Flexible porphyrin tetracarboxylic acids for crystal engineering

Article abstract of DOI:10.1039/c0ce00510j

Tetrakis[4-(carboxymethyleneoxy)phenyl]porphyrin, a flexible tetraacid ligand, is a new attractive building block for the formulation of coordination polymers and hydrogen bonding supramolecular assemblies in the solid state.

Full text of DOI:10.1039/c0ce00510j

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COMMUNICATION
www.rsc.org/crystengcomm | CrystEngComm
Flexible porphyrin tetracarboxylic acids for crystal engineering†
Anirban Karmakar and Israel Goldberg*
Received 8th August 2010, Accepted 8th October 2010
DOI: 10.1039/c0ce00510j
Tetrakis[4-(carboxymethyleneoxy)phenyl]porphyrin, a flexible tet-
raacid ligand, is a new attractive building block for the formulation
of coordination polymers and hydrogen bonding supramolecular
assemblies in the solid state.
Metal–organic frameworks (MOFs) are highly ordered crystalline
coordination polymers with well-defined porous networks, having
1
enormous fundamental structural interest, due to their potential
applications in e.g., gas storage, molecular separations, sensing,
selective catalysis, molecular recognition and fabrication of nanoscale
2
reactors. Porphyrins are excellent building blocks for the construc-
3
tion of MOFs. They can be readily tailored, as programming
elements, with various molecular recognition functions on their
periphery, as well as with metal ions of different oxidation states and
4
coordination preferences in their core. The supramolecular
networking capacity of suitably functionalized porphyrin scaffolds
Scheme 1 A general scheme of the porphyrin tetraacid building block
and formation of porphyrin-based open framework solids have been
5
widely demonstrated in recent years. The square-planar tetradentate
appended with flexible spacer groups involved in this project, and the first
such system (TCMOPP) with an oxomethylene spacer used in this study.
tetra(3-/4-carboxyphenyl)porphyrin (TmCPP/TpCPP) derivatives
provide attractive scaffolds to this end due to their capacity to
interconnect into extended supramolecular arrays through exocyclic
with copper and zinc ions. We describe here the structural features, as
characterized by X-ray crystal structure determination, of the
porphyrin ligand, its methyl ester, and the only polymeric assemblies
with zinc and copper ions that could be resolved thus far in a crys-
talline form.
6,7
metal-ion templates. The rigidity and bulkiness of the tetraaryl-
porphyrin backbone are favorable for the generation of porosity
desired in practical applications. On the other hand, the use of flexible
peripheral functional groups may provide conformational freedom
and offer various possibilities for release of the steric strain imposed
by the metal–ligand association and relaxation of the network
architecture. In order to explore this potential, with a view to
construct more reactive and adjustable organic–inorganic hybrid
materials of larger diversity, we decided to expand on our earlier
studies with the TCPP system by examining the coordination poly-
merization behavior of the tetracarboxyporphyrin system with
various elements of added flexibility.
The TCMOPP was prepared on a mg scale by a three step
procedure. The first step involved the synthesis of the methyl-2-
(4-formylphenoxy) acetate starting material from commercially
available 4-hydroxybenzaldehyde (64% yield), by reacting the latter
with methyl bromoacetate in the presence of anhydrous potassium
carbonate and dry acetone. Standard porphyrin synthesis procedure
of condensation of methyl-2-(4-formylphenoxy) acetate with pyrrole
8
in propionic acid, in the second step, yielded the methyl tetra-ester (1,
Fig. 1a) of TCMOPP in 11% yield.‡ Alkaline hydrolysis of the tetra-
ester in the third step afforded TCMOPP (2, Fig. 1b and c) in 75%
yield (see ESI†).‡ X-Ray quality purple crystals of 1 were obtained by
slow evaporation from 4 : 1 ethylacetate : hexane solvent. Crystals
containing 2 were obtained in hydrothermal conditions by dissolving
In this communication we report on our preliminary findings in
this area, with the first such flexible system (Scheme 1). This involves
the synthesis of a newly expanded porphyrin tetraacid, tetrakis
[4-(carboxymethyleneoxy)phenyl]-porphyrin (TCMOPP), wherein
the tetraphenyl-porphyrin backbone is appended at the four lateral
positions by the aliphatic methyleneoxy-acetic acid functionality. This
scaffold was then utilized in coordination polymerization reactions
5
mg of 2 in 3 ml of dimethylformamide, heating the resulting mixture
ꢀ
in a capped glass vessel at 100 C for 2 days, followed by gradual
cooling to room temperature and slow crystallization. They represent
0
in fact a hydrogen bonded and hydrated ionic adduct, 2 of complex
School of Chemistry, Sackler Faculty of Exact Sciences, Tel Aviv
University, Ramat Aviv, 69978 Tel-Aviv, Israel. E-mail: anirban@iitg.
ernet.in; goldberg@post.tau.ac.il
composition (see crystal data below), of 2 with dimethylamine and
dimethylammonium ions (present in solution as a hydrolysis degra-
9
dation product of the DMF solvent ).
† Electronic supplementary information (ESI) available: Experimental
details on the synthesis of compounds 1–4 and the diffraction
Crystal data: 1, C H N O : formula weight 966.97, monoclinic,
46
56
4 12
ꢀ
experiment, atomic coordinates and hydrogen bonding data for
0
space group P2 /c, a ¼ 12.1131(4), b ¼ 16.3281(6), c ¼ 11.8739(4) A,
ꢀ
3
1
compound 2 , experimental and calculated powder diffraction diagrams
ꢀ
b ¼ 99.384(2) , V ¼ 2317.04(14) A , Z ¼ 2, T ¼ 110(2) K, Dcalc
¼
for compound 4. CCDC reference numbers 788145–788147 (for
structures 1, 3 and 4, respectively). For ESI and crystallographic data
in CIF or other electronic format see DOI: 10.1039/c0ce00510j
ꢁ3
ꢁ1
1
.386 g cm , m(MoKa) ¼ 0.10 mm , 18 406 collected data and 4661
ꢀ
unique reflections (qmax ¼ 26.36 ), Rint ¼ 0.091. The final R1 ¼ 0.064
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4
Fig. 1 Molecular structures of (a) 1, (b) TCMOPP in 2 , and (c) TCMOPP in 2 .
ꢁ
0
2ꢁ
0
for 2379 observations with F
for all unique data, |Dr|
o
> 4s(F
o
), R1 ¼ 0.151 (wR2 ¼ 0.161)
formed crystal lattices (1–4) in a given reaction was confirmed in each
case by repeated measurements of the unit-cell dimensions from
randomly chosen single crystallites. The bulk purity of 4 was also
confirmed by perfect fit between the calculated and experimental
powder X-ray diffraction analysis (see ESI†).
ꢀ
e A . Compound 2 ,
ꢁ3
0
#
0.26
4
ꢁ
2ꢁ
+
[
(C52
H
34
N
4
O
12
)
$(C52
36 4 12 2 8 2 7
H N O ) $6(C H N )$4(C H N)$
ꢁ
2
(H
2
O)]: formula weight 2308.6, triclinic, space group P1, a ¼
ꢀ
1
2.0941(8), b ¼ 14.1888(10), c ¼ 17.1626(13) A, a ¼ 87.069(4), b ¼
ꢀ
ꢀ
3
88. 836(6), g ¼ 87.735(3) , V ¼ 2938.5(4) A , Z ¼ 1, T ¼ 110(2) K,
Crystal data: 3, C52
H
42Cu
2
N
4
O
16: formula weight 1105.98,
ꢁ
D
calc ¼ 1.305. Preliminary R1 ¼ 0.167 for 11 253 observations to
triclinic, space group P1, a ¼ 6.4557(2), b ¼ 13.1407(4), c ¼
ꢀ
ꢀ
ꢀ
qmax ¼ 27.0 . The asymmetric unit contains two crystallographically
independent TCMOPP entities. The amine/ammonium species were
found severely disordered in the crystal lattice, which resulted in poor
quality of the crystal and the diffraction data collected from it.
Correspondingly, this structure could not be analyzed further with
acceptable precision, though it provides an unequivocal identification
16.9417(6) A, a ¼ 76.069(2), b ¼ 88. 500(1), g ¼ 88.541(2) , V ¼
ꢀ
3
1394.18(8) A , Z ¼ 1, T ¼ 110(2) K, D ¼ 1.317, m(MoKa) ¼ 0.83
calc
ꢁ1
mm , 17 583 collected data and 6278 unique reflections (q
ꢀ
¼
max
27.46 ), R ¼ 0.042. The final R1 ¼ 0.062 for 4880 observations with
int
F
o
> 4s(F
o
), R1 ¼ 0.081 (wR2 ¼ 0.171) for all unique data, |Dr| #
ꢀ
ꢁ3
1.04 e A . The lattice-trapped water of solvation clearly identified in
difference-Fourier maps could not be precisely modeled by discrete
atoms due to severe disorder. Its contribution was subtracted from
the diffraction pattern by the Squeeze method in the PLATON
0
of the contents of 2 and the molecular structure of the porphyrin
species. It is clear, however, from the available structural model that
ꢁ
the COOH/COO groups (the reaction, carried out in a mildly basic
10
environment, was associated with either full or partial deprotonation
of the TCMOPP units and proton transfer to the amine Lewis base)
67 9 3
software. Compound 4, C67H N O17Zn : formula weight 1466.41,
ꢁ
triclinic, space group P1, a ¼ 10.8912(3), b ¼ 12.5679(3), c ¼
ꢀ
ꢀ
are surrounded by and interact with the amine/ammonium moieties
ꢀ
14.0268(4) A, a ¼ 100.727(1), b ¼ 101. 248(1), g ¼ 107.802(2) , V ¼
ꢀ
3
(at N/O distances within the range of 2.67–3.13 A), and no direct
1729.73(8) A , Z ¼ 1, T ¼ 110(2) K, D ¼ 1.408, m(MoKa) ¼ 1.11
calc
ꢁ1
porphyrin–porphyrin hydrogen bonding occurs. The supramolecular
mm , 19 046 collected data and 7454 unique reflections (q
¼
max
ꢀ
hydrogen bonding between the various units extends throughout the
0
27.00 ), R ¼ 0.037. The final R1 ¼ 0.071 for 5202 observations with
int
crystal in three dimensions. In 1 and 2 the porphyrin entities are
F
o
> 4s(F
ꢁ3
o
), R1 ¼ 0.101 (wR2 ¼ 0.230) for all unique data, |Dr| #
ꢀ
located on centers of inversion.
1.84 e A . In 3 and 4, the porphyrin entities are located on centers of
inversion.
4ꢁ
The molecular structures of 1 and 2 (in its TCMOPP and
2ꢁ
TCMOPP forms) in the corresponding crystals are illustrated in
Fig. 1. They are characterized in the two crystals by an essentially
planar porphyrin core, but varying orientations of the peripheral
substituents in accordance with the conformational flexibility
imparted to the molecular recognition functions of the TCMOPP
Disappointingly, product 3 represents an incomplete coordination
polymerization reaction between the CuTCMOPP metalloporphyrin
and the additional copper ions on the periphery. It reveals, instead,
supramolecular assemblies stabilized by a combination of equally
probable coordination and hydrogen-bonding interactions. The
resulting structure can be best described in the following modular
way. The copper-metalated porphyrin units are arranged in the
crystal in flat linear arrays. Adjacent inversion-related moieties along
the chain interact with one another through cis-related pairs of the
carboxylic arms which are bridged either by coordination to
ꢁ
building block. More specifically, the COOH/COO groups may
adapt a range of orientations, from horizontal to vertical, with respect
to the square molecular backbone of this ligand, allowing diverse
geometries of its supramolecular assembly with other species.
The reactions of TCMOPP with metal ions were carried out in
hydrothermal conditions, i.e., by heating stoichiometric mixtures
2 2
Cu(H O) connectors or by hydrogen bonding with the two mole-
(
in 1 : 3 molar ratio) of 2 with either Cu(NO
: 1 MeOH : NH OH) or Zn(NO $6H
DMF : EtOH) reagents, in a sealed reactor at about 80 C for either
4 or 48 hours. After gradually cooling the reactors to room
temperature, this led to metalation of the porphyrin cores with
3
)
2
$2½H
2
O (dissolved in
cules of water, as shown in Fig. 2. This model emerges from the
crystallographic refinement for which best convergence was obtained
for full occupancy of the water sites (O35 and O36) and 50% occu-
pancy for the exocyclic copper ion site (Cu2). At the coordination
sites (Fig. 2a), the Cu2 bridging ions enjoy mainly a square-planar
2
4
3
)
2
2
O (dissolved in 3 : 1
ꢀ
2
II
II
ꢀ
coordination environment with 1.867(4) and 1.978(4) A bonds to the
either Cu or Zn ions and formation of the supramolecular
crystalline adducts sustained by interporphyrin hydrogen bonding
and coordination through auxiliary exocyclic linkers, 3 [Cu(TC-
ꢀ
water ligands, 2.174(4) A to O23 and 2.063(3) A to O34, with another
ꢀ
ꢀ
close approach Cu2–O33 of 2.660(4) A. At the hydrogen bonding
2ꢁ
2+
MOPP) $Cu (H O) $(H O) ] and 4 {Zn [Zn(TCMOPP)(DMF)]
2
sites (Fig. 2b), the four indicated hydrogen bonding O/O interac-
ꢀ
tions are within 2.736–2.984(5) A. Similar interporphyrin
2
2
2
2
(DMF)
2
}$2(DMF) in decent yields.x The uniform identity of the
4
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Fig. 2 The two possible binding modes between neighboring inversion-related porphyrin entities: (a) primarily by coordination via the Cu(H
2 2
O) ions,
(
b) at sites without Cu by hydrogen bonding (dashed lines) through the two molecules of water O35 and O36. The marked H-bonding distances are:
ꢀ
ꢀ
ꢀ
ꢀ
O23/O35 2.827(5) A, O23/O36 2.736(5) A, O34/O35 2.862(5) A and O34/O36 2.984(6) A.
coordination through Cu(H
2 2
O) nodes has been observed earlier for
3c
PdTCPP and PtTCPP scaffolds. The structural formula of 3 should
4
ꢁ
thus be better described as {[Cu(H O) ] [Cu(TCMOPP )]}
2 2
2
{[Cu(TCMOPP)](H O) }.
2 4
From the topological point of view, the polymeric network in 3 can
be represented as a (2, 4)-connected binodal net with a Schl €a fli
symbol of {4 }{4} , with a 4-connected Cu1–TCMOPP and the 2-
connected Cu2 secondary building block units (SBUs).
2
2
11
The supramolecular chains formed by either coordination or
hydrogen bonding arrange in layered arrays, parallel to the (1,1,3)
plane of the crystal, which are held together sideways by additional
inter-chain hydrogen bonding between the water molecules O35 and
ꢁ
O36 of one chain and the COOH/COO functions of adjacent chains
(Fig. 3). The layered arrays tightly stack along to normal direction
with additional hydrogen bonds between their hydrophilic sites. View
of the entire crystal structure down the a-axis of the crystal reveals
zones of offset stacked columns of the porphyrin entities and channel
voids between them. The latter are centered at y ¼ ½ and z ¼ 0, being
accommodated by disordered molecules of the water crystallization
solvent.
Fig. 3 Layered self-assembly pattern of the component species in 3
parallel to the (1,1,3) plane of the crystal. In the horizontal direction,
adjacent porphyrin units either coordinate to one another through pairs
of Cu(H
associate
2
O)
2
connectors as shown here or in the absence of the Cu-ions
ꢁ
Formulation of coordination networks with zinc ions turned out
more successful, as the reaction of zinc nitrate with 2 led to the
formation of two-dimensional coordination polymers of 2 : 1
with
hydrogen-bonding
synthons
COOH/COO /
ꢁ
(
H
2
2
O) / OOC/HOOC to the two water species (as shown in Fig. 2b).
Dotted lines indicate hydrogen bonding between neighboring chains in
the vertical direction.
2
+
4ꢁ
Zn : ZnTCMOPP
stoichiometry. The polymeric layers are
ꢁ
parallel to the (1,1,1) plane of the crystal. The exocyclic zinc ions form
dinuclear clusters, the two inversion-related metals in the cluster being
bridged by the carboxylate functions of four different neighboring
porphyrin units in a paddle-wheel manner. In addition, each zinc ion
coordination environment located on centers of inversion, wherein
the two trans-axial coordination sites are blocked by the DMF
ligands (Fig. 4). The carboxylate groups connect to the zinc-ion pair
coordinates an extra DMF ligand. The inter-porphyrin connectors
ꢁ
2
1
1
thus consist of Zn (COO )
2
4
(DMF)
2
clusters of octahedral
in a m -h -h -bridging mode (the two O-sites of a given carboxylate
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Fig. 4 The paddle-wheel-type coordination polymerization into layered coordination networks in 4. (a) An enlarged view of the coordination synthon.
Molecules of DMF that associate to the zinc ions in the porphyrin centers are not shown. (b) Wire-frame illustration (only the zinc ions are denoted by
ꢁ
small spheres) of the polymeric layer parallel to (1,1,1) plane of the crystal, along with the DMF species coordinated to the zinc ions and those
accommodated in the interface between adjacent layers.
group connect to two different metal centers) in the equatorial plane
of this coordination octahedron, thus inducing coordination pattern
moiety is surrounded from above and below by two molecules of
DMF, but only one of them is coordinated to the central zinc ion at
ꢀ
in two dimensions. All the Zn–O coordination bonds are within
ꢀ
Zn–O ¼ 2.145(6) A, while the other fills the space on the concave
1
.975(3)–2.087(3) A and the Zn/Zn distance within the cluster is
side of the ligand. These DMF species are oriented approximately
perpendicular to the polymeric layers lining (along with the DMF
species attached to the exocyclic metals) their top and bottom
surface. Stacking of the polymeric networks along the normal
direction is thus stabilized by common dispersion, incorporating
also additional molecules of the DMF solvent into the interface
between adjacent polymers (Fig. 4).
ꢀ
2
.957(1) A. The porphyrin scaffold adopts a vane-shape, interacting
at the four ends with four different Zn2 connectors, and filling
effectively the interporphyrin space within the layer. The paddle-type
ꢁ
Zn (COO ) inter-coordination between porphyrin moieties is
2
4
observed here for the first time, although a small number of similar
coordination patterns with other carboxylic acid ligands has been
12
reported recently.
In topological analysis, the coordination network is composed of
the four-connected Zn1–TCMOPP units (considering the paddle-
In the porphyrin unit the internal zinc ion is five-coordinate. It is
ꢀ
disordered about the inversion center, deviating slightly (by 0.31 A)
wheel ensemble as a single node) and the four-connected Zn
2
paddle-
either up or down from the porphyrin plane towards the O-site of
wheel centers, thus representing a binodal (4,4)-connected net of
11
2
Al Os-type topology (Fig. 5).
4ꢁ
the axial DMF ligand. Thus, at any given site the ZnTCMOPP
4
098 | CrystEngComm, 2010, 12, 4095–4100
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scaffold (in comparison with the protoype TCPP building block) on
the thermal stability of the crystalline coordination materials it forms
cannot be assessed at this time due to the limited results available thus
far.
This research was supported by The Israel Science Foundation
(grant no 502/08).
Notes and references
ꢁ
1
‡
Compound 1. FT-IR (cm ): 3371(b), 2946(w, nC–H), 1751(s, nC]O
asymmetric), 1602(s, nC]C), 1506(s, nC]C), 1431(m, nC]O symmetric),
295(m), 1214(m, nC–O), 1177(s), 1075(m), 974(w), 801(s), 710(w), 604(w).
1
1
H-NMR (CDCl
3
): 8.78 (8H, s), 8.07 (8H, d, J ¼ 8.6 Hz), 7.23 (8H, d, J ¼
ꢁ
1
.6 Hz), 4.88 (8H, s), 3.89 (12H, s). Compound 2 . FT-IR (cm ): 3384(b),
8
2
1
6
895(w, nC–H), 1729(s, nC]O asymmetric), 1598(s, nC]C), 1491(s, nC]C),
421(m, nC]O symmetric), 1222(bm, nC–O), 1173(m), 1065(s), 820(s),
1
87(m), 598(w), 520(w). H-NMR (DMSO-d ): 8.85 (8H, s), 8.13 (8H, d,
6
Fig.
5 The simplified network structure of complex 4. The
J ¼ 8.6 Hz), 7.36 (8H, d, J ¼ 8.6 Hz), 4.98 (8H, s).
x Compound 3. yield: 10% (based on Cu). FT-IR (cm ): 3448(bm),
343(bs), 2922(w, nC–H), 1602(s, nC]O asymmetric), 1504(m), 1415(m,
C]C), 1388(s, nC]O symmetric), 1340(w), 1229(s, nC–O), 1177(w),
066(m), 1001(m), 803(s), 720(m), 610(w). Compound 4. yield: 24% (based
Zn1–TCMOPP units and the peripheral Zn2 sites are indicated by pink
and brown dots, respectively.
ꢁ
1
3
n
1
Dinuclear M (COO)
2
4
paddle-wheel SBUs (M ¼ Co, Ni, Cu, Zn,
ꢁ
1
on Zn). FT-IR (cm ): 2925(w, nC–H), 1654(s, nC]O asymmetric),
506(m), 1421(m, nC]C), 1333(m, nC]O symmetric), 1219(s, nC–O),
1174(m), 1104(w), 1064(m), 993(m), 848(m), 802(w), 719(w), 610(w).
Cd, and Mn) offer two distinct coordination centers for organic
linkers, such as for carboxylate- as well as for pyridyl-based organic
1
13
building blocks. Several 2D and 3D porphyrin-based frameworks
14,6b–f
with Zn (COO) SBUs have been reported in the literature.
1 (a) O. M. Yaghi, M. O’Keeffe, N. W. Ockwig, H. K. Chae,
M. Eddaoudi and J. Kim, Nature, 2003, 423, 705–714; (b)
S. Kitagawa, R. Kitaura and S. Noro, Angew. Chem., Int. Ed.,
2004, 43, 2334–2375; (c) R. Matsuda, R. Kitaura, S. Kitagawa,
Y. Kubota, R. V. Belosludov, T. C. Kobayashi, H. Sakamoto,
2
4
Among them is the 2D coordination network composed of the tetra-
4-carboxyphenyl)porphyrin and exocyclic Zn -paddle-wheel-type
SBUs. It represents an open square-grid layer with interporphyrin
(
2
6d
ꢀ
2
T. Chiba, M. Takata, Y. Kawazoe and Y. Mita, Nature, 2005, 436,
2
voids of approximate 11.8 ꢂ 11.8 A size. The Zn/Zn distance
38–241; (d) N. L. Rosi, J. Eckert, M. Eddaoudi, D. T. Vodak,
ꢀ
within the dinuclear cluster is 2.875 A. On the other hand, the
J. Kim, M. O’Keeffe and O. M. Yaghi, Science, 2003, 300, 1127–
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2
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allows for an efficient intermolecular organization within the layered
ensembles without apparent porosity features.
2
1
078; (b) D. N. Dybtsev, A. L. Nuzhdin, H. Chun, K. P. Bryliakov,
In summary, we report here on the synthesis of a new tetra-
carboxylic acid porphyrin ligand, TCMOPP, as an attractive building
block for supramolecular self-assembly, and demonstrate its capacity
to form hydrogen bonding and coordination driven networks. There
is a considerable similarity in the crystal engineering context between
the ‘‘prototype’’ TCPP and the new TCMOPP porphyrin tetraacid
building blocks. For example, bearing four diverging –COOH
functions both species are prone to readily coordinate to exocyclic
transition metal ions and engage in the formation of coordination
chains and networks. The disposition of the carboxylic acid sites in
TCMOPP is more versatile, as each one of them can orient either up,
or down, or in a lateral direction, with respect to the central
porphyrin backbone, thus potentially enhancing the three-dimen-
sional connectivity features of TCMOPP and the variety of the
supramolecular aggregates it may form. Yet, in spite of the confor-
mational flexibility imparted to this ligand by inserting aliphatic
spacers between the aromatic core and the four diverging –COOH
groups, formation of only one-dimensional (3) and two-dimensional
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(
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8
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