Chemical Fixation of CO2 and Other Heterogeneous Catalytic Studies by Employing a Layered Cu-Porphyrin Prepared Through Single-Crystal to Single-Crystal Exchange of a Zn Analogue

Article abstract of DOI:10.1002/asia.201701384

A solvothermal reaction of Zn(NO₃)₂?6 H₂O, tetra-(4-pyridyl)porphyrin (H₂TPyP), and 4,4′-oxybis(benzoic acid) (H₂OBA) resulted in a new two-dimensional Zn- porphyrin metal–organic framework compound,

Full text of DOI:10.1002/asia.201701384

CHEMISTRY
AN ASIAN JOURNAL
www.chemasianj.org
Accepted Article
Title: Chemical Fixation of CO2 and Other Heterogeneous Catalytic
Studies Employing a Layered Cu-Porphyrin Prepared Through
Single-Crystal to Single-Crystal Exchange of a Zn-analogue
Authors: Srinivasan Natarajan, Gargi Dutta, and Ajay Kumar Jana
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To be cited as: Chem. Asian J. 10.1002/asia.201701384
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Chemistry - An Asian Journal
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FULL PAPER
Chemical Fixation of CO
2
and Other Heterogeneous Catalytic
Studies Employing a Layered Cu-Porphyrin Prepared Through
Single-Crystal to Single-Crystal Exchange of a Zn-analogue
[
a]
[a]
[a]
Gargi Dutta, Ajay Kumar Jana and Srinivasan Natarajan*
Abstract:
pyridyl)porphyrin (H
resulted in a new two-dimensional Zn-porphyrin MOF compound,
Zn )(DMA)](DMA)(H O) 1. The Zn(II) ions
present in 1 could be ion-exchanged employing Cu(NO .3H
solution at room temperature resulting
Cu )(DMA)](DMA)(H O) (Cu∊1) compound.
The extra-framework solvent molecules have been shown to be
A
solvothermal reaction of Zn(NO
3
)
2
.6H
2
O, tetra-(4-
years.[11] We have been investigating the porphyrin based
framework employing 5,10,15,20-tetrakis(4-
pyridyl)porphyrin(TPyP) along with aromatic dicarboxylates. In
continuation of the theme, we have now prepared a new
2
TPyP) and 4,4′-Oxybis(benzoic acid) (H
2
OBA)
[
12]
[
2
(C40
H
24
N
8
)
0.5(C14H O
8 5
2
6
,
)
3 2
2
O
porphyrinic MOF [Zn
1
2
(C40
H
24
+
N
8
)
0.5(C14
H
8
O
5
)(DMA)](DMA) (H
2 6
O) ,
in
employing TPyP, Zn2 ion and 4,4′-oxybisbenzoic acid
[
2
(C40
H
24
N
8
)
0.5(C14H
O
8 5
2
3
,
(H
2
OBA) (Scheme 1). The compound crystallizes with a two-
dimensional layered structure. The Zn2 ions were exchanged by
+
reversibly removed/exchanged without the collapse of the framework. Cu2+ ions by post-synthetic ion-exchange methods in a single-
The solvent-free Cu∊1 was explored as an active heterogeneous
crystal to single-crystal (SCSC) fashion forming the copper
catalyst towards three different organic reactions: (i) chemical
exchanged
[Cu
compound
(Cu∊1). The
fixation of CO
2
into cyclic carbonate at room temperature under 1
2
(C40
H
24
N
8
)0.5(C14
H
8
5
O )(DMA)](DMA)(H
2
O)
3
atm; (ii) nitroaldol reaction under solvent free condition and (iii) three
component coupling of aminopyridine, benzaldehyde and aryl
alkynes followed by 5-exo-dig cyclization to produce an important
pharmacophore imidazopyridine.
copper compound, Cu∊1, exhibits good catalytic activity for a
number of organic reactions. In this paper, we present the
synthesis, SCSC transformation studies, characterizations and
catalytic behavior of the Cu∊1 compound.
N
Introduction
Metal-Organic framework (MOF) compounds have been in
the forefront of research for the last two decades.[1] The
continued interest is due to the many properties exhibited by this
class of compounds in the areas of sorption, separation and
catalysis.[2] The MOFs also offer opportunities to control the
structure to realize properties such as proton-conduction,[3]
magnetism[4] etc. In recent times the structural emphasis of
NH
N
N
(i)
N
N
+L
1
HN
O
research on MOFs has migrated towards compounds with
targeted properties.
L= HOOC
COOH
N
The MOFs have been traditionally prepared by a cooperative
and synergistic assembly between the metal ions and the
organic ligand. The MOFs also encompass preassembled
o
Reaction condition : (i) Zn(NO ) .6H O/DMA/HBF /100 C/ 3days
3
2
2
4
molecular entities such as cyclodextrin, porphyrin[6] and metal-
oxo clusters[ as part of the structures. Such assemblage leads
to structures that are not only interesting but also exhibit newer
properties. We have been particularly intrigued by the porphyrin
based assemblies that are incorporated as part of the MOF
structures. Metalloporphyrins have been actively researched
over the years for their use in many areas. The foremost being
the Fe-porphyrin, which is an important co-factor in oxygen
transport.[ Many metalloporphyrins have also been explored for
catalysis.[ The versatility along with the rigidity of the
metalloporphyrin is attractive in building new MOFs. The
porphyrin MOFs can find applications in non-linear optics, ion-
[5]
7]
Scheme 1: Scheme showing the sovothermal synthesis of 1.
Results and Discussion
Structure of [Zn (C H N ) (C H O )(DMA)] (DMA) (H O) ,1:
2
40 24 8 0.5
14
8
5
2
6
Compound 1 crystallizes in triclinic P-1 space group. The
asymmetric unit contains 51 non hydrogen atoms (Figure S1 in
the supporting information) of which two zinc atoms are distinct.
Zn(1) exhibits a distorted square pyramidal geometry with four
pyrrole nitrogen atoms [N(1), N(2), N(1)(#1) and N(2)(#2)] in the
equatorial position and one oxygen atom [O(1)] from the solvent
molecule in the axial position (Figure S2 in the supporting
8]
9]
exchange,
selective
10]
catalysis,
photosensitization
and
photovoltoics.[ This area has attracted much attention over the
information). Zn(2) has
a tetrahedral geometry with two
carboxylate oxygen [O(2) and O(4)] from 4,4′-Oxybis(benzoic
acid) and two nitrogen atoms [N(3) and N(4)] from TPyP ligand
(Figure S2). The Zn(1) atom was observed to be moved away
from the porphyrin plane towards the axially coordinated solvent
molecule with a deviation of 0.610 Å. The Zn-O bond distances
are in the range of 1.940(3)Å-2.069(8)Å and the Zn-N bond
distances are in the range of 2.025(3)Å-2.139(4)Å. The structure
consists of a connectivity between the Zn-porphyrin units and
[
a]
Dr. G. Dutta, A. K. Jana, Prof. S. Natarajan
Framework Solids Laboratory, Solid State and Structural Chemistry
Unit, Indian Institute of Science, Bangalore-560012, India
E-mail: snatarajan@iisc.ac.in
Supporting information for this article is given via a link at the end of
the document.
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FULL PAPER
Zn-OBA units. Thus the Zn-porphyrin units are connected to
Zn(2) atoms forming a one-dimensional chain (Figure 1a). The
(
c)
1D chains are further connected by the 4,4′-Oxybis(benzoic
acid) forming the 2D structure (Figure 1b). The 2D layers are
stacked one over the other in an AAA… fashion (Figure 1c). The
two-dimensional layers encompasses
a large aperture of
26.3x21.6 Å (shortest atom-atom contact distance not including
the van der Walls radii) within the sheet. Such is the disposition
of the layers that pores of this diameter penetrate the entire
structure in a direction perpendicular to the layers, thus yielding
a solid with unidimensional pores. The channels are occupied by
disordered solvent molecules. A PLATON calculation reveals a
solvent accessible void volume of 62%.
The presence of channel-like features in 1 prompted us to
Figure 1. (a) Figure shows the connectivity between the Zn-porphyrinic units
through the Zn-centers forming a one-dimensional unit; (b) The connectivity
between the 1D units and the 4,4′-Oxybis(benzoic acid) forming two-
explore the possibility of transmetallation of Zn2+ ions with Cu2+
ions. To this end the as-synthesized crystal were soaked in DMA
solution of Cu(NO ) at room temperature. The copper nitrate
3 2
dimensional arrangement; (c) The arrangement of layers. Arranged in
a
AAA…type stacking.
solution was periodically replenished for better ion-exchange. It
was observed that all Zn2+ ions can be fully exchanged by Cu2+
ions in 8 days. The replacement (>98%) was confirmed by
UV-vis and Photoluminescence Studies:The optical property
of the compounds was examined at room temperature
EDAX and AAS (Figure S3 and S4 in the supporting information). employing UV-vis and photoluminescence studies. Expectedly,
We did not observe any change in the crystalline shape or size,
suggesting that the metal-ion exchange is facile. In addition we
observed that the Cu-exchanged sample (hereafter Cu∊1)
exhibited identical PXRD pattern as that of the parent Zn-
compound (Figure S5 in the supporting information). Thus we
have successfully carried out a single-crystal to single-crystal
transmetallation in the present study. A single crystal structure
study on the Cu-exchanged sample indicated an identical
structure to that of the Zn-compound. It may be noted that the
Cu∊1 sample would have a square-pyramidal copper within the
porphyrin and a tetrahedral copper coordinated by two oxygens
of OBA and two nitrogens from pyridine. We also explored the
reversible transmetallation of Cu∊1 to the present Zn-compound
by performing an similar experiment employing DMA solution of
the optical behavior strongly depends on the porphyrin unit in
the structure. The solid state UV-vis spectra of compound 1 and
Cu∊1 exhibited Soret bands at 410 nm and 406 nm (S
absorption) and four Q bands in the range 450 nm-610 nm due
to the π-π* transitions of the H TPyP ligand (S →S ) (Figure S6
in the supporting information). The red-shift of the absorption
bands in 1 and Cu∊1 compared to the H TPyP ligand and the
0 2
→S
2
0
1
2
reduction in the number of Q-bands indicate that the Zn2+ and
the Cu2+ ions have been incorporated in the porphyrin core.
The emission spectra of both the Zn and Cu compounds were
examined in the solid state at room temperature using an
excitation wavelength of 410 nm (Figure S7 in the supporting
information). The emission bands observed, in the range 532-
663 nm in 1 and 531-669 nm in Cu∊1, are due to the intraligand
Zn(NO
3
)
2
.6H
2
O. Even after 30 days of soaking, we did not
emission from the H
~532nm for 1 and Cu∊1 may correspond to the e
2
TPyP ligand. An emission band observed at
→a1u transition.
observe the transmetallation to the parent Zn-compound.
g
The bands observed in the range of 625 and 663 nm for 1; 631
and 669 nm for Cu∊1 can be ascribed to egx→a2u and egy→a2u
transitions respectively. The quantum yield for emission is 3.70
for 1 and 0.95 for Cu∊1 (Figure S7 in the supporting information).
(
a)
Thermal Stability:
Thermogravimetric analysis (TGA) was employed to investigate
the thermal stability of the compounds. Thermogravimetric study
on Zn-compound (1) (Figure S8 in the supporting information)
exhibits a weight loss of 39.7% in the temperature range 30-
(
b)
205ºC which would correspond to the loss of 2 DMA and 6H
2
O
molecules (calc. 39.6%). A flat region in the temperature range
2
3
05-335ºC indicates that the compound may be stable upto
35ºC. Above 335ºC a steady weight loss was observed
indicating collapse of the framework. We investigated the
removal of solvent molecules from 1 and the stability of the
framework. The as-synthesized 1 was kept in vacuum oven at
205°C. The evacuated sample exhibited a PXRD that is similar
to the as prepared parent compound suggesting that the
structural integrity is retained (Figure S9 in the supporting
information). The evacuated sample readily absorbs solvent
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molecules, when immersed into the solvent. The resolvated
sample exhibits a behavior that is comparable to the as-
synthesized sample under the TGA studies. The final calcined
product was found to be crystalline and corresponds to ZnO
reaction of epoxide with CO
2 2
-generally under high CO pressure
(>3Mpa) and high temperature (>100ºC).[14] This is
a
cumbersome process and involve considerable expenditure
towards energy costs. There is a need to search for new
heterogeneous catalytic systems which can effectively convert
(
JCPDS: 36-1451) (Figure S10 in the supporting information).
The removal of the water molecules from the compound was
also investigated using in-situ temperature programmed IR
measurements. The studies clearly indicated that the water
molecules are completely removed ~180ºC (Figure S11 in the
supporting information). The evacuated sample (solvent
removed) was also analyzed employing TGA studies. We
observed no major weight loss upto 225ºC, suggesting that the
solvent molecules have been removed from the compound.
The Cu-compound (Cu∊1) also exhibited a similar behavior as
that of 1 in the TGA study (Figure S8 in the supporting
information). A weight loss of 32.1% in the range 30-207ºC may
2
the CO into cyclic carbonate under milder conditions. There are
reports of the use of metalloporphyrin based compounds as
effective homogeneous catalysts for the synthesis of cyclic
carbonate with good turnover number.[ This prompted us to
explore the catalytic performance of Cu∊1 in the chemical
15]
fixation of CO
2
with different epoxides (Scheme 2) under
ambient conditions. We have employed Cu∊1 along with tetra-n-
tert-butylammonium bromide as a cocatalyst for this reaction.
The studies indicate efficient catalytic activity in the conversion
of 2-methyl oxirane to the corresponding cyclic carbonate under
ambient conditions (room temperature and 1 atm CO
2
pressure).
correspond to the loss 2DMA and 3H
2
O molecules (calc. 32.2%). The high efficiency and catalytic activity of the above reaction
The framework also appears to be stable upto 325ºC and starts
to collapse after that. The final calcined product was found to be
CuO (JCPDS: 65-2309) (Figure S13 in the supporting
information).
was also extended successfully to functionalized 2-methyl
oxirane and styrene oxide, which resulted in good catalytic
conversion and yields (Table 1).
2
Table 1: Table summarizing the Cu∊1 catalyzed cycloaddition of CO and
Catalytic studies on Cu∊1: To prepare the catalyst, we
activated Cu∊1 by immersing in MeOH for 5 days at room
temperature. This methanol soaked sample was heated at 60ºC
in vacuum oven for 24 hrs which resulted in activated Cu∊1
ready to be employed for catalytic investigations. A PXRD study
of the activated sample indicated that the structural integrity was
retained (Figure S14 in the supporting information). We have
attempted three different catalytic reactions employing the
activated Cu∊1catalyst.
epoxides to form cyclic carbonates
Entry
1
Catalyst
Substrate
Product
Yield
%)
(
Cu∊1
O
98%
O
O
O
2
Cu∊1
O
Cl
Cl
97%
O
O
O
1
atm, r.t.
R
R +CO2
1
mol% Cu1/TBAB
O
O
O
O
O
O
O
O
O
3
4
5
Cu∊1
O
O
O
89%
17%
<2%
O
Ph
Ph
Ph
O
O
Ph
Ph
Ph
-
Br +
CuII
R
O
R
O
CuII
1
O
O
CuII
O
O
R
Br
O
No
O
catalyst
CuII
R
CO2
O
-
O
Br
R
Br
6
7
Cu(OAc)
H O
2
2
.
O
O
No Product
No
Product
Scheme 2. Possible mechanism for the formation of cyclic carbonate
Ph
(
a) The cycloaddition reaction of epoxide and CO
ambient conditions: Cyclic carbonates, formed by the coupling
of epoxide and CO , have been of interest for their application as
aprotic polar solvents, electrolyte for lithium battery, fuel
additives, synthetic intermediates for polycarbonate etc. Many
different catalysts such as metal oxides, zeolites, titanosilicate
and ion-exchanged resins have been explored for the coupling
2
under
CuTPyP
8%
O
Ph
Ph
2
O
O
[
13]
In a typical reaction, 20 mmol of the epoxide substrate, 0.065 g
of tetra-n-tert-butylammonium bromide co-catalyst (TBAB, 10
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mol%) and 0.010 g (1 mol % based on Cu) Cu∊1 were added
into a Schlenk tube. The tube was purged with CO at 1 atm
2
Entry
1
Catalyst
Ar
Product
Yield
87%
under solvent free conditions onto a mechanical shaker for 30 h
for completing the catalytic reaction. The mixture was then
filtered and purified in a silica gel column to get the desired
product. The catalyst recovered from the reaction, have been
tested for recyclability. The studies confirmed that the catalyst
can be effectively used upto four cycles without losing any
activity (Figure S15 in the supporting information).
OH
Cu∊1
2
4-NO -Ph
NO2
2
O N
OH
2
Cu∊1
4-Br-Ph
79%
NO2
OH
Br
NO2
1
0 mol% Cu1
Ar-CHO + CH3NO2
Ar
OH
5oC/ 36 h
3
4
Cu∊1
Ph
83%
18%
6
NO2
OH
O
NO2
HO
R
II CH3NO2 + R
H
1
OH
4-NO
2
-Ph
[
Cu ]
NO2
O
NO2
R
N
H
-
O2N
O
O
CH2
[CuII]
H
II
[
Cu ]
N
5
6
No
Catalyst
4-NO
2
2
-Ph
-Ph
No Product
No
Product
O
-
O
R
C-C bond formation/
H -shift
II
OH
[
Cu ]
Cu(OAc)
H O
2
2
.
4-NO
31%
+
H
NO2
O
R
O2N
Scheme 3. A possible mechanistic pathway for the nitroaldol reaction
OH
7
CuTPyP
4-NO
2
-Ph
16%
NO2
(
b) The nitroaldol (Henry) reaction: The addition of
nitroalkanes to carbonyl compounds known as Henry reaction
or nitroaldol) is considered as an effective, powerful and atom-
O2N
(
economic synthetic tool for the formation of carbon-carbon
bond.[16] There have been a number of different catalysts such
as alkali metal hydroxides, alkoxides and many Zn and Cu-
complexes have been explored for the nitroaldol reaction.[17] It is
still a challenge to develop new catalysts that can be effective in
this nitroaldol reaction especially under mild conditions with
recyclability.
Table 2: Summary of nitroaldol reaction of aromatic aldehyde and
nitromethane catalyzed by Cu∊1
(
c) Synthesis of imidazopyridine by three component
coupling and 5-exo-dig cyclization: Imidazopyridine is an
Our compound contains tetrahedral copper center [Cu(2)] and
we explored the nitroaldol reaction between aromatic aldehyde
with nitromethane (Scheme 3) under solvent free conditions to
generate the corresponding product (Table 2). To a mixture of
important pharmacophore. It has been found in many
biologically active compounds.[18] Imidazo[1,2-a] is one of the
key component present in several anxiolytic drugs like alpidem,
necopidem, zolpidem etc. which are used for the treatment of
insomenia.[19] Various methodologies have been developed for
0.01 mmol (0.6 mL) nitromethane and 0.05 mmol aromatic
aldehyde 10 mol% Cu∊1 was added. The mixture was refluxed
at 65ºC over a period of 36 hrs. The progress and completion of
the reaction was confirmed by TLC. The filtrate was evaporated
in vacuum to obtain the product, which was further purified in a
silica gel column using petroleum ether and ethyl acetate as the
eluent. The catalyst was recovered by filtration, washed several
times with methanol and kept in a vacuum oven at 60ºC for 24 h.
The recyclability studies indicate that the catalyst remains active
for upto three cycles (Figure S16 in the supporting information).
the preparation of imidazopyridine and derivatives but mostly
require multiple steps.[20] A three component coupling reaction
between aryl/heteroaryl/alkyl aldehydes, aminopyridine and
terminal alkyne, catalyzed by copper compounds appears to be
an effective method for this transformation. The reaction
proceeds through the formation of the intermediate
propargylamine which further undergoes a 5-exo-dig cyclization
forming the imidazopyridine. We desired to explore the catalytic
activity of Cu∊1 for this three component reactions.
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NH2
N
successfully synthesized employing
Oxybis(benzoic acid) . The accessibility of Zn ions facilitates a
post-synthetic metathesis with Cu2+ in a single crystal-single
TPyP and 4,4′-
O
N +Ph
5 mol% Cu1
Ph
2+
+ R
H
H
o
1
20 C/ 20h
N
crystal fashion (Cu∊1). The Cu∊1 compound was found to be a
R
good catalyst for a number of heterogeneous catalytic reactions.
N
2
Thus the conversion of CO to cyclic carbonate under ambient
Ph
condition, the nitroaldol reaction under solvent free conditions
and the synthesis of imidazopyridine via three component
coupling reaction have been explored and the Cu∊1 was found
to be a good heterogeneous catalyst. In all the studies, we have
observed catalytic activity only with Cu∊1 samples and not over
the parent Zn-compound, suggesting that the catalytic activity is
due to the presence of Cu(II) ions. The extra-framework solvent
molecules can be reversibly removed/exchanged without the
collapse of the framework. It appears that the porphyrin based
MOFs with their considerable open structures provide
opportunities to explore ion-exchange, sorption and
heterogeneous catalysis. These studies are being pursued
actively and the results would be reported elsewhere.
N
R
H
5-exo-dig
R
[Cu]2+
H
N
Ph
R
H
N
[Cu]+
N
[
Cu]+
NH2
R
O
[
Cu]+
+
R
Ph
H
N
N
Ph
H
R
N
H
N
Scheme 4: Possible mechanistic pathway for the three component synthesis
of imidazopyridine
Experimental Section
Compound
1
was prepared employing
a
A
solvothermal method
mixture of tetra-(4-
For this reaction, 5 mol% Cu∊1 was added to the mixture
containing 2-aminopyridine (1.1 mmol), benzaldehyde (1.2
mmol) and aryl alkynes (1mmol) in 1 ml toluene at 120ºC under
(
Supporting Information Scheme S1).
pyridyl)porphyrin (H TPyP) (0.02 mmol= 0.012 g); 4,4′-Oxybis(benzoic
2
acid) (H
2
OBA) (0.04 mmol=0.010g) and Zn(NO
3
)
2 2
.6H O (0.1 mmol=
0
.029 g) was dissolved in 2 ml DMA. A small quantity of HBF
4
(12 μL)
N
2
atmosphere (Scheme 4). The resulting mixture was stirred for
was added to the reaction mixture and the resulting solution was
homogenized under continuous stirring for 30 min. The reaction mixture
with a composition, 5 [Zn(NO
20 hrs for the reaction to complete and the desired
imidazopyridine was obtained in good yields (87-91%) (Table 3).
We have also attempted the same reaction in the presence of
simple copper salt such as copper acetate, which resulted in
poor conversion and yield (Table 3, entry 6). The progress of the
reaction was much poorer in the absence of any catalyst (Table
3 2 2 2 2
) . 6H O] : 2 H OBA : 1 H TPyP : 1075
DMA : 5 HBF was transferred into a PTFE lined stainless steel autoclave
4
and heated at 100°C for 3 days. The product contained needle shaped
purple colored crystals, which were filtered, washed with dry MeOH/DMA
mixture and vacuum dried at room temperature (yield ~ 53% based on
3
, entry 5. The recovered Cu∊1 from the above reaction was
H
[
5
2
TPyP).
Zn
4.21(54.13), H 5.85(5.83), N 6.88(6.66)].
CHN
analysis
(%)
for
C
2
(C40
24 8
H N )
0.5(C14H O
8 5
)(DMA)](DMA)(H O)
2
6
,
1
[Found (calcd) :
found to be active for upto three cycles (Figure S17 in the
supporting information) suggesting that the catalyst is stable and
useful for multiple attempts.
Table 4. Crystal Data and Structure Refinement Parameters for the prepared
compounds
Table 3: Summary of the three component coupling reaction catalyzed by
Cu∊1
1
Cu∊1
Empirical Formula
FormulaWeight
Crystal System
Space Group
a(Å)
b(Å)
c(Å)
α (deg)
β (deg)
C
34
H
20
N
4
O
6
Zn
2
34 2 4 6
C H20Cu N O
Entry
Catalyst
R
Yield
711.32
Triclinic
P-1
14.125(3)
14.216(3)
16.080(3)
81.516(8)
75.377(8)
89.547(9)
3088.5(10)
2
298(2)
0.765
707.64
Triclinic
P-1
14.180(3)
14.490(3)
16.141(3)
83.821(8)
78.757(8)
85.967(9)
3229.8(10)
2
298(2)
0.728
1
2
3
4
5
6
7
Cu∊1
Cu∊1
Cu∊1
1
Ph
88%
4-F-Ph
4-Me-Ph
Ph
91%
87%
γ (deg)
Volume (Å )
<2%
3
Z
No catalyst
Ph
No Product
14%
Temperature (K)
-
3
ρ
c
(gcm )
Cu(OAc)
2
.H
2
O
Ph
-1
μ(mm )
0.803
2.35-22.94
0.71073
0.0933, 0.2549
0.1204, 0.2747
0.683
1.29-25.00
0.71073
0.0887, 0.2441
0.1062, 0.2632
θ range (deg)
Wavelength (Å)
R1, wR2 [I>2σ(I)]
R1, wR2 (all data)
CuTPyP
Ph
11%
Conclusions
a
2
− F 2
)]/Σ [w(F 2
2
1/2
2
)2
R
1
= Σ||F
o
| − |F
c
||/Σ|F
o
|; wR
o
2
= {Σ|w(F
o
c
o
) ]} . w = 1/[ρ (F
o
+
A
new
Zn-based
2D
porous
MOF
was
2
,
2
(aP) + bP]. P = [max (F
O) + 2(F ) ]/3, where a= 0.1623 and b= 0.0000 for 1;
c
[
Zn
2
(C40
H
24
N
8
)0.5(C14
H
8
5
O )(DMA)](DMA)(H
2
O)
6
,
1,
a= 0.1597 and b= 0.0000 for Cu∊1
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Metal Exchange Studies:
parameters for all the hydrogen atoms. Crystallographic data (excluding
structure factors) for the structures in this paper have been deposited
with the Cambridge Crystallographic Data Centre, CCDC, 12 Union Road,
Cambridge CB21EZ, UK. Copies of the data can be obtained free of
charge on quoting the depository numbers (1566676 for 1 and 1566677
for Cu∊1). The detail of structure determination is presented in Table4.
Important bond length and bond distances are given in Table S2 and S3
in the supporting information.
Exchange of the Zn ions by Cu ions was attempted in a single crystal to
single crystal (SCSC) fashion. To this end few single crystals of the Zn
compound was immersed in a glass vial containing 0.1 M solution of
Cu(NO
was replaced periodically. The metal-exchanged crystals (Cu∊1)
Cu )(DMA)](DMA)(H O) were collected and
3 2 2 3 2 2
) .3H O in DMA at 298K for 8 days. The Cu(NO ) . 3H O (0.1M)
[
2 24 8
(C40H N )
0.5(C14H O
8 5
2
3
soaked in DMA for 3 days to remove any excess free cations occluded in
the pores. The Cu-exchanged samples as well as the Zn-sample were
dark in color and in order to learn about the extent of metal exchange, we
have performed EDAX (Figure S3) as well as AAS analysis (Figure S4).
CHN analysis (%) for [Cu (C40H N )0.5(C14H O )(DMA)](DMA)(H O) ,
2 24 8 8 5 2 3
Cu∊1 [Found (calcd) : C 54.86(54.80), H 4.20(4.24), N 8.45(8.41)]. This
sample (Cu∊1) was used for all the studies reported in the manuscript.
Acknowledgements
SN would like to thank the Science and Engineering Research
Board (SERB), Government of India for the award of a research
grant as well as a J. C. Bose National Fellowship. GD is thankful
to DST SERB for research grant and IISc for infrastructure.
Council of Scientific and Industrial Research (CSIR),
Government of India, is thanked for a research grant (S.N.) and
a research fellowship (A.K.J.).
Physical Measurements:
Elemental analysis was performed in a Thermo Finnigan EA Flash 1112
series instrument. Powder X-ray diffraction patterns were recorded in the
2θ range of 5–50° using Cu-Kα radiation (Philips X’pert Pro). The
experimental PXRD patterns were found to be consistent with the
simulated powder X-ray patterns generated from the single crystal
structures (Mercury software version 1.4.1) (Figure S5 in the supporting
information). IR spectra for the compounds were recorded (KBr pellet)
using an FTIR spectrometer (Perking-Elmer Spectrum 1000) (Figure S18
Keywords: MOF • Porphyrin • Synthesis • Structure• Catalysis
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Entry for the Table of Contents (Please choose one layout)
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Gargi Dutta,[a] Ajay Kumar Jana
and Srinivasan Natarajan*
[a]
Synthesis, structure and Cu-
exchange (SCSC fashion) of a
porphyrin-based MOF has been
described. Copper exchanged
[
a]
Page No. – Page No.
compound
activity towards (i) chemical
fixation of CO under ambient
condition, (ii) nitroaldol reaction
and (iii) three component coupling
reaction.
exhibits
catalytic
2
Chemical fixation of CO and
other Heterogeneous Catalytic
Studies employing a Layered Cu-
Porphyrin Prepared Through
Single-Crystal to Single-Crystal
Exchange of a Zn-analogue
2
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