II
III
Synthesis and Catalytic Application of Mixed Valence Iron (Fe /Fe )-Based…
The organic phase was evaporated under reduced pressure
and the reaction mixture was then subjected to column chro-
matography (n-hexane:ethyl acetate=4:1, V/V) to give the
corresponding aza-Michael products. All products and char-
2.3.6 Butyl 3-(phenylamino)propanoate: Viscous Liquid
1
H NMR (300.13 MHz, CDCl ): δ=1.24–1.29 (t, J=7.2 Hz,
3
3H), 1.61–2.18 (t, J=7.2 Hz, 2H), 3.42–3.47 (t, J=6.3 Hz,
1
acterized by comparison of their physical properties, H and
2H), 4.09–4.21 (m, 2H), 6.54–7.13 (m, Ar, 5H), 7.27 (s, 1H).
1
3
13
C spectra with those of already reported [17, 39, 40].
C NMR (75.46 MHz, CDCl ): δ=14.17, 35.74, 37.8,
3
6
1.33, 114.82, 117.65, 120.78, 121.92, 135.18, 142.80, 171.01.
2.3.1 Methyl-3-(phenylamino)propanoate: Viscous Liquid
3
Result and Discussion
1
H NMR (300.13 MHz, CDCl ): δ=2.63–2.67 (t, J=6.4 Hz,
3
2
H), 3.46–3.5 (t, J = 6.4 Hz, 2H), 3.72 (s, 3H), 6.64–7.27
In spite of more attention of MOFs, the design of MOFs con-
taining unsaturated metal center has also been use to prepare
materials with improved adsorption capacity for gas-storage
and catalysis application [41–46]. The as-synthesized crys-
talline 3D MIL-100(Fe), with contained terminal molecules
(
m, Ar 5H).
1
3
C NMR (75.46 MHz, CDCl ): δ=33.67, 39.47, 76.64,
3
7
7.06, 77.48, 113.14, 117.85, 129.33, 147.44, 172.84.
−
−
2
.3.2 Ethyl-3-(phenylamino)propanoate: Viscous Liquid
such as F , H O and OH anions in Fe(III) octahedral, can
2
II
III
created open metal site of mixed valence iron (i.e. Fe /Fe )
OMS-MOF via departure of terminal anion ligand or water
molecules under vacuum and thermal activation between
150 and 250 °C [38]. Among the catalytic system by MOFs,
MIL-100(Fe) family by cubic and octahedral morphology
have been employed [47, 48]. In our hydrothermal method,
1
H NMR (300.13 MHz, CDCl ): δ=1.27–1.30 (t, J=7.2 Hz,
3
2
H), 2.60–2.65 (t, J=6.3 Hz, 2H), 3.45–3.49 (t, J=6.3 Hz,
2
H), 4.13–4.20 (q, J=6.9 Hz, 2H), 5.82 (s, 3H), 6.64–7.22
(
m, Ar, 5H).
1
3
C NMR (75.46 MHz, CDCl ): δ=14.18, 34.04, 39.46,
3
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III
6
0.65, 76.60, 77.02, 113.09, 117.74, 129.31, 147.56, 172.48.
the open metal site Fe /Fe -MOF was prepared with polyg-
onal morphology using Fe-dust as Fe-source (Fig. 1).
FT-IR spectra of MIL-100(Fe) showed in Fig. 2. The
2
.3.3 Ethyl 3-((4-methoxyphenyl)amino)propanoate:
−
1
broad band between 3100 and 3434 cm is associated to
Viscous Liquid
the ν
stretching vibrations, originating from the water
O−H]
[
molecules coordination with open metal site center in the
1
H NMR (300.13 MHz, CDCl ): δ=1.27–1.32 (t, J=7.2 Hz,
3
structure MIL-100(Fe). The significant changes of stretch-
2
H), 2.65–2.69 (t, J=6.9 Hz, 2H), 3.41–3.45 (t, J=6.3 Hz,
ing vibration from C=O of H BTC acid ligand from 1716
3
2
H), 3.81 (s, 3H), 4.16–4.20 (q, J=7.2 Hz, 2H), 6.74–7.27
−
1
to 1632 cm indicating that C=O carboxyl from BTC have
been deprotonated then coordinated with iron ions to form
MOF. The characteristic absorption peaks of the MIL-
(
m, Ar, 5H).
1
3
C NMR (75.46 MHz, CDCl ): δ=14.10, 35.73, 37.88,
3
5
2
5.81, 61.35, 113.7, 115.10, 139.55, 152.75, 171.24.
−
1
1
00(Fe) sample presented at 1632, 1445 and 1374 cm
−
1
were ν
stretching vibration. 1568 cm , which could
C−O]
[
.3.4 3,3′-(Phenylazanediyl)dipropanenitrile: Viscous
mainly originate from the C=C of aromatic groups vibra-
Liquid
−
1
tions and 762 and 712 cm were fingerprints assigned to
ν
stretching vibration of benzene ring, respectively.
1
[C−H]
H NMR (300.13 MHz, CDCl ): δ=2.62–2.66 (t, J=6.3 Hz,
3
−1
Besides that, the vibration characteristics of 479 cm may
be assigned as Fe–O stretching vibration in which the oxy-
gen atom coordinated with Fe ions [49, 50].
2
H), 2.78–2.82 (t, J=6.9 Hz, 2H), 3.53–3.58 (t, J=6.9 Hz,
2
7
H), 3.71–3.75 (t, J=6.3 Hz, 2H), 6.96–7.33 (m, Ar, 5H).
1
3
C NMR (75.46 MHz, CDCl ): δ=16.91, 18.84, 76.69,
3
The crystallinity and purity of synthesis sample were
checked by powder X-ray diffraction (PXRD) measurement
7.54, 114.33, 117.74, 122.39, 128.94, 130.80, 142.09.
(
Fig. 3). The result demonstrate that the peak positions
2
.3.5 3-((3-chlorophenyl)amino)propanenitrile: Viscous
matched well with that of the simulated diffraction pattern
of MIL-100(Fe) in the range of 3–30 degree, which indicate
that the crystalline state of the sample was consistent with
open metal site MOF of MIL-100(Fe) [51]. The porosity
properties of the OMS-MIL-101(Fe) were determined by
nitrogen adsorption–desorption isotherm after heating under
vacuum at 150 °C for 4 h. The BET surface area for the
Liquid
1
H NMR (300.13 MHz, CDCl ): δ=2.63–2.67 (t, J=6.3 Hz,
3
2
H), 3.72–3.76 (t, J=6.3 Hz, 2H), 6.49–6.72 (q, J=6.3 Hz,
2
7
H), 6.74 (s, 3H), 7.08–7.14 (t, J=6.3 Hz, 2H), 7.27 (s, 1H).
1
3
C NMR (75.46 MHz, CDCl ): δ=19.39, 39.54, 66.52,
3
2
−1
6.66, 111.43, 113.19, 119.07, 130.74, 147.47.
developed OMS-MIL-100(Fe) are 763 m g .
1
3