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ChemComm
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DOI: 10.1039/C5CC09814A
COMMUNICATION
Journal Name
benzimidazole compounds (Table 2).13 We have carried out
reaction of o-phenylenediamine with different p-substituted
benzaldehyde (X= H, NO2, Cl, CH3 and OCH3) at room
temperature.14 The quantitative analysis of product conversion
is monitored by GC-MS analyser at regular intervals of times.
The conversion of products with benzaldehyde (X= H) is 62%
after 3 h, after 6 h the product conversion is increased to 97%,
suggesting that the conversion is almost complete within 6 h
(for X= H). We did not find any detectable amount of the
desired benzimidazole product through GC-MS data analysis
when homogeneous CuII catalyst, dehydrated cupric acetate
was used as a catalyst under similar conditions as employed
‡ The CCDC number of AMOF-1 is 1431244.
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for CuII@AMOF-1'
.
This reflects the heterogeneous
CuII@AMOF-1' is a superior catalyst than the homogeneous
CuII catalyst.14 We have carried out reaction of o-
phenylenediamine and benzaldehyde in the presence of only
AMOF-1', which shows no conversion of product even after 12
hours. This suggests that AMOF-1' could not act as a catalyst.
The pristine solvated CuII@AMOF-1' also does not show any
catalytic activity as the coordinated water molecules inhibits
any Lewis acid catalytic activity.14 In another reaction using
CuII@AMOF-1' catalyst, we have removed the catalyst after a
time period of 3 h by filtration and the reaction mixture was
further stirred for additional 3 h. After 6 h, there was no
increase in the yield (62%), suggesting that CuII sites indeed act
as the catalytic sites. ICP analysis of the filtrate obtained after
removing the solid catalyst from the reaction mixture shows
no detectable CuII ions suggesting that no leaching of CuII ions
occurs during the catalysis. This result indicates that the
AMOF-1' stabilizes Lewis acidic CuII sites on the pore surface.
Furthermore, experiments were performed with various
aromatic aldehydes having different substituents with reaction
time of 6 h (Table 2). Although the conversion of the products
are significant for X= H, NO2 and Cl, the yield is significantly
reduced for X= CH3 and OCH3 group (the purity of the products
Yang, Z. Wang, B. Chen and G. Qian, Nat Chem, 2013, 4:
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1
is verified through the H NMR measurements of the pure
compounds14). This suggests that an electron withdrawing
group at para position of aldehyde enhance electrophilic
nature of the carbonyl carbon thereby increasing its reactivity,
while electron donating methoxy and methyl groups exhibit
lesser yield (Table 2). The recyclability experiment14 was
studied with benzaldehyde (X = H), which suggest that the
solid catalyst could be reused for at least 3 cycles.
,
,
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In conclusion, we have developed a new porous AMOF that
allows easy access of desired exogeneous cations and offers a
unique way to post-synthetically modify the AMOF. The AMOF
effectively capture toxic metal ions from their aqueous
solutions. The CuII exchanged AMOF shows good catalytic
activity towards the synthesis of benzimidazole derivatives at
room temperature. Such PSMet in water stable AMOFs will
ensue a new route to capture toxic metal ions from industrial
waste water. Suitable AMOF would also act as the platform to
immobilize different cationic groups to obtain versatile
targeted functions.
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14 See ESI.
Notes and references
4 | J. Name., 2012, 00, 1-3
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