Oriented Controllable Fabrication of Metal-Organic Frameworks Membranes as Solid Catalysts for Cascade Indole Acylation-Nazarov Cyclization for Cyclopentenone[ b]indoles

Article abstract of DOI:10.1021/acs.cgd.8b01050

Creating ordered metal-organic frameworks (MOFs) membranes with a scalable fabrication for continuous and homogeneous nanoarchitecture represents a category of tunable and functionalizable heterogeneous catalysts. In this work, we demonstrate a facile synthetic strategy for controlling Cu-MOF (1) to fabricate highly oriented MOF membranes (1a) with good controllability in membranes thickness on the macroporous Ni foam as the supporting scaffold, which can promote the growth of the uniform and high-quality MOF-based membranes with the benefit of readily accessible active sites. Nanoscale crystals of 1b also can be acquired by using surfactants as templates without Ni foam as surface-supported. Furthermore, MOFs-based 1-1b have indicated to be efficient heterogeneous catalysts to promote cascade indole acylation-Nazarov cyclization for producing cyclopentenone[b]indoles skeletons. In particular, their unique membrane structure of 1a, containing ordered structure and molecular tunability, affords a well-defined platform to highly effectively facilitate cyclization reactions by enhancing the diffusional rate and permeability with the minimum diffusion distance but does little for their selectivity.

Full text of DOI:10.1021/acs.cgd.8b01050

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Article
Oriented Controllable Fabrication of Metal-Organic
Frameworks Membranes as Solid Catalysts for Cascade Indole
Acylation-Nazarov Cyclization for Cyclopentenone[b]indoles
Chao Huang, Yingying Zhang, Haiyan Yang, Dandan Wang,
Liwei Mi, Zhichao Shao, Mengjia Liu, and Hongwei Hou
Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/acs.cgd.8b01050 • Publication Date (Web): 07 Aug 2018
Downloaded from http://pubs.acs.org on August 7, 2018
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Oriented Controllable Fabrication of Metal-Organic Frameworks
Membranes as Solid Catalysts for Cascade Indole Acylation-Nazarov
Cyclization for Cyclopentenone[b]indoles
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Chao Huang,*,† Yingying Zhang,† Haiyan Yang,† Dandan Wang,† Liwei Mi,*,† Zhichao Shao,‡
Mengjia Liu‡ and Hongwei Hou*,‡
†Center for Advanced Materials Research, Zhongyuan University of Technology, Zhengzhou 450007,
P. R. China.
‡College of Chemistry and Molecular Engineering, Zhengzhou University, Zhengzhou 450001, P. R.
China.
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ABSTRACT: Creating ordered metalꢀorganic frameworks (MOFs) membranes with a scalable
fabrication for continuous and homogeneous nanoarchitecture represent a category of tunable and
functionalizable heterogeneous catalysts. In this work, we demonstrate a facile synthetic strategy for
controlling CuꢀMOF (1) to fabricate highly oriented MOF membranes (1a) with good controllability
in membranes thickness on the macroporous Ni foam as the supporting scaffold, which can promote
the growth of the uniform and highꢀquality MOFꢀbased membranes with the benefit of readily
accessible active sites. Nanoscale crystals of 1b also can be acquired by using surfactants as
templates without Ni foam as surfaceꢀsupported. Furthermore, MOFsꢀbased 1ꢀ1b have indicated to
be efficient heterogeneous catalysts to promote cascade indole acylationꢀNazarov circularization for
producing cyclopentenone[b]indoles skeletons. In particular, their unique membranes structure of 1a,
containing ordered structure and molecular tunability, afford a wellꢀdefined platform to highly
effective facilitate cyclization reactions by enhancing the diffusional rate and permeability with the
minimum diffusion distance but does little for their selectivity.
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INTRODUCTION
As the numerous heterogeneous catalysts utilized in industry, it is necessary to develop
newꢀgeneration molecular catalysts on porous carrier which are suitable for industrial engineering.1,2
Metalꢀorganic frameworks (MOFs), also called cellular materials which are made by metal
coordination nodes and organic ligands, had demonstrated a multifunctional tunable hathpace to
simulate these capabilities of natural enzymes and immobilize molecular catalysts for many
important organic transformations.3ꢀ12 Although MOFs with uniformly dispersive isolated catalytic
sites or synergistic catalysts have been examined, the catalytic property of MOFs is toujours
restricted by the diffusion distances and rates of products and substrates in the cavities (pores) of the
frameworks.13ꢀ28 To circumvent this problem and improve significantly catalytic active, it is central
to relieve the diffusional constraint by decreasing single dimension (1D) of bulk MOFs samples to
micrometer or nanometer in thickness to provide an interesting classification of highly ordered
membranes materials, MOFꢀbased membranes.29ꢀ33 Unlike threeꢀdimensional (3D) MOF crystals,
MOFꢀbased membranes have large specific surface area promoting the touch of substrates with the
readily accessible active centers on the membranes surface with minimal diffusion distance during
the catalytic processes.29,30,34ꢀ37 On the other hand, MOFꢀbased membranes inherit the high porosities,
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along with controllable channel sizes and functional active sites for maximum of the sieving effects
and to construct wellꢀdefined multiꢀactive platforms to increase the holistic penetrability of the
membrane materials but does little for their highly selectivity.29,38ꢀ39 Moreover, highly ordered
MOFꢀbased membranes catalysts can realize precise control for fundamental structureꢀproperty
investigations to simulate the active centers of numerous catalytic enzymes in nature.29,40ꢀ42 More
important, MOFꢀbased membranes also retain the heterogeneous characteristic, molecule
functionality and tunability, and ordered structure of MOF catalysts, and have the possible to precise
control of the catalytic microenvironments for the rational design and assembly of better solid
catalysts to minimize the diffusional constrains.30,39,40,43,44
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On the other side, our laboratory has paid close attention to develop MOFꢀbased heterogeneous
catalysts to execute tandem acylationꢀNazarov cyclization reactions.45ꢀ47 It belongs to a class of
acidꢀcatalyzed acylation followed by 4πꢀelectrocyclization to construct fiveꢀmembered carbocycles
for synthesizing of cyclopentenone frameworks, which are important intermediates in preparing
numerous natural products, such as roseophilin, bruceolline E, taiwaniaquinol and so on.48ꢀ51 We
recently showed that the ZnꢀMOF and AgꢀMOF had displayed to be valable solid catalysts to
facilitate cascade pyrrole dervatives cyclization reactions for producing cyclopenta[b]pyrrole
skeletons.45,46 Inspired by preliminary results, we would like to explore MOFsꢀbased catalysts for
cascade indole derivatives circularization reactions for producing cyclopentenone[b]indoles
skeletons. However, employing a series of Brønsted acids (such as TFA, HCl, or H3PO4), Lewis
acids (such as BBr3, anhydrous AlCl3, SnCl4, anhydrous FeCl3, or ZnCl2), or MOFs (AgꢀMOFs and
ZnꢀMOFs) as homogeneous or heterogeneous catalysts usually produced no products or the acylation
products with a modicum of the circularization products since indole had the lesser electron cloud
density compared with that of pyrrole.52ꢀ57 Therefore, immobilizing of the high density of Lewis
acidic active sites with continuous and ordered membranes utilizing a solid support to construct
stable MOFꢀbased membranes to simulate the complex characteristics of natural calssification for
tandem reactions, can provide an interesting approach to afford the benefit of readily accessible
active sites with minimum diffusion distance for the cascade indole circularization reaction for
producing cyclopentenone[b]indoles skeletons.
Herein, we demonstrate a strategy for the scalable fabrication of continuous and uniform
nanoarchitecture MOFꢀbased membranes on the macroporous substrate as catalysts to explore
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cascade indole acylationꢀNazarov circularization reactions. In order to acquire the benefit of readily
accessible active sites in highꢀquality membranes, we incorporate a rigid and Yꢀshaped H3CPCDC
ligand to link Cu2(COO)4 to construct a twoꢀdimension (2D) layer structure [Cu(HCPCDC)H2O]n (1)
with many large open channels. Then, highly oriented membranes (1a) with good controllability in
membranes thickness were fabricated on the macroporous Ni foam as the supporting scaffold to
facilitate their homogeneous and wellꢀdefined growth of MOFꢀbased membranes. Nanoscale samples
of 1b also can be obtained without Ni foam as surfaceꢀsupported. Furthermore, we demonstrate the
catalytic performances of MOFsꢀbased 1ꢀ1b with regard to the cyclization to prepare
cyclopentenone[b]indoles skeletons. This suggested that the catalytic performance of 1a was more
effective than that of 1 and 1b, because of the homogeneous and continuous membranes, which can
provide the tunable and functionalizable platform for the cyclization reaction by minimizing the
diffusion distance and enhancing the diffusion rate but does little for their selectivity. As far as we
know, until now, the cascade indole circularization reactions, which could be facilitated by the
MOFꢀbased membranes catalysts, have not been reported.
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EXPERIMENTAL SECTION
Materials and Physical Measurements. H3CPCDC ligand and Nꢀtosylindole were synthesized
with the procedure modified from the literature.56,58 Ni foam was treated by 2M HCl, and then dried
under vacuum oven overnight. The molarity of HNO3 was 16 mol/L. Other reagents were supplied
by business purchase and utilized without distillation. A series of characterization, including 1H
spectra, FTꢀIR spectra, Powder Xꢀray diffraction (PXRD), elemental analyses, Xꢀray photoelectron
spectroscopy (XPS), thermal analyse, scanning electron microscopy (SEM), gas sorption isotherms,
atomic absorption spectrum (AAS), inductively coupled plasmaꢀatomic emission spectrometry
(ICPꢀAES), and supercritical CO2 (SCꢀCO2) of complexes 1ꢀ1b were tested by series of instruments
(Supporting Information). In addition, general process of cascade indole circularization reactions
for 4aꢀf was provided in Supporting Information.
Synthesis of [Cu(HCPCDC)H2O]n (1). Cu(NO3)2·3H2O (0.048 g), H3CPCDC (0.037 g), 2 mL
H2O, 3 mL DMF and HNO3 (50 ꢁL) were placed inside the bottle (10 mL). The bottle was aged 4
days under 85 °C, then blue rodlike samples of 1 were procured (yield, 62% depended on Cu).
Analysis calculated (%) for C21H13CuNO7: C, 55.45 %; H, 2.88 %; N, 3.08 %. Found: C, 55.46 %; H,
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2.85 %; N, 3.10 %. IR: 3435 (vs)，2929 (vw), 1654 (w), 1607 (vs), 1511 (m), 1472 (w), 1389 (vs),
1234 (m), 1025 (vw), 920 (w), 780 (s), 724 (vw).
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Synthesis of MOFs-based membranes 1a on Ni foam. In a typical synthesis, Cu(NO3)2·3H2O
(0.048 g) and PVP (0.2 g) were mixed in 2 mL H2O and stirred for 20 min in a 10 mL vial. The Ni
foam was well immersed into the above solution and sonicated for 30 min. Subsequently, 3 mL DMF
contained 0.1 mmol of H3CPCDC (0.037 g) and HNO3 (50 ꢁL) were added and further sonicated for
1 hour. The mixture solution in the bottle was aged 4 days under 85 °C. After, the Ni foam was
extracted, lined dry by H2O and EtOH, and dried under vacuum oven overnight.
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Synthesis of Nanocrystals 1b with PVP. In a typical synthesis, Cu(NO3)2·3H2O (0.048 g) and
PVP (0.2 g) were mixed in 2 mL H2O and stirred for 20 min in a 10 mL vial until all PVP was
dissolved. Subsequently, 3 mL DMF contained 0.1 mmol of H3CPCDC (0.037 g) and HNO3 (50 ꢁL)
were added and further sonicated for 1 hour. The mixture solution in the bottle was aged 4 days
under 85 °C. After, the nanocrystals could be centrifuged at ten thousand rpm for fifteen minutes to
transfer the supernatant. The nanocrystals were achieved, and further washed by EtOH (3×5 mL)
and centrifuged at ten thousand rpm for fifteen minutes to isolate the crystal nanocrystals.
Crystal Data Collection and Refinement. 1 was carried out by the Bruker D8 VENTURE
diffractometer (λ = 0.71073 Å, MoꢀKα). The SAINT and SADABS program were used to control the
restoring data and semiempirical absorption correction.59,60 The structure of 1 was worked out and
refined by the SHELXLꢀ1997 in Supporting Information.61 The detailed crystallographic data, bond
lengths (Å), and angles (°) of 1 are afforded in Table S1 and Table S2, respectively (Supporting
Information). The corresponding CCDC number is 1821724.
RESULTS AND DISCUSSION
Crystal structure. 1 crysalizes in the orthorhombic space group Pnna, and possesses a
twoꢀdimensional framework with the dimesions of the large open channels (25.27 ×16.14 Å2)
(Figure 1a) (In view of van der Waals radii). In 1, the asymmetric unit includes one Cu2+ cations, one
HCPCDC2ꢀ ligand and one coordinated water. Cu1 cations are binded with five O atoms (O1, O2, O5,
O6, and O7) from one coordinated H2O and four HCPCDC2ꢀ ligands, respectively. Carboxylate
groups build the plates of each variety of polyhedron and water molecules locate in the axial of
acmes (Figure S1a).
In 1, the two carboxyl groups in the H3CPCDC ligands are completly deprotonated and act as a
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bismonodetate bridging linker to connect two Cu centers (Cu1 and Cu1a) with the Cu···Cu distance
of 2.61 Å. Pairs of Cu2+ ions combine four carboxyl groups to give a {Cu2(COO)4} as the secondary
building units (SBUs) (Figure S1b). Furthermore, these SBUs can be connected by carboxyl perssad
of the HCPCDC2ꢀ ligands to provide a 2D layer structure, revealing a rhombus windows and a cavity
suitable to put a sphere of 14 Å in diam (In view of van der Waals radii) (Figure S1c). Moreover, the
2D layers, stacked by π···π reciprocities with the adjacent carbazole rings (separation of 3.65 Å),
give a supermolecule with an open architecture framework (Figure 1b).
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(Figure 1 here)
Synthesis of controllable fabrication of MOFs-based membranes. Heterogeneous catalysts
generally indicate morphologyꢀdependent performaces, since the catalytic property rusts upon the
diffusion rates and permeability of substrates and products within the surface of channels. The
superiority of MOFsꢀbased membranes as catalysts is that they keep wellꢀorganized structure,
molecular controllaility and functionalization of MOFꢀbased catalysts, and hold much promise for
giving the wellꢀdefined platforms with readily accessible active sites in the membranes layer to
increase the catalytic efficiency.30,39,40,62 Therefore, Ni foam, which was low cost and hig
macroporsity, was used to develop a facile yet versatile approach, oriented surfaceꢀsupported
metalꢀorganic frameworks (SURMOFs) controllable fabrication to in situ prepare MOF membranes
with good controllability in membranes thickness (Figures 2a and 2b), because of its relatively low
cost and high macroporosity.
(Figure 2 here)
By employing polyvinylpyrrolidone (PVP) as a surfactant, continuous and stabilized MOFꢀbased
membrane (1a) formed on the Ni foam (Figures 2cꢀd and Figure S2a). From the crossꢀsection SEM
images, it can be found that the membranes of 1a were uniformly anchored onto the Ni foam, and the
membranes were well continuous growth with the thickness of approximately 500 nm (Figures 2eꢀf
and Figure S2b). Clearly, energy dispersive spectrometry (EDS) and elemental mappings of the
membranes of 1a further demonstrated the uniform and continuous distribution of the related
elements (Cu, O, N, and C) in the membrane, displaying the homogenous growth of crystalline
samples on the substrate (Figure S2c and Figure 3a). Moreover, ICPꢀAES analysis of the membranes
of 1a revealed that only copper was found in the membranes, and XPS analysis indicated that their
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observation of Cu 2p3/2 peak at 934.67 eV demonstrated the CuII ions as the unique chemical states
in 1a (Figure 3b). Moreover, PXRD study showed there were no remarkable variations among the
datas of MOFs membranes, synthesis samples and simulated, which demonstrated that the crystal
structures of the membranes and bulk samples kept unchanged (Figure S2d).
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In addition, without Ni foam as surfaceꢀsupported, the sizes of 1 (~ 0.35 × 0.26 × 0.26 mm3,
Figure S3a) can be minished to the nanometer dimension of about 300 nm in width by 1.0 ꢁm in
length at the same conditions, giving nanoscale crystals of 1b (Figures 3cꢀd and Figures S3bꢀc).
PXRD analysis revealed that the nanoscale crystals of 1b excellently matched the simulated and
synthesized PXRD patterns of bulk crystals 1 (Figure S3d), and the XPS spectrum of 1b indicated
the posotions of Cu 2p3/2 at 934.78 eV, suggesting CuII ions as the single chemical states in 1b
(Figure S3e). As the result, diverse morphologies and granular sizes of MOFs can be ascribed to the
influence of the surfaceꢀsupported. A Ni foam can be used to anchor copper cations on the
carboxylꢀgroupꢀterminated organic surface to provide a macroporous framework as the carrier to
promote the growth of a wellꢀproportioned and highꢀquality SUMOF membranes.24 In contrast, the
growth of crystalline particles can be stemed by PVP as the capping agent that can not dominate the
interactions between the MOF structure and the substrate in the absence of Ni foam.
(Figure 3 here)
Moreover, nitrogen sorption measurements of 1ꢀ1b after supercritical SCꢀCO2 activation displayed
the N2 uptake of 156, 188, and 251 cm3gꢀ1 at the saturated pressure, respectively (Figures S4aꢀc).
According to the N2 adsorption isotherm, 1ꢀ1b possess the BET specific surface area of 585, 703,
and 937 m2gꢀ1, respectively. Derived from the N2 adsorption isotherm, it clearly demonstrated that
the MOFꢀbased membranes had the large BET surface areas to afford the benefit of readily
accessible active centers for the cascade indole circularization reactions. In further studies, to study
the effect of the concentrations of surfactant upon the formation of the thickness of membranes,
many attempts for synthesizing crystalline 1a with various morphology and thickness were
conducted by using PVP with different concentrations (0.3, 0.20, 0.15, 0.10, and 0.05 g) (Figures
S4dꢀf). The results showed that wellꢀdefined morphology and thickness distributions of 1a could be
obtained when the PVP concentration of 0.2 g. Thus, this research clarifies the property to regulate
the functionalization of MOFsꢀbased membranes with the same skeleton from the large scale to the
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nanograde by developing Ni foam as surfaceꢀsupported.
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The catalytic performance of 1a. To catalyze the cascade indole circularization reactions to
prepare cyclopentenone[b]indoles skeletons, it is still a conundrum for delveloping new kinds of
catalysts for controlling the highly efficient and selective Nazarov cyclizations to facilitate the
mutiꢀsteps transformations. Encouraged by the high density of active sites in MOFsꢀbased
membranes, we were interested in probing whether an idea multiple active platform could be
afforded by MOF membranes as catalysts for cascade indole circularization reactions to produce
cyclopentenone[b]indoles skeletons as the single products.
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To convert these stoichiometric experiments for preparing cyclopentenone[b]indoles frameworks
by cascade indole circularization reactions, the solvent resistance performance of 1a in DCE was
preliminary tested by immersing the samples for 36 h in boiling DCE, because DCE was choosen as
reaction solvent for this reaction. It was found that 1a had well solvent resistance performances,
which could keep stable and remain original shapes boiling in DCE after 36 h. Besides, the
thermogravimetric analysis (TGA) data was studied by inspecting the thermal stability of 1 (Figure
S1e). Furthermore, we commenced optimization examines with Nꢀtosylindole (2), TFAA, and
crotonic acid (3a) as substrates for 3 h in different conditions (Table S3). After carefully massive
testing of menstruums and temp, the optimal status was acquired in the existence of TFAA and 20
mol % of MOF membranes of 1a in DCM at 90 ºC for 3 h, providing the desired
cyclopentenone[b]indoles frameworks (yield of 92%) via the tandem acylationꢀNazarov cyclization
process. Furthermore, attempts to substitute 1a with Ni foamed, 1, or 1b resulted in no or incomplete
conversion of Nꢀtosylindole and the cyclization product was given in yield of 0, 32 or 63%,
respectively (Table S3, entries 15, 12 and 13). Moreover, the tandem acylationꢀNazarov cyclization
proceeded in poor to moderate yield in toluene (21%), DCM (39%), and CHCl3 (17%), but MeCN,
THF, and Et2O were unsuitable solvents. For comparison, Cu(OTf)2 as homogeneous catalysts (Table
S3, entry 14), which were usually used as homogeneous catalysts for this reaction, giving a few of
cyclization products (21%). Therefore, it showed that 1a was highly efficient and selective catalyst to
execute this reaction to produce cyclization products as the only products. In consideration of
efficiency, selectivity, stability and simplicity, we identified 1a/TFAA/DCM/90 ºC as our optimal
reaction conditions for this cyclization reactions.
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(Tables 1 here)
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Subsequently, the MOFꢀbased membranes 1a catalytic methods was tested to be universal for
promoting cyclization reaction with 3aꢀf and Nꢀtosylindole (2) (Table 1). In all instances,
heterogeneous catalyst 1a possesses excellent activity to facilitate these reactions, producing 4aꢀf
with well and moderate selectivity for the cyclopentenone[b]indoles skelectons (yields, 86ꢀ92%).
Moreover, when 1 or 1b was utilized as heterogeneous catalyst, the yileds of 4aꢀf were less than that
of 1a as heterogeneous catalyst under uniform conditions, corresponding to the decrease of BTE
surface area (1 < 1b < 1a). Furthermore, using 1, 1a and 1b as catalysts, the reaction gave the
different conversion of Nꢀtosylindole (2) during the reaction processes (Figure S5), which showed
that the surface area played a vital role to infulence the diffusional rate in the reaction. To avoid the
probability of the various activities of 3aꢀf resulting in such tendency, further experiments were
implemented with the homogeneous catalysts (Cu(OTf)2, Table 1) under the same reaction
conditions. Substrates 3aꢀf under the catalysis of Cu(OTf)2 provided a few of Nazarov cyclization
products (yields, 16ꢀ21%), which do not match the decrease order of BTE surface area (1 < 1b < 1a).
Furthermore, when the reaction time was extended 10h for 3f (bulky substrate) in the existence of 1
or 1b, the productivity risen from 39 to 84% or 53 to 87%, respectively (Table 1, entries 21 and 23).
Thus, these results clearly indicated that an increase of the surface area leads to the increase in rate of
reaction but has no influence on the selectivity.
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(Figure 4 here)
The distinct and high catalytic performance of the present 1a system is attributed to spring from its
picturesque structural characteristics and membranes materials. Structural study demonstrates that 1
includes the characteristic rhombus channel with the mesh size of 25.27 ×16.14 Å2 , which can act as
a suitable space to promote the transport of organic substrates (3a: 5.80 × 3.07 Å2, 3b: 6.26 × 3.90
Å2, 3c, 6.19 × 4.09 Å2, 3d: 6.37 × 4.51 Å2, 3e: 8.75 × 3.83 Å2, 3f: 12.98 × 5.11 Å2) and products
(4aꢀf). Moreover, SEM images show that the asꢀsynthesized membranes of 1a with a thickness of
approximate 500 nm, which possess the superiority of readily accessible active centers in the
membranes to reduce the diffusion distance and enhance the products turnover and diffusion rates of
substrates. The membrane of 1a is significant and display distinct substrateꢀcatalyst interactions that
can take advantage of regulating selectivity, synergistically increase the overall permeability of the
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material to facilitate the tandem reactions and produce Nazarov cyclization products. Therefore, we
hypothesized that the membranes of 1a can steady the intermeium provided in the circularization
system and gave the tunable and functionalizable platform to execute cyclization in the large pores
and demonstrate unique selective performance (Scheme S1). To certify the hypothesis, mapping
experiments were utilized to explore the substrates and catalysts transformations. To acquire the
changes of elements in the membranes, the various reaction processes (0 h, 1.5 h and 3 h) were
elaborately regulated to research their reaction systems. The mapping images obviously display the
distribution of Cu, N, O, C and S constituents during the reaction process (Figures 4aꢀc). The source
of S element in the mapping images was ascribed to the Nꢀtosylindole (2) utilized in the cyclization
reaction. Moreover, considerable researches have been executed to explore the catalysts 1a with XPS
(Figure 4d), aiming to demonstrate their tune of catalytic microenvironments of membranes 1a in
various reaction times (0, 1.5, and 3 h). Therefore, the observation of Cu 2p3/2 peak at 934.59,
934.57, and 934.65 eV in XPS displayed that the valence state of Cu kept uniquely CuII during the
reaction processes, which invariably retained the Lewis catalytic activity to facilitate cyclization
reactions.
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In contrast, the low catalytic performance of 1 or 1b was ascribed to the particle sizes and BET
surface areas, which not only limit the overall diffusional rates and diffusion distance, but also
decrease the permeability of substrates and products transported in the channels. Therefore,
emphasizing the advantage of membranes catalysts 1a over bulk crystals 1 or nanoscale crystals 1b
as heterogeneous catalysts as diffusional constraints can be released.
The heterogeneous feature of the membranes catalyst 1a was first verified by the filtration
experiment. After 35% conversion of 2 in the presence of 1a for 1h, 1a was transfered by
centrifugation and the mixture supernatant continue to work on for 2h. The result displayed that the
conversion kept nearly unchanged in this period of time. Next, AAS analysis of the supernatant was
examined at the end of the reaction. It was found that the existence of litte filtrating of Cu (< 1 ppm)
from 1a was observed during the reaction. Thus, these consequences unambiguously revealed that 1a
was truly heterogeneous catalyst.
We have also evaluated the recyclability of heterogeneous 1a for the reaction with 2 and 3a. To
conduct the recyclability experiments, 1a was carefully collected from the mixture by centrifugation,
then the collected catalyst only slight deteriorated after ten runs (Figure S6a). Moreover, PXRD
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patterns and SEM images studies identified that the membranes catalyst 1a kept the same
morphologies and frameworks after at least ten runs, which were possibly the reasons for the distinct
catalytic performace and recyclability (Figures 6bꢀe).
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In summary, we successfully revealed a moderate and versatile preparation strategy for the
construction of SURMOFꢀderived nanoarchitecture membranes, in which the growth of
wellꢀproportioned and highꢀquality membranes can be anchored on macroporous Ni foam. The
oriented nanoarchitecture membranes on the platform were proved to be able to accelerate the coring
and the development of MOFs on the Ni foam, and importantly can regulate the continuous growth
of crystalline samples in forming the membrane. Furthermore, with the benefit of readily accessible
active centers in the MOFꢀbased membranes, the membranes of 1a as a high performance
heterogeneous catalyst to significantly outperform bulk crystals 1 or nanoscale crystals 1b to execute
circularization with indole, give the tunable and functionalizable terrace for facilitating
circularization by enhancing the diffusional rate and permeability with the minimum diffusion
distance but does little for their selectivity.
Supporting Information
The detailed crystallographic data, bond lengths, angles of 1, TGA plots, PXRD patterns for 1ꢀ1b,
details of results, and nitrogen isotherm data. These materials are available free of charge on the
website.
Corresponding Author
*Eꢀmail: houhongw@zzu.edu.cn (H. Hou).
*Eꢀmail: huangchao@zut.edu.cn (C. H)
*Eꢀmail: mlwzzu@163.com (L. M)
Notes
The authors declare no competing financial interest.
Acknowledgments
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The research was financially supported through the National Natural Science Foundation of China
(Nos. 21701201, 21601212, 21671205, 21671174, and 21371155), the Key Natural Science
Foundation of Henan Province, and the Scientific and technological project of Henan Province
(182102210528).
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Figure 1. (a) View of the 2D framework of 1 with large open channels (25.27 × 16.14 Å2) along the
b axis (considering van der Waals radii). Hydrogen atoms are omitted for clarity. (b) A spaceꢀfilling
view of the porous network along the b axis, showing the channels of 1.
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Figure 2. (a) Illustration of the synthesis process for the MOFsꢀbased membranes catalysts. (b) A
detailed SEM image of Ni form before deposition. (c, d) SEM images of MOFsꢀbased membranes 1a
on Ni foam with various magnifications. (e, f) Surface and crossꢀsection SEM images of membranes
1a on Ni foam with various magnifications.
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Figure 3. (a) Elemental mapping images of membranes 1a (b) XPS spectrum of 1a. (c, d) The
morphologies and particle sizes of 1b induced by PVP with various magnifications.
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Table 1. MOFsꢀbased 1ꢀ1b catalyzed tandem acylationꢀNazarov cyclization for the synthesis of
cyclopentenone[b]indoles.a
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α,βꢀunsaturated
carboxylic acids
Yield % of
4aꢀfb
Entry
1
Catalysts
Products
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1
92
63
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91
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88
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87
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Cu(OTf)2
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Cu(OTf)2
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1a
1b
Cu(OTf)2
1
1a
1b
Cu(OTf)2
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1
1a
55
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Cu(OTf)2
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39, 84c
86
1a
53, 87c
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1b
Cu(OTf)2
aReaction conditions: Nꢀtosylindole (1.0 mmol), α,βꢀunsaturated carboxylic acid (1.5 mmol), catalyst (0.20
mmol), TFAA (1.5 mmol), DCE (25 mL), reflux (3h). bIsolated yield of the product after 3h. cReflux (10h).
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Figure 4. (a) Elemental mapping images of 1a at the beginning (0 h). (b) Elemental mapping images
of 1a with reacting 1.5 h. (c) Elemental mapping images of 1a at the end (3 h). (d) XPS spectrum of
1a during different reaction times (0, 1.5, and 3 h).
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For Table of Contents Use Only
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Oriented Controllable Fabrication of Metal-Organic Frameworks
Membranes as Catalysts for Tandem Indole Acylation-Nazarov Cyclization
to Cyclopentenone[b]indoles
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Chao Huang,*,† Yingying Zhang,† Haiyan Yang,† Dandan Wang,† Liwei Mi,*,† Zhichao Shao,‡
Mengjia Liu‡ and Hongwei Hou*,‡
The continuous and uniform nanoarchitecture MOFꢀbased membranes (1a) as a highly efficient
heterogeneous catalyst was fabricated on porous Ni foam as the supporting scaffold to significantly
outperform bulk crystals 1 or nanoscale crystals 1b to execute tandem acylationꢀNazarov cyclization
reaction with indole and α,βꢀunsaturated carboxylic acids.
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