Assembling Porphyrins into Extended Network Structures by Employing Aromatic Dicarboxylates: Synthesis, Metal Exchange, and Heterogeneous Catalytic Studies

Article abstract of DOI:10.1002/chem.201700985

Three new metal–organic porphyrinic framework compounds of zinc and 5,10,15,20-tetrakis(4-pyridyl)porphyrin (TPyP) have been synthesized under solvothermal conditions. The compounds [Zn₅(C₄₀H₂₄N₈)(C₈H₄O₄)₂(NO₃)₆(DMA)₂] (DMA)₃(H₂O)₈ (1; DMA=dimethylacetamide), [Zn₃(C₄₀H₂₄N₈)(C₈H₄O₄)₂(DMF)](DMF)₅(H₂O)₁₂ (2), and [Zn₃(C₄₀H₂₄N₈)(C₁₂H₆O₄)₂(DMA)₂](H₂O)₇ (3) have two (1) and three dimensionally (2 and 3) extended structures. All the three structures contain porphyrinic units connected through the carboxylate linkers. The nitrates bind the metal centers and are not hydrogen bonded. The different binding modes of nitrate in the structure of 1 are observed for the first time in a porphyrin-based MOF. The openness of the structure allowed us to explore metal exchange through a room-temperature metathetic route. Compound 2 undergoes 100 % exchange with copper, whereas compound 3 exchanges 70 % with copper. The copper-exchanged compounds Cu∈2 and Cu∈3 were observed to be good heterogeneous catalysts for many important organic reactions. The chemo and regioselective enamination of β-ketoesters, preparation of propargylamine derivatives as well as regioselective cycloadditions of alkyne and azide (click reactions) have been carried out with good yields and selectivity. All the compounds have been characterized by PXRD, IR, UV/Vis, atomic absorption spectroscopy (AAS), and energy-dispersive X-ray spectroscopy (for Cu exchange).

Full text of DOI:10.1002/chem.201700985

A Journal of
Accepted Article
Title: Assembling Porphyrins into Extended Network Structures
Employing Aromatic Dicarboxylates: Synthesis, Metal-exchange
and Heterogeneous Catalytic Studies
Authors: Srinivasan Natarajan, Gargi Dutta, and Ajay Kumar Jana
This manuscript has been accepted after peer review and appears as an
Accepted Article online prior to editing, proofing, and formal publication
of the final Version of Record (VoR). This work is currently citable by
using the Digital Object Identifier (DOI) given below. The VoR will be
published online in Early View as soon as possible and may be different
to this Accepted Article as a result of editing. Readers should obtain
the VoR from the journal website shown below when it is published
to ensure accuracy of information. The authors are responsible for the
content of this Accepted Article.
To be cited as: Chem. Eur. J. 10.1002/chem.201700985
Link to VoR: http://dx.doi.org/10.1002/chem.201700985
Supported by

Chemistry - A European Journal
10.1002/chem.201700985
FULL PAPER
Assembling Porphyrins into Extended Network Structures
Employing Aromatic Dicarboxylates: Synthesis, Metal-exchange
and Heterogeneous Catalytic Studies
[a]
[a]
[a]
Gargi Dutta, Ajay Kumar Jana and Srinivasan Natarajan*
Abstract: Three new metal-organic porphyrinic framework
compounds of zinc and 5,10,15,20-tetrakis(4-
pyridyl)porphyrin(TPyP) have been synthesized under solvothermal
photonic devices, conductive polymers, chemical sensors and
[
5]
selective catalysis.
During the past few years, there has been considerable
[6]
conditions.
The
compounds
interest in the post-synthetic modifications of MOFs. Majority of
the studies concentrated towards functionalizing the organic
linkers and there have been attempts at transmetallation
[
[
[
Zn
5
Zn
3
Zn
3
(C40
(C40
(C40
H
H
H
24
24
24
N
N
N
8
8
8
)(C
)(C
8
H
H
4
O
O
4
)
)
2
(NO
3
)
6
(DMA)
2
](DMA)
(H
O)
3
(H
2
O)
8
,
1;
8
4
4
2
(DMF)](DMF)
(DMA) ](H
5
2
O)12
,
2;
and
[
7]
)(C12
H
6
O
4
)
2
2
2
7
, 3 have two- (1) and three-
employing the Irving-Williams approach. The transmetallation
studies, on the other hand, has been limited in porphyrinic
dimensionally (2 and 3) extended structures. All the three structures
contain porphyrinic unit connected through the carboxylate linkers.
The different binding modes of nitrate in the structure of 1 has been
observed for the first time in a porphyrin based MOF. The nitrates in
the structure are metal binding and not hydrogen bonded. The
openness of the structure allowed to explore the metal exchange
[
8]
MOFs.
Zn
[Zn
We have now prepared new porphyrinic MOFs
)(C (NO (DMA) ](DMA) (H O) ,(1);
)(C (DMF)](DMF) (H O)12,(2);[Zn
(DMA) (3) employing porphyrin TPyP
(scheme 1). As a model study we have attempted to exchange
5
(C40
(C40
O
H
H
24
N
8
8
H
4
O
4
)
2
3
)
6
2
3
2
8
3
24
N
8
8
H
4
O
4
)
2
5
2
3 24 8
(C40H N )
(C12
H
6
4
)
2
2 2 7
](H O) ,
2
+
2+
through
a
room temperature metathetic route. Compound
2
3
Cu in place of Zn ions in 2 and 3 and prepared the
corresponding Cu∊2 and Cu∊3 compounds.
undergoes 100% exchange for copper, whereas compound
exchanges 70% for copper. The copper exchanged compounds
Cu∊2 and Cu∊3 were observed to be good heterogeneous catalysts
for many important organic reactions. The reactions, chemo and
regioselective enamination of β-ketoesters, preparation of
propargylamine derivatives as well as regioselective cycloaddtion of
alkyne and azide (click reaction) have been carried out with good
yields and selectivity. All the compounds have been characterized by
PXRD, IR, UV-vis, AAS and EDAX (for Cu-exchange).
In this paper we present the synthesis, structure,
transmetallation studies and heterogeneous catalytic studies of
these new porphyrinic MOFs.
N
(
i)
1
2
3
NH N
N HN
(ii)
N
N
+
L
Introduction
(i)
Porphine is
a biologically important fully conjugated
N
macrocyclic compound. Substituted porphines are known as
porphyrins and metallo porphyrins. The iron containing ones are
important for oxygen transport in vertebrates and have been
investigated in detail over the years. Many other
metalloporphyrins have been studied for a wide range of
HO
OH
O
[3]
L= HOOC
COOH [1 and 2]
;
O
[
1]
o
Reaction condition : (i)
(
Zn(NO
)
.4H
O/ DMA/ 100 C/ 3 days ;
applications. Metal-organic frameworks (MOFs) or inorganic
coordination polymers (CPs) have attracted considerable
3
2
2
o
ii)Zn(NO ) .4H O/ DMF/ 100 C/ 3 days
3
2
2
[
2]
attention during the last two decades.
Porphyrins and
metalloporphyrins are easy to synthesize with multiple
functionalities and exceedingly useful building blocks for the
construction of framework solids through interporphyrin van der
waals interactions, hydrogen bonding and metal-organic
Scheme 1. Synthesis of 1, 2 and 3 using solvothermal technique
[
3]
coordination bonding. Robson, Suslick, Strouse, Goldberg and
their co-workers have reported porphyrin and metalloporphyrin
Results and Discussion
[
4]
based framework solids since early 1990s. The porphyrinic
MOFs exhibit interesting properties that find applications in
Structure
of
1:
[
5 24 8 8 4 4 2 3 6 2 3 2 8
Zn (C40H N )(C H O ) (NO ) (DMA) ](DMA) (H O) ,
Compound 1 crystallizes in orthorhombic I222 space group. The
asymmetric unit of the framework contains 29 non-hydrogen
atoms of (Figure S1 in the supporting information) which two
zinc atoms are distinct. Both the zinc atoms are octahedrally
coordinated. Zn(1) occupies a special position (2a) with a site
multiplicity of 0.25. Zn(1) is octahedrally coordinated with four
pyrrole nitrogen atoms [N(1), N(2), N(1)(#1), N(2)(#2)] in the
equatorial position and by two oxygen atoms from the solvent
[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@sscu.iisc.ernet.in
Supporting information for this article is given via a link at the end of
the document.
This article is protected by copyright. All rights reserved.

Chemistry - A European Journal
10.1002/chem.201700985
FULL PAPER
molecules [O(1), O(1)(#2)] in the axial position. Zn(2) is
coordinated by two oxygens from the terephthalate [O(2), O(3)];
one pyridyl nitrogen from the porphyrin [N(3)] and three oxygens
from nitrate species [O(4), O(5) and O(7)]. The Zn-N bond
distances are in the range of 2.026(6)Å-2.094(5)Å [average :
(c)
2
2
.039Å] and Zn-O bond distance are in the range of 1.961(6)Å-
.449(13)Å [average : 2.249 Å] (Table S1 in the supporting
information). The structure of 1 can be considered from simpler
building units. Thus the metalloporphyrin units are connected to
each other via a zinc nitrate bridge forming a one-dimensional
arrangement as shown in Figure 1a. There have been reports of
nitrate bridging as well as terminal nitrate units in MOF
[
9]
structures, but a single nitrate unit bridging two metal centers
appears to be a new structural feature in the present compound
[
10]
(
Figure 1a). As can be seen that there are two distinct nitrate
species in the structure, while one satisfies the coordination
requirement of Zn(2), the other bridges two metalloporphyrin
units leading to a one dimensional chain arrangement (Figure
Figure 1. (a) Figure shows the connectivity between the Zn-porphyrinic units
through the nitrate units forming a one-dimensional arrangement (note the
unusual nitrate binding, highlighted by green bonds), (b) The connectivity
between the 1D porphyrinic networks through the 1,4-benzenedicarboxylate
forming the 2D structure, (c) The arrangement of layers. Note the formation of
ABAB…type stacking. The solvent molecules are not shown for clarity.
1
a). The 1D chains are connected by the terephthalate units
forming an extended two-dimensional structure (Figure 1b). The
D layers are stacked one over the other in an ABAB….fashion
Figure 1c).
2
(
O(5)] for Zn(2); [O(6), O(7), O(8) and O(9)] for Zn(3) from the
terephthalate units and two nitrogen atoms [N(7), N(8) for Zn(2);
N(5) and N(6) for Zn(3)] from the pyridyl groups of the TPyP
ligand. The Zn(1) was found to be deviated by 0.324 Å from the
plane of the porphyrin unit and moved towards the axially
coordinated solvent molecule. The Zn-O bond distances are in
the range of 1.9411(19) Å-2.095(2) Å [average: 1.966Å for Zn(2)
and 1.957Å for Zn(3)]. The Zn-N bond distances are in the range
of 2.036(2)-2.077(2) Å [average: 2.070Å for Zn(1); 2.052 Å for
Zn(2) and 2.048Å for Zn(3)] (Table S2 in the supporting
information). Similar to the structure of 1, compound 2 can be
understood by considering simpler building units. Thus the
metalloporphyrin units are linked through the Zn(2) and Zn(3)
units forming a one-dimensional chain as shown in Figure 2a. Of
the two terephthalate units, one of them links two 1D chains
3 24 8 8 4 4 2 5 2
Structure of [Zn (C40H N )(C H O ) (DMF)](DMF) (H O)12, 2:
Compound 2 crystallizes in triclinic P-1 space group. The
asymmetric unit of the framework of 2 contains one TPyP ligand,
two 1,4-benzenedicarboxylic acid and three crystallographically
2
+
distinct Zn ions (Figure S2 in the supporting information). Zn(1)
exhibits a distorted square pyramidal geometry with four pyrrole
nitrogen atoms [N(1), N(2), N(3) and N(4)] and one oxygen atom
from the solvent molecule [O(1)]; and Zn(2) and Zn(3) are in a
distorted octahedral geometry with four carboxylate oxygen
[
O(2), O(3), O(4) and
(a)
forming
a
two-dimensional layer (Figure 2b). The two
dimensional layers are further cross-linked by the other
terephthalate unit forming a three-dimensional structure (Figure
2c). The 3D structure possesses a large one-dimensional
channel of 27ÅХ23Å (shortest atom-atom contact distance not
including the van der waals radii). The disordered solvent
molecules occupy these channels.
A PLATON calculation
indicates a solvent accessible volume of ~60% in this structure.
(
b)
(
a)
This article is protected by copyright. All rights reserved.

Chemistry - A European Journal
10.1002/chem.201700985
FULL PAPER
Out of the two 1,4-napthalenedicarboxylates one bridges the two
1D chains which results in the 2D layer (Figure 3b). These 2D
layers are further connected through the other 1,4-
napthalenedicarboxylate forming the three dimensional structure
(
b)
(
Figure 3c). The 3D structure possess a large one dimensional
2
cavity of 25.83Х23.72 Å where the disordered guest solvent
molecules reside. The solvent accessible void volume is 51%
(
(
calculated from PLATON).
a)
(
c)
(
b)
Figure 2. (a) Figure shows the connectivity between the Zn-porphyrinic units
through the metal-centers forming a one-dimensional unit, (b) The connectivity
between the 1D units and the 1,4-benzenedicarboxylate forming two-
dimensional arrangement, (c) The three-dimensional structure of 2 resulting
from the connectivity between the 2D arrangement and the carboxylates. The
solvent molecules are not shown for clarity.
(
c)
Structure of [Zn
3
(C40
H
24
N
8
)(C12
H
6
O
4
)
2
(DMA)
2
](H
2
O)
7
,
3:
Compound 3 crystallizes in monoclinic C2/c space group. The
asymmetric unit of the framework consists of 43 non-hydrogen
2
+
atoms. Two crystallographically independent Zn
ions are
present in the asymmetric unit (Figure S3 in the supporting
information). Zn(1) occupies a special position (4d) with a site
multiplicity of 0.5 and is octahedrally coordinated with four
nitrogen [N(1), N(2), N(1)(#1), N(2)(#1)] and two oxygens [O(5),
O(5)(#1)] from the solvent molecule. The coordination geometry
around Zn(2) is also octahedral with two nitrogens from the
pyridyl group of the porphyrin [N(3), N(4)] and four oxygens
Figure 3. (a) The connectivity between the Zn-porphyrinic units through the
metal centers forming one-dimensional network, (b) The connectivity
between the 1D units and the 1,4-napthalenedicarboxylate forming two-
dimensional arrangement, (c) The 3D structure of resulting from the
[
O(1), O(2), O(3), O(4)] from 1,4-napthalenedicarboxylic acid.
a
The average Zn-O and Zn-N distances are 2.567 Å and 2.033 Å
for Zn1; 1.955 Å and 2.068 Å for Zn(2) (Table S3 in the
supporting information). The porphyrin ring is essentially flat and
Zn(1) lies in plane with the porphyrin macrocycle. Structural
arrangement of 3 is similar as that of 2. In this case, the Zn(2)
links the metalloporphyrin units to form a 1D chain (Figure 3a).
3
connectivity between the 2D arrangement and the dicarboxylates. The solvent
molecules are not shown for clarity.
This article is protected by copyright. All rights reserved.

Chemistry - A European Journal
10.1002/chem.201700985
FULL PAPER
Table 1. Crystal Data and Structure Refinement Parameter
1
2
3
Empirical Formula
FormulaWeight
Crystal System
Space Group
a (Å)
b (Å)
c (Å)
α (deg)
β (deg)
C
56
H
32
N
14
O
28 Zn
5
C
56
H
32
N
8
O
9
Zn
3
C
64 36 8 3
H N O10Zn
1675.91
Orthorhombic
I 2 2 2
10.3770(7)
17.2302(11)
28.198(2)
90
90
90
5041.7(6)
2
1157.07
Triclinic
P-1
1273.18
Monoclinic
C 2/c
14.123(3)
36.166(9)
18.341(4)
90
99.380(6)
90
14.1504(15)
19.257(2)
19.430(2)
69.873(6)
82.011(6)
75.484(7)
4804.4(10)
2
γ (deg)
Volume (Å )
3
9242(4)
8
Z
Temperature (K)
120(2)
1.104
1.236
120(2)
0.800
0.778
120(2)
0.915
0.815
-3
ρ
c
(gcm )
-1
μ(mm )
θ range (deg)
Wavelength (Å)
R1, wR2 [I>2σ(I)]
R1, wR2 (all data)
2.92-25.00
0.71073
0.0692, 0.1991
0.0833,0.2088
1.118-27.650
0.71073
0.0521, 0.1120
0.1040, 0.1231
2.93-25
0.71073
0.0866, 0.2026
0.1859, 0.2429
a
2
2
c
2 2 1/2
2
2
2
,
2
R
1
= Σ||F
o
| − |F
c
||/Σ|F
o
|; wR
2
= {Σ|w(F
o
− F
)]/Σ [w(F
o
) ]} . w = 1/[ρ (F
o
) + (aP) + bP]. P = [max (F
o
O) + 2(F
c
) ]/3, where a =
0.1151 and b = 14.5934 for 1, a = 0.0435and b =0.0000 for 2, a = 0.1346 and b = 0.0000 for 3.
Photophysical Studies:
The fluorescence emission is characterized by the enhancement
of emission bands in the region around ~620-660 nm while the
band at 734 nm is quenched for the compounds. This spectral
change in the emission bands could be due to insertion of zinc
into the porphyrin core. The bands observed at 668nm, 662nm
All the compounds have the porphyrinic ring system and were
expected to exhibit interesting absorbance and emission
[
11]
behavior.
To investigate the optical behavior of the
compounds, we have evaluated the pristine ligand, tetra-(4-
pyridyl)porphyrin as well. The UV-vis spectrum of the ligand
tetra-(4-pyridyl)porphyrin exhibits an intense Soret band at 349
g
and 663 nm for 1, 2 and 3 could be due to the e → a2u transition.
nm [a1u→e
64, 555, 587 and 644 nm [a2u→e
spectra of the compounds exhibit a red-shift compared to the
ligand H TPyP. Similar observations have made in many MOF
compounds. Thus the soret band was observed to be shifted
to 394, 395 and 388 nm for the compounds 1, 2 and 3
respectively. The insertion of zinc within the ring resulted in the
g
(allowed)] along with a series of Q bands at 425,
Thermal Stability Studies:
4
g
(forbidden)]. The UV-vis
The thermal stability of the compounds was investigated
employing thermogravimetric analysis (TGA). The TGA study of
1 (Figure S6 in the supporting information) exhibits weight loss
of 35.1% in the range of 30-295ºC which would correspond to
the loss of 5 DMA and 8 H O molecules (calc.34.6%). A weight
2
loss of 48.7% in the range of 290-500ºC could be due to loss of
the porphyrin and three nitrate molecules (calc. 48.1%).
2
[
12]
2
disappearance of a number of Q-bands. The free base, H TPyP
has a rectangular geometry with a D2h symmetry and after the
metalation the four nitrogens of the pyrrole become equivalent
which results a change in geometry (D4h symmetry) and reduces
the number of Q-bands. Thus the Q-bands appear in the range
In the case of 2 the observed weight loss of 57% in the
temperature range of 30ºC to 200ºC may be due to the loss of 6
DMF and 12 H O molecules (calc.56.5%). A flat region in the
2
temperature range 200-400ºC indicates that the framework may
be stable until 400ºC. A steady weight loss was observed above
400ºC suggesting a collapse of the framework. We explored the
possibility of removing the solvent molecules from 2 under
vacuum. The vacuum treated samples (Figure S6 in the
supporting information) exhibits a small initial weight loss which
could be due to surface adsorbed water molecules. The
evacuated compound exhibits a sharp weight loss at 400ºC
suggesting the collapse of the framework. A PXRD study on the
evacuated sample also indicates that the compound is
crystalline and retains the structural integrity on the removal of
guest solvent molecules (Figure S7) in the supporting
452 - 598 nm in 1; 446 - 594 nm in 2 and 451nm- 600 nm in 3
(
Figure S4 in the supporting information).
Solid state photoluminescence studies were carried out on the
powdered samples of the compounds 1-3, as well as the ligand
H
2
TPyP at room temperature using an excitation wavelength of
390 nm (Figure S5 in the supporting information). The emission
bands observed in the range of 445-670 nm range are due to
the intraligand emission from porphyrin ligand. An emission
bands observed at ~446 nm for the ligand as well as for the
g
synthesized compounds could be due to the e → a1u transition.
This article is protected by copyright. All rights reserved.

Chemistry - A European Journal
10.1002/chem.201700985
FULL PAPER
information). The evacuated sample was immersed in DMF
which readily absorbs the solvent molecules. The solvent re-
absorbed sample behaves similar to the as-synthesized sample
under TGA studies (Figure S6 in the supporting information).
Compound 3 exhibits similar behavior as that of compound 2 in
the initial TGA studies. A weight loss of ~28.5% in the
temperature range of 30-250ºC corresponds to the loss of DMA
and water molecules (calc.27.8%). A broader weight loss of 65%
in the temperature range 350ºC-600ºC corresponds to the
collapse of framework.
100% in compound 2 whereas it was around 70% in compound
3. The copper-exchanged products were also fully characterized
similar to the starting compounds (Figure S16, Figure S17 in the
supporting information).
Catalytic activity of Cu∊2 and Cu∊3:
Activation of Cu∊2 and Cu∊3: Cu∊2 and Cu∊3 was soaked in
MeOH at room temperature for a period of 6 days. It was filtered
and kept in vacuum oven at 60°C to get the active Cu∊2 and
Cu∊3 which was used for the catalysis.
The final calcined product in all the three cases was found to be
ZnO (JCPDS: 36-1451) (Figure S8 in the supporting information).
O
O
R
O
NH
Cu∈2/Cu∈3 (5 mol%)
+
R-NH
2
O
r.t.
Gas Adsorption Studies:
To probe the possible openness of the structure, we carried out
O
1
mmol
1 mmol
N
2
adsorption studies. The compound was degassed and
R
activated at 120ºC for 1 and 200ºC for 2. The nitrogen
NH
O
O
O
adsorption measurements were carried out employing Belsorp
Cu]2
+
[
O
Max equipment at liq N
type-I isotherm for both the compounds up to a relative pressure
P/P ) of 1.0 bar (Figures S9 and S10 in the supporting
information). The layer compound (1) exhibited a BET surface
2
temperature. The studies indicated a
O
2
-H O
(
0
CuI
R
2
-1
HN
O
area of 93m g and the three-dimensional compound (2)
Cu
HO
2
-1
O
H
O
exhibited a much larger surface area of 400 m g . Under the
conditions of the activation, compound 3 was found to lose the
original crystallinity and did not exhibit any significant adsorption
O
H
H
O
H
(
Figures S11 in the supporting information)
R-NH
2
Scheme 2. Synthesis of different β-enaminoester using Cu∊2 and Cu∊3 as
catalyst under solvent-free condition
Metal ion metathesis: We have made attempts to prepare
isomorphous frameworks of 1, 2 and 3 with other first-row
transition elements employing similar synthesis protocols. Our
attempts were not successful and we employed a post-synthetic
modification of the compounds 1-3 by performing a metal-ion
exchange through the metathetic pathway. Earlier studies
towards the preparation of isomorphous frameworks through this
approach were successful and there were reports of the
(
a) Chemo and regioselective enamination of β-ketoester:
Compounds 2 and 3 were found to exchange for copper and we
desired to explore the possible catalytic behavior of the Cu∊2
and Cu∊3 samples. It has been shown that a coordinatively
unsaturated copper (II) centers can act as a good Lewis acid
catalytic center for many organic reactions such as Henry
reaction, Diels-Alder reaction, azide-alkyne cycloaddition, ring
[
13]
systematic metal exchange in MOF compounds. It appears
that a successful and facile exchange is possible whenever
there is a solvent molecule binds with the metal along with a
reasonable openness of the structure. The present compounds
have coordinated solvent molecules as well as porosity in their
structures, which made us believe that the present structures
could be amenable for the metal exchange. To this end, we
[
14]
opening of epoxides etc.
β-enamino esters have been
considered as an important feed stock for the synthesis of a
number of anti-inflammatory, antibacterial and antitumor
[
15]
pharmaceuticals. Among the many synthetic routes available
[
16]
2
+
2+
2+
in the literature
with amines is considered to be one of the best. Many catalysts
such as Zn(OAc) .6H O/MgSO , NaAuCl , ZrOCl .8H O, InBr
3
the condensation of β–dicarbonyl compounds
have made attempts with Co , Ni and Cu ions as possible
2
+
exchanging ions for Zn ions. All the ion-exchange reactions
were carried out at room temperature in DMF solution of the
corresponding metal salts and the compounds 1-3 were
immersed in the metal salt solution. The metal salt solutions
were replenished every alternate day and the exchange
reactions were carried out for a period of 12 days. We find that
the copper ions exchange facilely in the case of compound 2
and 3 whereas other ions are partially exchanged which were
confirmed by EDAX (Figure S12, Figure S13 in the supporting
information) and AAS analysis (Figure S14, Figure S15 in the
supporting information). In the case of compound 1 no metal –
ion exchange was observed even after many attempts over
several days. The copper ion exchange was found to be close to
2
2
4
4
2
2
[17]
etc. have been employed for this reaction. Unfortunately, the
separation and recovery of the catalysts after the reaction have
been a problem. Recently, a Cu MOF was shown to be an
II
effective catalyst for the enamination of β-ketoester with good
[
18]
selectivity. We desired to test the catalytic activity of Cu-
exchanged compounds, Cu∊2 and Cu∊3 for this reaction. The
synthesis of β-enaminoesters by the condensation reaction of
primary aromatic amines with β-ketoester was carried out under
solvent free conditions at room temperature (Table 2). For this
reaction ethyl acetoacetate (1 mmol), aromatic amine (1 mmol)
and Cu∊2/Cu∊3 (0.05 mmol) were stirred at room temperature
for 1 hr. The reaction was quenched by adding distilled water.
This article is protected by copyright. All rights reserved.

Chemistry - A European Journal
10.1002/chem.201700985
FULL PAPER
The catalyst was filtered off and the filtrate was extracted with
ethyl acetate (2Х10 mL) and dried over magnesium sulphate.
The solvent was evaporated under reduced pressure to obtain
the desired product. The results are summarized in Table 2. The
reaction probably preceded by the nucleophilic attack of the
amine with the ketone of the ethyl acetoacetate, giving rise to
the corresponding amide. Such studies have been reported
(b) Synthesis of propargylamine derivatives by three
component coupling reaction (A -coupling)
3
Propargylamines and their derivatives are known to be an
important intermediate in the preparation of useful
[
16]
heterocycles. One of the established routes for the synthesis
of propargylamine is to react an aldehyde, alkyne and amine
3
(commonly known as A -coupling), in the presence of a catalyst.
[
15]
II
before. The same reaction was also carried out without the
catalyst as well as in the presence of the parent Zn-compounds
A number of Cu complexes have been shown to be a good
[17]
3
catalyst for this reaction. We have attempted the A -coupling
(
2 and 3) under similar condition. We did not observe the
reaction using the Cu-exchanged 2 and 3 (Cu∊2 and Cu∊3)
formation of the amide even after 12 hrs of the reaction (Table 2). employing para-formaldehyde/different aromatic aldehydes with
piperidine and phenyl acetylene. In a typical reaction, the
Table 2. Results for the β-enaminoester formation using Cu∊2 and Cu∊3
as catalyst under solvent-free condition
aldehyde (1 mmol), piperidine (1 mmol) and phenylacetylene (1
mmol) were stirred in the presence of 0.04 mmol of Cu∊2/Cu∊3
at 40ºC in DCM under nitrogen for 10-12 hrs. After the reaction
the catalyst was filtered and the DCM was evaporated under
reduced pressure to obtain the product. The different reactions
undertaken in the present study are listed Table 3. The catalytic
reactions gave the desired product with good yields.
Entry Catalyst
R
Time (h)
Yield (%)
96
92
97
93
89
87
92
90
1
2
3
4
5
6
7
8
9
Cu∊2
Cu∊2
Cu∊2
Cu∊2
Cu∊3
Cu∊3
Cu∊3
Cu∊3
2
Ph
1
1
1
1
1
1
1
1
4-Br-Ph
4-I-Ph
4-OMe-Ph
Ph
4-Br-Ph
4-I-Ph
4-OMe-Ph
Ph
Table 3. Results of Cu∊2 and Cu∊3 catalyzed three component coupling
reaction
Entry
Catalyst
Cu∊2
Cu∊2
Cu∊2
Cu∊3
Cu∊3
Cu∊3
2
R
H
Time (h)
10
12
10
10
12
10
24
24
Yield (%)
97
94
93
91
87
91
<2
<3
1
2
3
4
5
6
7
8
9
12
No
Ph
4-F-Ph
H
Ph
reaction
No
reaction
No
1
0
1
3
Ph
Ph
12
12
1
No
4-F-Ph
catalyst
reaction
H
H
H
H
H
3
O
+
No catalyst
CuI
Cu(OAc)
24
10
10
<4
84
79
Cu∈2/Cu∈3 (4 mol%)
+
R
1
1
0
1
N
H
H
DCM/40°C
N
2
1mmol
1mmol
1mmol
R
The same reaction was also carried out in the absence of the
catalyst as well as in the presence of Zn-compounds, which
resulted in the formation of negligible amounts of the
propargylamine derivative (Table 3). It may be noted that the
catalytic activity observed in the present study is comparable to
those obtained employing other Cu-salts (Table 3). The
recyclability of the catalysts was tested for this reaction and the
catalysts were found to be active for at least 3 times (Figures
S20 and S21 in the supporting information).
H
N
OH
+
R
O
N
H
R
H
+
[Cu]
Ph
N
2
H O
Ph
H
R
H
Cu]+
[
[
Cu]2+
Ph
H
(
c) Regioselective Alkyne-Azide Cycloaddition :
N
Copper based compounds have also been employed as a
catalyst for the addition of organic azides and terminal alkynes
and such reactions are known as Huisgen cycloaddition.
Though majority of the reactions reported in the literature
R
[
18]
Scheme 3. Cu∊2 and Cu∊3 catalyzed three component coupling reaction
I
II
employs Cu salts, there are reports of the use of Cu
[
19]
compounds as well in the literature for this reaction. As part of
this study, we have explored this reaction employing Cu∊2 and
Cu∊3 as the catalyst. A reaction of benzyl azide with various
phenyl acetylenes have been attempted in the presence of
In order to test the recyclability and reusability of the catalysts
Cu∊2 and Cu∊3), the catalysts recovered after washing with
ethyl acetate and methanol was employed for the same reaction.
Our studies clearly indicate that the catalyst is active for upto
four cycles (Figures S18, S19 in the supporting information).
(
This article is protected by copyright. All rights reserved.

Chemistry - A European Journal
10.1002/chem.201700985
FULL PAPER
Cu∊2/Cu∊3 to obtain the 1,4-regioisomer. To this end, benzyl Conclusions
azide (1 mmol), substituted phenyl acetylene (1 mmol) were
reacted in the
The synthesis, single crystal structures, metal exchange through
metathetic route have been carried out on three porphyrin based
metal-organic framework compounds. The compounds have
two- and three- dimensionally extended structures formed by the
connectivity between the porphirinic units and metals through
N
3
Cu∈2/Cu∈3 (5 mol%)
N
N
N
N
N
R
+
R
R
+
DCM/45°C
N
the carboxylates. A new nitrate binding mode has been
(1 mmol)
(
1 mmol)
a
observed for the first time in porphyrinic MOFs. The metal-
exchanged (copper) compounds, Cu∊2 and Cu∊3 exhibits
excellent catalytic behavior with good yields and selectivity. Our
continuing research in this area suggests that many related
compounds can be prepared by employing subtle variations in
the synthetic compositions and conditions. We are actively
pursuing this lead.
b
N
N
R
N
Cu(II)
R
H
H+
R
Cu(I)
H+
Experimental Section
N
N
3
N
R
Materials:
The
chemicals
Zn(NO
3
)
2
.4H
2
O,
3 2 2
Cu(NO ) .3H O,
N
dimethylformamide (DMF), dimethylacetamide (DMA), methanol (MeOH),
acetone were purchased from SDfine, India and 5,10,15,20-tetrakis(4-
Cu(I)
2
pyridyl)porphyrin(H TPyP),
1,4-benzenedicarboxylic
acid,
1,4-
Scheme 4. Cu∊2 and Cu∊3 catalyzed Alkyne-Azide cycloaddition
napthalenedicarboxylic acid were obtained from Sigma-Aldrich and used
as received.
Synthesis:
presence of 0.05 mmol of Cu∊2/Cu∊3 in DCM under nitrogen
atmosphere at 45°C for 5 hrs. After the reaction, the catalyst
was filtered and the solvent was evaporated under vacuum. The
product was found to be 1,4-substituted triazole and the results
are summarized in Table 4. The catalyst was found to be active
for this reaction upto four cycles, which indicates the reusability
of the catalyst. A blank reaction in the absence of the catalyst as
well as in the presence of initial Zn compounds (2 and 3) did not
yield the desired triazole product (Table 4).
All the compounds were synthesized employing solvothermal method.
In a typical synthesis for 1, tetra-(4-pyridyl)porphyrin (H
mmol = 0.024 gm); 1,4-benzenedicarboxylic acid (0.08 mmol=0.012 gm)
and Zn(NO .4H O (0.2 mmol = 0.058 gm) were added with 2 ml DMA in
2
TPyP) (0.04
3
)
2
2
a 7 ml polytertafluoroethylene (PTFE) lined autoclave (stainless steel).
The reaction mixture was heated at 100°C for 3 days, which resulted in
formation of purple colored rod shaped crystals. The crystals were
filtered, washed (dry methanol) and vacuum-dried at room temperature
(Yield ~ 58% based on Zn).
Table 4. Cu∊2 and Cu∊3 catalyzed Alkyne-Azide cycloaddition
Compound 2 and 3 were also prepared employing similar synthetic
procedure (see Table 5)
Entry Catalyst
R
Time (h)
Yield of
%)
a
(
1
2
3
4
5
6
7
8
Cu∊2
Cu∊2
Cu∊3
Cu∊3
2
3
Ph
4-F-Ph
Ph
4-F-Ph
Ph
Ph
5
5
5
5
10
10
10
10
97
94
92
90
Cu- exchange: The Copper exchange studies were carried out at room
temperature by soaking 100 mg of the compound in the metal nitrate (0.1
M) solution in DMF for 12 days. The soak solution was replenished every
alternate day for facilitating the ion-exchange. The cation- exchanged
products were washed thoroughly with DMF. The products after washing
was soaked in pure DMF for another 6 days to remove any excess metal
salt occupying the pores of the compound.
No reaction
No reaction
<3
8
No Catalyst
Cu(NO
Ph
Ph
3
)
2
.3H
2
O
Initial Characterizations and Physical Measurements: All the
prepared samples were characterized by a number of techniques.
Elemental analysis (C, H, N) was carried out using Thermo Finnigan EA
Flash 1112 series. Powder X-ray diffraction (PXRD) patterns were
recorded employing Philips X’pert in the 2θ range of 5-50° (Cu Kα
radiation). The simulated powder XRD patterns were generated from the
single crystal structures using Mercury software (version 1.4.1). The
experimental PXRD pattern was found to be entirely consistent with the
simulated PXRD patterns for the compounds 1-3 which indicates phase
purity (Figures S24 in the supporting information). The IR spectrum of the
ligand as well as the compounds 1-3 were recorded in the mid IR region
The structural integrity of the catalyst after repeated use in this
reaction was checked employing PXRD, which indicates that the
catalyst has the same pattern as the initial compounds (Cu∊2,
Cu∊3) (Figures S22 and S23 in the supporting information ). The
3 2 2
same reaction when carried out employing Cu(NO ) , 3H O gave
the desired triazole product with a small yield (8%) after 10 hrs.
This suggests that the framework copper plays an important role
in this reaction.
This article is protected by copyright. All rights reserved.

Chemistry - A European Journal
10.1002/chem.201700985
FULL PAPER
-
1
(
4000-400 cm ) on a KBr pellet (PerkinElmer, SPECTRUM 1000) (Figure
at 120 K on an Oxford Xcalibur (Mova) diffractometer equipped with an
EOS CCD detector. For collecting data the X-ray was generated by
operating generator at 50kV and 0.8 mA using Mo Kα (λ = 0.71073 Å)
S25 in the supporting information). The room temperature IR spectra
exhibited sharp characteristics bands for the different functional groups
Table S4 in the supporting information). The ligand (H
[
20]
(
2
TPyP) exhibited a
radiation. Crysalis Red
was used for cell refinement and data
reduction. The structure was solved by direct methods and refined using
[
21]
WINGX (version 1.63.04a). The solvent molecules were found to be
disordered in all the three compounds and were accounted by the
SQUEEZE option present within the WinGX PLATON program. The
hydrogen positions were located initially from the difference Fourier maps,
and for the final refinement, the hydrogen positions were fixed in a
geometrically ideal position and refined employing a riding model. The
final refinements included the atomic positions for all the atoms,
anisotropic thermal parameters for all the non-hydrogen atoms, and
isotropic thermal parameters for all the hydrogen atoms. The details of
the structure solution and final refinement parameters are given in Table
Table 5. Synthesis Conditions for the Compounds 1-3
Compounds Composition
Temp (° C)
Time
Yield
(days)
1
2
3
5Zn(NO
BDC/1H
MA
3
)
2
.4H
2
O/2H
2
100
3
58
2
TpyP/537D
2. The CCDC numbers for the compounds 1, 2 and 3 are 1535743,
5Zn(NO
3
)
2
.4H
2
O/
100
100
3
3
44
51
1535744 and 1535745 respectively. These data can be obtained free of
2
2H BDC/1H TpyP/
2
charge from The Cambridge Crystallographic Data Center (CCDC) via
www.ccdc.cam.ac.uk/data_request/cif.
1300 DMF
5 Zn(NO
(1,4-
3 2 2
) .4H O/
2
Naphthalenedicarbo
xylic
acid)/1H TpyP/1075
2
Acknowledgements
DMA
GD would like to thank DST SERB for research grant and IISc
for infrastructure. SN thanks 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.
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.).
-1
band at ~3312 cm corresponding to the N-H stretching of the free base
porphyrin. No such N-H stretching frequency was observed in the
synthesized compounds (1-3), which suggests that zinc atom has been
introduced into porphyrin ring. Similar observations have been commonly
seen in many metallated porphyrin systems. A broad band in the region
-1
~
3600-3100 cm can be assigned to the presence of lattice water
Keywords: Porphyrin • MOF • Transmetallation • Catalysis •
-1
molecules (O-H stretch). A band at ~2900 cm can be assigned to the
aromatic C-H stretching. The bands at 1616, 1658 and 1609 cm for the
compounds 1, 2 and 3 respectively can be assigned to the coordinated –
COO moiety. The band at 1393 cm in 1 could be for the coordinated
-1
[
1]
a) S. J. Lindsey, Chem. Rev. 2015, 115, 6534-6620; b) J. P. Collman, R.
Boulatov, C. J. Sunderland, L. Fu Chem. Rev. 2004, 104, 561-588.
a) H. C. Zhou, J. R. Long, O. M. Yaghi, Chem. Rev. 2012, 112, 673–
-1
[
2]
nitrate.
674; b) L. R. MacGillivray, Metal Organic Frameworks: Design and
Applications; Wiley, New York, 2010; c) D. Farrusseng, Metal Organic
Frameworks: Applications from Catalysis to Gas Storage, Wiley-VCH,
New York, 2011.
Thermo- gravimetric analysis (TGA) was carried out in the presence of
nitrogen (flow rate = 20 mL/min) in the temperature range 30−800°C
heating rate = 5°C/min) (Figure S3). UV−Vis spectra of tetra-(4-
Pyridyl)porphyrin and the compounds 1-3 were recorded at room
temperature using a Perkin-Elmer Lambda 35 spectrophotometer (Figure
S6 in the supporting information). Room temperature solid state
photoluminescence studies were carried out using a PerkinElmer LS 55
luminescence spectrophotometer (Figure S5 in the supporting
information). EDAX analysis was carried out employing Quanta 200
FESEM (Figure S12 and Figure S13 in the supporting information).
(
[
3]
4]
a) P. Bhyrappa, S. R. Wilson, K. S. Suslick, J. Am. Chem. Soc. 1997,
119, 8492–8502; b) P. Bhyrappa, K. S. Suslick, Supramol. Chem. 1998,
9, 169–174; c) L. Pan, B. C. Noll, X. Wang, Chem. Commun. 1999,
157–158; d) D. W. Smithenry, S. R. Wilson, K. S. Suslick, Inorg. Chem.
2003, 42, 7719-7721.
[
a) B. F. Abrahams, B. F. Hoskins, R. Robson, J. Am. Chem. Soc. 1991,
13, 3606-3607; b) B. F. Abrahams, B. F. Hoskins, D. M. Michail, R.
1
Robson, Nature 1994, 369, 727–729; c) M. E. Kosal, J. H. Chou, S. R.
Wilson, K. S. Suslick, Nat. Mater. 2002, 1, 118-121; d) M. E. Kosal, J.
H. Chou, K. S. Suslick, J. Porphyrins Phthalocyanines 2002, 6, 377-
Atomic absorption spectroscopy (AAS) was recorded using PerkinElmer
1
Analyst 200 (Figures S14 and S15 in the supporting information).
H
NMR spectral data (Figures S26-S34 in the supporting information) was
collected using a Bruker 400 MHz spectrometer using CDCl as solvent
3
81; e) K. S. Suslick, P. Bhyrappa, J. H. Chou, M. E. Kosal, S.
Nakagaki, D. W. Smithenry, S. R. Wilson, Acc. Chem. Res. 2005, 38,
83 – 291; f) M. P. Byrn, C. J. Curtis, I. Goldberg, Y. Hsiou, S. I. Khan,
P. A. Sawin, S. K. Tendick, C. E. Strouse, J. Am. Chem. Soc. 1991,
13, 6549-6557; g) M. P. Byrn, C. J. Curtis, Y. Hsiou, S. I. Khan, P. A.
Sawin, S. K. Tendick, A. Terzis, C. E. Strouse, J. Am. Chem. Soc.
993, 115, 9480-9497; h) I. Goldberg, Chem. Eur. J. 2000, 6, 3863-
3
at room temperature. Chemical shifts are reported in ppm using
tetramethylsilane as the internal reference.
2
1
Single Crystal Structure Determination:
1
The structure of the compounds (1-3) was determined using single
crystal X-ray diffraction. A suitable single crystal of each compound was
carefully selected under a polarizing microscope and mounted carefully
to a thin fiber loop using paratone oil. Single crystal data were collected
3870. i) I. Goldberg, CrystEngComm 2002, 4, 109-116; j) M. Shmilovits,
Y. Diskin-Posner, M. Vinodu, I. Goldberg, Cryst. Growth Des. 2003, 3,
855-863.
This article is protected by copyright. All rights reserved.

Chemistry - A European Journal
10.1002/chem.201700985
FULL PAPER
Looper, Angew. Chem., Int. Ed., 2011, 50, 684-687.
[
[
20] H. B. Chen, Y. Zhaoa, Y. Liao, RSC Adv., 2015, 5, 37737-37741.
21] a) R. Huisgen, Pure Appl. Chem. 1989, 61, 613-628; b) R. Huisgen,
G. Szeimies,; L. Moebius, Chem. Ber. 1967, 100, 2494-2507.
[5]
a) M. H. Beyzavi, N. A. Vermeulen, A. J. Howarth, S. Tussupbayev, A. B.
League, N. M. Schweitzer, J. R. Gallagher, A. E. Platero-Prats, N.
Hafezi, A. A. Sarjeant, J. T. Miller, K. W. Chapman, J. F. Stoddart, C. J.
Cramer, J. T. Hupp, O. K. Farha, J. Am. Chem. Soc. 2015, 137, 13624–
[22] a) C. W. Tornøe, C. Christensen, M. Meldal, J. Org. Chem. 2002, 67,
3057-3064; b) V. V. Rostovtsev, L.G. Green, V. V. Fokin, K. B.
Sharpless, Angew. Chem. Int. Ed. 2002, 41, 2596-2599.
13631; b) J. A. Johnson, B. M. Petersen, A. Kormos, E. Echeverria, Y.
[
23] CrysAlis Pro Red, version 1.171.33.34d, Oxford Diffraction Ltd., Abingdon,
S. Chen, J. Zhang, J. Am. Chem. Soc. 2016, 138, 10293-10298; c) G.
Lin, H. Ding, D. Yuan, B. Wang, C. Wang, J. Am. Chem.
Oxfordshire, England, 2009.
Soc. 2016, 138, 3302-3305; d) P. Deria, D. A. Go
-
, I. Hod,
[24] G. M. Sheldrick, SHELXS-97, Program for crystal structure solution and
refinement, University of Göttingen, Germany, 1997.
R. Q. Snurr, J. T. Hupp, O. K. Farha, J. Am. Chem.
Soc. 2016, 138, 14449-14457; e) S. Huh, S. J. Kimb, Y. Kim, Cryst Eng
Comm. 2016, 18, 345-368 and references cited therein.
[
6] Z. Wang, S. M. Cohen, Chem. Soc. Rev. 2009, 38, 1315-1329.
7] a) M. Lalonde, W. Bury, O. Karagiaridi, Z. Brown, J. T. Hupp, O. K.
Farha, J. Mater. Chem. A. 2013, 1, 5453-5468; b) Y. Kim, S. Das, S.
Bhattacharya, S. Hong, M. G. Kim, M. Yoon, S. Natarajan, K. Kim,
Chem. Eur. J. 2012, 18, 16642-16648; c) K. S. Asha, R. Bhattacharjee,
S. Mandal, Angew. Chem. Int. Ed. 2016, 55, 11528-11532.
[
[
8] a) Z. Zhang, L. Zhang, L. Wojtas, P. Nugent, M. Eddaoudi, M. J.
Zaworotko, J. Am. Chem. Soc. 2012, 134, 924-927; b) W. Morris, B.
Volosskiy, S. Demir, F. G´andara, P. L. McGrier, H. Furukwa, D. Cascio,
J. F. Stoddart, O. M. Yaghi, Inorg. Chem., 2012, 51, 6443-6445.
[
9] a) D. A. Safin, K. M. N. Burgess, I. Korobkov, D. L. Bryce, M. Murugesu,
CrystEngComm. 2014, 16, 3466-3469; b) L. Hashemi, A. Morsali,
CrystEngComm. 2014, 16, 4955-4958.
[
10] a) D. Dermitzaki, C. P. Raptopoulou, V. Psycharis, A. Escuer, S. P.
Perlepes, T. C. Stamatatos, Inorg. Chem. 2015, 54, 7555-7561; b) B.
Wang, Z. Zang, H. Wang, W. Dou, X. Tang, W. Liu, Y. Shao, J. Ma, Y.
Li, J. Zhou, Angew. Chem. Int. Ed. 2013, 52, 3756-3759.
[11] a) R. Grigg, W. D. J. A. Norbert, J. Chem. Soc. Chem. Commun.
1992, 1298 – 1300; b) D. F. Marsh, L. M. Mink, J. Chem. Educ. 1996,
73, 1188-1190; c) S. Abad, M. Kluciar, M. A. Miranda, U.
Pischel, J. Org. Chem. 2005, 70, 10565 – 10568; d) A. Fateeva, P. A.
Chater, C. P. Ireland, A. A. Tahir, Y. Z. Khimyak, P. V. Wiper, J. R.
Darwent, M. J. Rosseinsky, Angew. Chem. Int. Ed. 2012, 51, 7440 –
7444.
[12] a) S. Bhattacharya, M. Gnanavel, A. J. Bhattacharyya, S. Natarajan,
Cryst. Growth. Des. 2014, 14, 310-325; b) S. Bhattacharya, A. J.
Bhattacharyya, S. Natarajan, Inorg. Chem. 2015, 54, 1254-1271.
13] a) S. Das, H. Kim, K. Kim, J. Am. Chem. Soc., 2009, 131, 3814-3815;
b) D. Denysenko, T. Werner, M. Grzywa, A. Puls, V. Hagen, G.
[
Eickerling, J. Jelic, K. Reutere, D. Volkmer, Chem. Commun., 2012, 48
1236-1238.
[14] a) J. Park, J. R. Li, Y. P.Chen, J. Yu, A. A. Yakovenko, Z. U. Wang, L. B.
Sun, P. B. Balbuena, H. C. Zhou, Chem. Commun., 2012, 48, 9995-
9997; b) S. K. Yoo, J. Y. Ryu, J. Y. Lee, C. Kim, S. J. Kim, Y. Kim
Dalton Trans., 2003, 1454-1456; c) D. A. Evans, S. J. Miller, T. Lectka,
P. V. Matt, J. Am. Chem. Soc., 1999, 121, 7559-7573; d) Y. Gong, T.
Wu, P. G. Jiang, J. H. Lin, Y. X. Yang, Inorg. Chem., 2012, 52, 777-784;
e) D. Jiang, T. Mallat, F. Krumeich, A. Baiker, J. Catal., 2008, 257, 383-
390; f) I. H.Hwang, J. M. Bae, W. S. Kim, Y. D. Jo, C. Kim, Y. Kim, S. J.
Kim, and S. Huh, Dalton Trans. 2012, 41, 12759-12765.
[
15] a) N. N. Salama, K. R. Scott, N. D. Eddington, Biopharm. Drug
Dispos.,2004, 25, 227-236; b) N. D. Eddington, D. S. Cox, M. Khurana,
N. N. Salama, J. P. Stables, S. J. Harrison, A. Negussie, R. S. Taylor,
U. Q. Tran, J. A. Moore, J. C. Barrow, K. R. Scott, Eur. J. Med. Chem.,
2003, 38, 49-64; (c) A. P. Marcus, R. Sarpong, Org.Lett., 2010, 12,
4560-4563.
[
16] a) A. R. Katritzky, A. E. Hayden, K. Kirichenko, P. Pelphrey, Y. Ji,
J. Org. Chem., 2004, 69, 5108–5111; b) D. S. Reddy, T. V. Rajale, K.
Shivakumar, J. Iqbal, Tetrahedron Lett., 2005, 46, 979–982.
[
17] a) R. K. Vohra, J. L. Renaud, C. Bruneau, Collect. Czech.Chem.
Commun., 2005, 70, 1943-1952; b) A. Arcadi, G. Bianchi, S. D.
Giuseppe, F. Marinelli, Green Chem., 2003, 5, 64-67; c) Z. H. Zhang,
T. S. Li, J. J. Li, Catal. Commun., 2007, 8, 1615-1620; d) Z. H. Zhang,
L. Yin, Y. M. Wang, Adv. Synth. Catal., 2006, 348, 184-190.
[18] Y. Zhao, D. S. Deng, L. F. Ma, B. M. Ji, L. Y. Wang, Chem. Commun.,
2013, 49, 10299-10301.
[19] a) R. K. Arigela, R. Kumar, S. Samala, S. Gupta, B. Kundu, Eur. J. Org.
Chem.,2014, 6057-6066; b) G. Naresh, R. Kant, T. Narender, Org. Lett.,
2014, 16, 4528-4531; c) M. J. Gainer, N. R. Bennett, Y. Takahashi, R. E.
This article is protected by copyright. All rights reserved.

Chemistry - A European Journal
10.1002/chem.201700985
FULL PAPER
Entry for the Table of Contents (Please choose one layout)
Layout 1:
FULL PAPER
[
a]
[a]
Synthesis of three new porphyrin
based MOFs are presented. The
porous porphyrinic MOFs have
been shown to undergo facile
metal-exchange with copper. The
copper-exchanged compounds
exhibit excellent catalytic
Gargi Dutta, Ajay Kumar Jana
[
a]
and Srinivasan Natarajan*
Page No. – Page No.
Assembling Porphyrins into
Extended Network Structures
Employing Aromatic
Dicarboxylates: Synthesis, Metal-
exchange and Heterogeneous
Catalytic Studies
behavior for important organic
reactions.
This article is protected by copyright. All rights reserved.