 M) aqueous solutions at room temperature for 24 h,
respectively. After being collected and washed with DI
water (3×5 mL) and acetone (3×5 mL), the samples were
activated under vacuum at 100 °C for 10 h on ASAP 2020
system. These activated samples were then measured for
2
in a toluene/CS mixture (1:1, 3×10 mL) for 8 h. After filtra-
2
tion, the combined filtrate was collected and evaporated
the solvent under vacuum. Finally, the identities and the
yields of the products were determined by HPLC-MS with
C70 as an internal standard (detailed information is in
section 3 of Supporting Information).
N sorption at 77 K.
2
Encapsulation Studies. In a typical experiment, PCN-
624 (20 mg) was dispersed into a toluene (3 mL) solution
of different fullerene derivatives (2.0 µmol) under a nitro-
gen atmosphere in a 4 mL vial. The electronic absorption
spectra of the solution were recorded after stirring for
every 2 h and standing for 10 min at room temperature.
Recycle of Catalyst. The used PCN-624 sample was re-
covered via centrifugation, washed with toluene and CS2.
After soaking in a toluene/CS mixture (50% by volume,
2
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Journal of the American Chemical Society
×10 mL) for 8 h. The PCN-624 was dried under vacuum
Page 4 of 9
3
tetrafluorobenzaldehyde to form the fluorinated free base
porphyrin. The obtained product, was further metallized
by nickel acetate, generating the tetrakis(2,3,5,6-
tetrafluorophenyl)-porphyrin nickel 1 in a total yield of
20%. In the meanwhile, the N–H bond in 4-iodo-pyrazole
was protected with a trityl unit producing compound 2,
which was then subjected to a palladium-catalyzed direct
cross-coupling reaction with 1 to form the intermediate 3
in a 75% yield. This coupling reaction was conducted in
the presence of t-BuLi and CuCl, which enabled the syn-
thesis of 3 in high yield under mild conditions. After that,
the compound 3 was treated with trifluoroacetic acid to
remove the trityl groups, and subsequently replaced by
the tert-butyloxycarbonyl (Boc) group. Finally, the Boc
group was removed after heating in a mixture of DMF and
MeOH for 48 h, resulting in the
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at 120 °C for 5 h for the use in the next cycle.
RESULTS AND DISCUSSION
Design and Synthesis of Ligand. We started the syn-
thesis work with the electron-deficient pentafluoroben-
zaldehyde monomer which can easily be transformed to
the polydentate porphyrin ligand. The synthesis of
polyfluorinated ligands with several pyrazoles as terminal
23
groups is challenging and suffers from low yield. Here,
we report a simple reaction where the 5,10,15,20-
tetrakis(2,3,5,6-tetrafluoro-4-(1H-pyrazol-4-yl)phenyl)-
porphyrin nickel (4, TTFPPP, Scheme 1) with four per-
fluorophenylene units was synthesized from commercial-
ly available 2,3,5,6-tetrafluorobenzaldehyde and 4-iodo-
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pyrazole.
The
pyrrole
reacted
with
2,3,5,6-
Figure 2. (a) PXRD profiles of PCN-624. Experimentally observed (black curve), powder XRD patterns for PCN-602 (red curve),
simulated XRD patterns for PCN-624 (blue curve), and their difference (green curve). (b) Nitrogen-sorption isotherm curves for
PCN-624 at 77 K. (c) Pore size distribution profile for PCN-624. (d) PXRD patterns of PCN-624 after treatment for 12 h in differ-
ent solvents. (e) Residue weight percentage of PCN-624 after treatment for 24 h in different solvents. (f) Nitrogen-sorption iso-
therm curves of PCN-624 after treatment for 24 h in different solvents, including pristine sample (black curve), after treatment
in water (red curve), ethanol (blue curve), 1M HCl aqueous solution (green curve), 3M Na CO aqueous solution (brown curve),
2
3
and
3M
K PO
aqueous
solution
(purple
curve).
3
4
final product 4. Matrix-assisted laser desorp-
tion/ionization time-of-flight spectrometry (MALDI-TOF)
was employed to determine the molecular weights of in-
termedia compound and TTFPPP (Figures S1-S7, see Sup-
porting Information).
5,10,15,20-tetrakis(2,3,5,6-tetrafluoro-4-(1H-pyrazol-4-
yl)phenyl)-porphyrin (TTFPPP) as linkers (Figure 1). The
reaction was conducted under solvothermal conditions in
DMF at 120 °C for 24 h. The PCN-624 was obtained as a
purple crystalline powder in a yield of 74% and character-
ized by various methods. FT-IR spectrum displayed that
PCN-624 exhibited a stretching vibration band at 1622
Synthesis and Characterization of PCN-624. We
constructed the PCN-624 using [Ni ] cluster as knots and
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Journal of the American Chemical Society
−
1
−1
cm that was assigned to the C=N bond (Figure S8).
Thermal gravimetric analysis demonstrated that PCN-624
273 K and 1.73 mmol g at 298 K (Figure S10). The isoster-
1
2
3
4
5
6
7
8
9
ic heat of adsorption (Q ) for CO adsorption was calcu-
lated as high as 34.6 kJ mol (Figure S11). It can be at-
tributed to the high electronegativity of fluorine atoms,
st
2
−
1
was stable up to 400 °C under N (Figure S9). Powder X-
2
ray diffraction (PXRD) measurement revealed that PCN-
624 adopted an ftw-a topology, which is consistent with
that of PCN-602 and simulated results (Figures 2a and
Table S1). Each face of the cubic cages in PCN-624 was
consisted of a fluorinated porphyrin ligand (Figure 1c, d).
The average Ni−Ni distance between opposite faces is 19.8
which mostly promote CO adsorption through electro-
2
static interactions. The N adsorption capacity of PCN-
2
−
1
−1
624 was 0.27 mmol g and 0.13 mmol g at 273 K and 298
K, respectively (Figure S12). Using pure-component iso-
therm fits, we evaluated the CO /N selectivity based on
2
2
3
Å, and the inner void volume was 3332 Å . The window
size in the resulting framework is about 6.6 × 14.5 Å ,
the ideal absorbed solution theory (IAST). The IAST se-
lectivity was calculated as 39.7 at 1 bar (Figure S13).
2
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2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
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1
2
3
4
5
6
7
8
9
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1
2
3
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9
0
which is large enough for some bulky substrates to diffuse
inside this framework. To evaluate the porosity of PCN-
Chemical Stability. Owing to the strong coordination
bond between Ni and the pyrazolide groups, and the
2+
6
24, we performed N sorption measurement at 77 K.
2
high connectivity number of [Ni ] clusters, PCN-624 was
8
3
−1
PCN-624 exhibited N2 uptakes of 678 cm
g
at 1
expected to possess excellent chemical stability. To inves-
tigate its chemical stability, we dispersed PCN-624 sam-
ples in different solutions, including water, ethanol, HCl
(1M), Na CO (2M), and K PO (2M) aqueous solutions.
atm(Figure 2b), and the experimental Brunau-
er−Emmett−Teller (BET) surface area is calculated as high
2
−1
as 2010 m g . The pore size distribution calculated by
using the nonlocal density functional theory (NLDFT)
method resulted in a pore size of 1.9 nm (Figure 2c),
2
3
3
4
After soaking in these solutions for 24 h, the PXRD pat-
terns of these treated PCN-624 samples are almost un-
which is close to the theoretical value. Interestingly, PCN-
changed,
which
suggests
the
−1
6
24 also exhibited high CO capacities of 3.10 mmol g at
2
Figure 3. Schematic diagram of the encapsulation of C An into PCN-624, forming a host-guest system C An ⊂PCN-624.
60
2
60
2
maintenance of its crystallinity (Figure 2d). As shown in
Figure 2e, the residue weight percentage of the PCN-624
samples remained very high (>96%) in these harsh condi-
tions. In water and ethanol, PCN-624 exhibited almost
no weight loss (<5wt%). Under the ultra-harsh conditions
of aqueous acid (1M HCl) and base (2M Na CO ) solu-
the broadest pH range among previously reported por-
phyrinic MOFs despite its extremely large linker. Even
PCN-624 samples were soaked in pH harsh conditions for
four weeks, they still remained high crystallinity and po-
rosity (Figures S15−S17). This pyrazolide-based MOF with
elongated linkers successfully realizes the combination of
large porosity and extraordinary chemical stability, which
would be of great potential for application in nanoscale
chemistry.
2
3
tions, the residual weight percentages were 94 wt% and
5wt%, respectively. To further confirm the PCN-624
9
networks were intact, we conducted N sorption meas-
2
urements for these samples after different treatments. N2
Encapsulation Studies. Among the various fullerene
derivatives, their bisadducts as electron acceptors have
shown outstanding photo conversion efficiency, especially
in the field of organic solar cells. For example, the indene-
C60 bisadduct (ICBA) has been widely employed as a typi-
cal kind of high-performance acceptor material in poly-
sorption isotherms of these treated PCN-624 have mini-
mal deviations from the one of the pristine sample (Fig-
ure 2f and Figure S14). Moreover, PCN-624 displays much
higher chemical stability than its counterpart PCN-602 in
acidic aqueous solution, which might be attributed to the
high hydrophobicity of its fluorinated cages. To the best
of our knowledge, PCN-624 exhibits the high stability in
24
mer solar cells. However, the mono-, bis- and tris- C -
60
adducts are always obtained as a mixture during synthesis
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Journal of the American Chemical Society
Page 6 of 9
and have to be separated by tedious column chromatog-
promising as a catalytic nanoreactor for the efficient syn-
thesis of C An bisadduct.
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
raphy. Therefore, it is of great significance to develop an
efficient approach to synthesize and separate desired bis-
C -adducts from their mixtures. The PCN-624 network
60
2
60
Table 1. Catalytic Performance of PCN-624 for Selec-
contains cubic cages with highly electron-deficient sur-
a
3
tive Catalysis of Fullerene-Anthracene bisadduct
face, which has an inner void volume of 3243 Å (Figure
S18). According to Rebek’s rule, these cages could selec-
tively encapsulate guest molecules with volumes around
3
1783 Å . Compared with other fullerene adducts, the C –
60
3
anthracene bisadduct (C An ) with a volume of 1802 Å
60
2
was calculated as the optimum guest molecule among
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
60
numerous derivatives (Table S2). The ellipsoidal C An2
molecule has a minor diameter of 6.4 Å and a major di-
25
2
ameter of 1.1 nm. The window size (6.6×14.5 Å ) of PCN-
24 is large enough to accommodate the entry and exit of
C An . Based on the electron-deficient nanopores, we
6
Entry
1
Catalyst
Solvent Ratio
t (h)
12
Yield (%)
60
2
No cata-
lyst
b
d
e
f
utilized PCN-624 to trap C An by dispersing the crystal-
toluene
1:6
23 /19 /3
60
2
line powder into the toluene solution at 50 °C.
No cata-
lyst
2
CH CN
1:6
12
<1
The capture process of C An was monitored closely by
3
60
2
electronic absorption spectra (Figures S19 and S20). Time-
dependent spectral change demonstrates that the maxi-
mum absorption band at 323 nm decreased with the pas-
sage of time. After 36 h, the residual C An concentration
3
4
5
6
7
8
9
PCN-624
PCN-624
PCN-624
PCN-624
PCN-624
PCN-624
PCN-602
toluene
toluene
1:6
1:6
1:6
1:6
1:6
1:10
12
16
12
25/20/3
24/21/3
43
CH CN
3
60
2
−
1
in the solution was lower than 0.1 mmol L . This result
suggests that over 86% of C An was captured by PCN-
CH CN
16
24
12
40
3
60
2
CH CN
38
3
6
24. As control experiments, the adsorption of C60 mon-
c
CH CN
52
3
omer and C -anthracene monoadduct (C An) was con-
60
60
CH CN
1:10
1:10
24
24
<1
3
ducted under the same conditions. However, no evidence
of the encapsulation of C60 and C An was observed from
10
PCN-602 toluene
25/20/3
60
a
the UV spectra because the volume of C60 and C An is
60
Determined by HPLC with C70 as an internal standard.
Reaction conditions: anthracene (7.2 mg, 40.2 mmol), fuller-
b
not high enough to occupy the void optimally. In addition,
the additional PXRD patterns of C An ⊂PCN-624 also
ene (4.8 mg, 6.7 mmol), PCN-624 (10 mg), and acetonitrile
(10 mL) at 50 °C. Reaction conditions: anthracene (12 mg,
67.4 mmol), fullerene (4.8 mg, 6.7 mmol), PCN-624 (10 mg),
and acetonitrile (10 mL) at 50 °C. The yield for C60An. The
60
2
c
indicate the encapsulation of C An in the framework
60
2
(
Figure S21). Meanwhile, the fluorine-free PCN-602 was
d
e
also employed as a host material for the capture of C An ,
60
2
f
yield for C An . The yield for C An .
yet very low encapsulation levels were detected (Figures
S22). Therefore, the combination of suitable void volume
and electron-deficient inner surface in PCN-624 required
60
2
60
3
In order to optimize the synthetic conditions, we at-
tempted to investigate the effects of a range of factors,
including solvents, substrate ratios and reaction time
(Table 1). The yield of all the products was determined by
standard working methods (Figures S24− S39). And all the
products were analyzed by elemental analysis (Table S3).
Without any catalyst in toluene, the reaction between C60
to achieve the efficient capture of C An .
60
2
Selective Synthesis of C An . Encouraged by the ex-
60
2
cellent C An capture performance of PCN-624, we fur-
60
2
ther attempted to employ this network as a nanoreactor
to selectively synthesize C An other than other products
60
2
(
Figure 3). The Diels−Alder reaction between C60 and an-
thracene was conducted in acetonitrile in the presence of
PCN-624. Both of C60 and anthracene alone cannot form
any host−guest inclusion with PCN-624, which can be
attributed to the poor solubility of C60 and anthracene in
acetonitrile. In addition, control experiments between
C60 and anthracene without PCN-624 or in the presence
of the fluorine-free PCN-602 in acetonitrile at 50 °C can-
not produce the C -anthracene adducts. Interestingly,
and anthracene generated a mixture of C60An, C60An
trisadduct C60An in the yields of 23%, 19%, and 3%, re-
and
2
3
spectively (Table 1, entry 1). However, very little product
was detected in acetonitrile owing to the poor solubility
of both substrates (Table 1, entry 2). In the presence of
PCN-624 in toluene, the Diels−Alder reaction still pro-
duced a mixture of three adducts with similar yields after
12 h and 16 h (Table 1, entries 3 and 4), suggesting that the
introduction of PCN-624 made no difference in the ho-
mogeneous reactions. Interestingly, when we conducted
the reaction in acetonitrile with PCN-624 after 12 h, only
bisadduct C60An
5). We ascribed this result to the remarkable capture abil-
ity of PCN-624 toward the bisadduct C60An , which sup-
plies sustained chemical driving force in the heterogene-
60
when we added PCN-624, fullerene, and anthracene in
acetonitrile and heated the mixture at 50 °C for 12 h, and
then filtered and soaked the residual PCN-624 in toluene,
high-performance liquid chromatography-mass spec-
was formed in 43% yield (Table 1, entry
2
trometry (HPLC-MS) measurement revealed the C An2
60
bisadduct was generated as the only product (Figures S23).
All of these results indicated that PCN-624 might be
2
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Journal of the American Chemical Society
ous catalysis process. When the reaction time was pro-
lent chemical stability in both acid and base conditions.
In addition, the electron-deficient nature together with
the optimal pore size and pore volume supply a strong
driving force to selectively bind particular fullerene deriv-
atives. This unveiled a new efficient method for the puri-
fication and the selective synthesis of fullerene adducts
with rationally designed MOFs. Considering the availabil-
ity of various linkers with different sizes and electronic
properties, the creation of electron-deficient interfaces
provides a new chemical platform for structural and func-
tional designs. Therefore, these advancements open new
perspectives in the design of MOFs with specific func-
tionalities for the sustainable production of fine chemi-
cals.
1
2
3
4
5
6
7
8
9
longed to 16 h and 24 h, slightly lower yields of 40% and
38% were obtained owing to the retro-Diels−Alder reac-
tion (Table 1, entries 6 and 7). The highest yield of 52%
was obtained by increasing the ratio of C60 and anthra-
cene after 12 h (Table 1, entry 8). As control experiments,
the non-fluorinated PCN-602 was employed in acetoni-
trile and toluene, while no obvious catalytic effect was
observed (Table 1, entries 9 and 10). Therefore, PCN-624
appears to enable the Diels−Alder reaction between an-
thracene and C60 to selectively generate the bisadduct,
whereas the substrates would not ordinarily react at all
under the same conditions. We infer that the inner nano-
environment of PCN-624 favors the formation of the la-
bile C An product, generated in a thermodynamically
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
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2
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3
3
3
3
3
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4
4
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4
4
4
5
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5
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5
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6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
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9
0
1
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9
0
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0
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3
4
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7
8
9
0
60
2
ASSOCIATED CONTENT
controlled reaction between C60 and anthracene.
Supporting Information. Chemicals and instrumentation,
full details for sample preparation, characterization results,
additional PXRD patterns, and TGA. This material is availa-
ble free of charge via the Internet at http://pubs.acs.org.
Recyclability of PCN-624. Cycling performance of
heterogeneous catalysts is crucial for practical applica-
tions. Interestingly, the PCN-624 can be easily separated
and recovered from the reaction mixture through filtra-
tion and washing with solvents for next cycles. The regen-
erated PCN-624 can be subjected to the next round cata-
lytic synthesis of C An bisadduct. After five cycles, the
AUTHOR INFORMATION
Corresponding Author
60
2
PCN-624 network still retained its crystallinity and poros-
ity, which were confirmed by its PXRD patterns and N2
sorption isotherms at 77 K (Figures S40−S42). In addition,
in the presence of the recycled PCN-624, the yield of the
C An almost has no difference with that of the original
zhou@chem.tamu.edu
Author Contributions
N.H. and K.W. contributed equally.
Notes
The authors declare no competing financial interest.
60
2
cycle (Figure S43). All of the results demonstrated that
PCN-624 could well maintain its high catalytic activity
and selectivity.
ACKNOWLEDGMENTS
This work was supported as a part of the Center for Gas Sep-
arations Relevant to Clean Energy Technologies, an Energy
Frontier Research Center (EFRC) funded by the U.S. De-
partment of Energy (DOE), Office of Science, and Office of
Basic Energy Sciences under Award Number DE-SC0001015.
It was funded in part by the Advanced Research Projects
Agency−Energy (ARPA-E), U.S. Department of Energy, under
Award Number DE-AR0000249. We gratefully acknowledge
the Robert A. Welch Foundation (A-1725) for support of this
work. Use of the Advanced Photon Source, an Office of Sci-
ence User Facility operated for the U.S. Department of Ener-
gy (DOE) Office of Science by Argonne National Laboratory,
was supported by the U.S. DOE under Contract No. DE-
AC02-06CH11357.
In addition, the light-harvesting nature of porphyrins
made them quite promising for photocatalytic applica-
tions. In nature, one of the well-known porphyrin assem-
blies is the antenna complex in the photosynthetic light-
harvesting system. To realize artificial photosynthesis,
MOFs are one kind of ideal scaffolds to assemble different
functional molecules. There have been many examples of
MOFs for light harvesting and photocatalytic CO reduc-
2
24
tion and hydrogen evolution. As in most catalytic sys-
tems, heterogeneous photocatalysts are easily separated
from the reaction mixtures for recycling use. However, it
remains a challenge to develop highly stable MOFs in
most catalytic reactions. Combining the intrinsic light-
harvesting properties of porphyrins and the extraordinary
stability, PCN-624 is one of the best choices for practical
photocatalytic applications on account of its ability to be
recovered and reused. In the future work, we will further
explore the light-harvesting and photocatalytic perfor-
mance of the pyrazolide-based MOFs, especially in CO2
reduction, proton reduction, and organic transformations.
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(
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