One-pot Synthesis of a Truncated Cone-shaped Porphyrin Macrocycle and Its Self-assembly into Permanent Porous Material

Article abstract of DOI:10.1002/asia.202100787

Here, we report the synthesis of a truncated cone-shaped triangular porphyrinic macrocycle, P₃L₃, via a single step imine condensation of a cis-diaminophenylporphyrin and a bent dialdehyde-based linker as building units. X-ray diffra

Full text of DOI:10.1002/asia.202100787

CHEMISTRY
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Accepted Article
Title: One-pot Synthesis of a Truncated Cone-shaped Porphyrin
Macrocycle and Its Self-assembly into Permanent Porous
Material
Authors: Ikjin Kim, Avinash Dhamija, In-Chul Hwang, Hochan Lee,
Young Ho Ko, and Kimoon Kim
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One-pot Synthesis of a Truncated Cone-shaped Porphyrin
Macrocycle and Its Self-assembly into Permanent Porous Material
†
[a]
† [b]
[b]
[a]
[b]
[b,c]
Ikjin Kim , Avinash Dhamija , In-Chul Hwang, Hochan Lee, Young Ho Ko, and Kimoon Kim*
Dedicated to the memory of Professor Si-Jung Kim (1932 - 2017), one of the founding fathers of the inorganic chemistry division of
the Korean Chemical Society.
[
[
a]
b]
I. Kim, H. Lee
Division of Advanced Materials Science
Pohang University of Science and Technology (POSTECH)
Pohang 37673, Republic of Korea
Dr. A. Dhamija., Dr. I.-C. Hwang, Dr. Y. H. Ko, Prof. Dr. K. Kim
Center for Self-assembly and Complexity (CSC)
Institute for Basic Science (IBS)
Pohang 37673, Republic of Korea
Email: kkim@postech.ac.kr
[
[
c]
Prof. Dr. K. Kim
Department of Chemistry
Pohang University of Science and Technology (POSTECH)
Pohang 37673, Republic of Korea
Email: kkim@postech.ac.kr
†]
These authors equally contributed in executing the experiments.
Supporting information for this article is given via a link at the end of the document.
Abstract: Here, we report the synthesis of a truncated cone-shaped
aminophenyl)porphyrin and 24 units of 2-hydroxy-1,3-
benzendicarboxyaldehyde-based linkers.[12] The X-ray crystal
structure of the gigantic porphyrinic cage revealed that the
cuboctahedron structure is composed of trimeric and tetrameric
porphyrinic macrocycle subunits (Figure S6a). Interestingly, these
subunits have unusual truncated cone-like geometries that help
in the formation of the gigantic porphyrinic cage. During the
investigation on the formation mechanism of the gigantic
porphyrinic cage, we envisioned that similar truncated cone-
shaped trimeric and tetrameric macrocycles could be synthesized
selectively by using a 2-hydroxy-1,3-benzenedicarboxyaldehyde-
based linker and a cis-di(4-aminophenyl)porphyrin instead of the
tetra(4-aminophenyl)porphyrin as building units. Thanks to the
truncated cone shape and intrinsic cavity, such macrocycles may
3 3
triangular porphyrinic macrocycle, P L , via a single step imine
condensation of a cis-diaminophenylporphyrin and a bent dialdehyde-
based linker as building units. X-ray diffraction analysis reveals that
3 3
the truncated cone-shaped P L molecules are stacked on top of each
other by π⋯π and CH⋯π interactions, to form 1.7 nm wide hollow
columns in the solid state. The formation of the triangular macrocycle
is corroborated by quantum chemical calculations. The permanent
3 3
porosity of the P L crystals is demonstrated by several gas sorption
experiments and powder X-ray diffraction analysis.
Introduction
self-assemble into porous materials useful for various
Macrocycles are one of the most fascinating molecular systems
that have played an important role in establishing and developing
applications including guest encapsulation and sensing.[8c-e]
Here, we report the construction of a new triangular imine-
based porphyrin macrocycle (P L ) via an one-pot imine
3 3
condensation reaction[10,13] of 5,10-bis(4-aminophenyl)-15,20-
diphenylporphyrin (P) and bent-shaped 5-bromo-2-hydroxy-1,3-
benzedicarboxyaldehyde linker (L) as building blocks (Figure 1).
supramolecular chemistry.[1,2] So far,
a wide variety of
macrocycles with varying degrees of size, shape, and rigidity have
been developed and investigated.[3] One of the important classes
of macrocycles includes shape-persistent, truncated cone-
[
4]
shaped skeletons, which are useful for the construction of host
molecules, for example, molecular capsules,[5] containers,[6]
cavitands,[7] etc.[8] Furthermore, the truncated cone-shaped
macrocycles have a tendency to self-assemble into higher-order
nanostructures such as channels and columns, which have
potential applications in ion transport, sensing, gas separation,
construction of liquid crystalline materials.[9] To make better use
of the diverse properties of macrocyclic self-assembly,
macrocycles must be prepared from easily accessible building
blocks by a single-step reaction[10] and have shape-persistency to
enhance non-covalent interactions.[11]
The resulting shape persistent, truncated cone-shaped P
macrocycle maintains an intrinsic cavity, and the solid-state
packing of P molecules forms 1D hollow channels, which is
confirmed by single crystal X-ray analysis. The permanent
porosity of the channels is also demonstrated through several gas
sorption and PXRD experiments.
3 3
L
3 3
L
Results and Discussion
Considering the geometries of P and L, the imine condensation
between them would produce, at least in principle, P L or P L or
3 3 4 4
both (Figure 1). At the outset of this work, therefore, we performed
quantum chemical calculations to compare the geometric stability
In 2020, we reported the synthesis of cuboctahedron
shaped gigantic organic cages, the largest one among this kind,
via the imine condensation of 12 units of tetra(4-
1
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Chemistry - An Asian Journal
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of P
3
L
3
and P
4
L
4
macrocycles. The optimized structure of P
3
L
3
Einstein equation was around 3.3 nm, which is closer to the
exhibited a truncated cone-shaped geometry, which was also
observed in the X-ray crystal structure of the gigantic porphyrinic
cage (Figures 1b and S6). The angle between the ditopic linker
and the two imine nitrogen atoms (∠NCN', where N and N'
denote two imine nitrogen atoms, and C denotes the center of
phenyl ring) is 118° (Figure S6b), which is close to that of imine-
based architectures using the same linker.[14] On the other hand,
3 3 4 4
expected diameter of P L than that of P L (Figures S6b and S6c).
In order to grow X-ray diffraction quality single crystals of
P L , slow vapor diffusion of ether (for 1 week) in a 1:1 toluene
3 3
and carbon disulfide solution of P
yielded rectangular-shaped crystals (Figure S8). Single crystal X-
ray diffraction (SCXRD) study exhibited that P crystallized in
the centrosymmetric triclinic space group, P-1, with four P
molecules in the unit cell. A close inspection of the crystal
structure of P revealed that two conformational isomers of the
two have 124°, deviating from the ideal 120° (Figures 1b and S6c). macrocycle (A and B) exist together depending on the orientation
3 3
L was carried out, which
3 3
L
3 3
L
4 4
the model structure of P L showed a distorted planner geometry,
in which two ditopic linkers have the ∠NCN' of 112° and the other
3 3
L
Moreover, the formation energy (ΔE) for P
gas phase is 45.0 kcal/mol lower (more favorable) than that of
macrocycle (Figure S7). These results substantiated that the
combination of P and L would prioritize the formation of P
macrocycle over P macrocycle.
3
L
3
macrocycle in the
of the imine bonds with respect to the hydroxy group of L. In
conformer A, three porphyrin units are connected by (syn-, syn-),
(anti-, anti-) and (syn-, anti-) conformations of the imine bonds.
Whereas in conformer B, all porphyrin units are linked by the (syn-,
anti-) conformation of the imine bonds (Figure 2a). The overall
shape of the two conformers is best described as a truncated-
cone, where three P units lean downwards and three L units lean
upwards, resulting in a cone angle of ~ 120° (Figures S9c and
4 4
P L
3 3
L
4 4
L
3 3
S9d). In the truncated cone-shaped structure of P L , the
minimum diameter (a circle formed by connecting the oxygen
atoms of Ls) and the maximum diameter (a circle formed by
connecting the endpoints of Ps) are estimated to be around 1.7
and 3.2 nm, respectively (Figure S9b), for both A and B
conformers.
In the crystal, the A and B conformers are paired up with the
same orientation to form
supramolecular dimer” AB via CH⋯π and π⋯π interactions
between slipped porphyrin units and between phenyl groups
Figure S10a). Two neighboring AB dimers meet at the inversion
a
truncated cone-shaped
“
(
center, where two B conformers are interdigitated upside down
via π⋯π interactions between porphyrin units and phenyl groups
(
“
Figure S10b). As a result, the A and B conformers form a
supramolecular tetramer” ABBA (Figure 2c), which acts as a
repeating unit to produce 1D hollow columns with a pore diameter
of ~ 1.7 nm (Figures S11 and S12). In addition, several short N⋯H
interactions (2.46 ~ 2.70 Å) between the neighboring macrocycles
and solvent molecules were observed, which seems to contribute
3 3
to stabilization of the packing structure of P L .
To investigate the stability of the crystalline macrocyclic
assembly, powder X-ray diffraction (PXRD) studies were
performed on the material before and after the removal of solvent
molecules. The experimental and simulation PXRD data showed
that the crystallinity is well maintained even after removal of
solvent molecules by high vacuum treatment (10-2 Pa) at 80 °C
Figure 1. (a) Schematic representation for the design and synthesis of
porphyrinic macrocycles. (b) Optimized structures of P L and P L macrocycles
3 3 4 4
obtained by B3LYP/6-31G(d,p) level of calculations.
As anticipated by the quantum chemical calculations, the
3 3
for 12 h (Figure 3a). Complete desolvation of P L crystals after
reaction of P and an equivalent amount of L in the presence of a
the vacuum treatment and their thermal stability were confirmed
by thermogravimetric analysis (TGA) (Figure S5). Furthermore,
even after the P L crystals were exposed to aqueous media, the
3 3
diffraction pattern still mostly remained as such, although their
shinny faces were lost (Figure S13).
catalytic amount of scandium triflate (Sc(OTf)
temperature for one day resulted in the exclusive formation of the
triangular porphyrinic macrocycle, P (Figure 1). MALDI-TOF
peak at m/z 2514.9,
with a molecular formula
3
) at room
3 3
L
mass spectrometry revealed
corresponding to the [M+H] ion of P
a
=
+
3
L
3
After establishing the presence of 1D channels of P
crystals, permanent porosity of P was confirmed by several
gas sorption studies. Prior to the gas sorption measurement of
crystals, supercritical CO activation was performed by
washing the crystals with liquid CO . The N sorption behavior of
crystals followed a type I isotherm with a small hysteresis
Figures 3b and S14). The reason behind the hysteresis is not
3 3
L
of C156
trace of P
H
100
N
18
O
3
Br
3
(Figure S1). Mass spectrometry exhibited no
clearly
3 3
L
4
L
4
macrocycle. The FTIR spectrum of P L
3 3
showed the emergence of imine C=N stretching bands at 1625
P
3
L
3
2
and 1579 cm-1 (Figure S2). The H NMR spectrum of P
1
L
3
was
3
2
2
relatively simple, reflecting the symmetric structure and diffusion-
ordered spectroscopy (DOSY) NMR confirmed the existence of a
3 3
P L
(
single species (P
corresponding hydrodynamic diameter calculated by the Stokes-
3 3
L ) in solution (Figure S3). In addition, the
well understood at the moment, but a similar behavior has been
observed in flexible MOFs and organic cages.[15] The Brunauer-
Emmett-Teller surface area (SBET) was found to be 205 m2g-1
2
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Chemistry - An Asian Journal
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FULL PAPER
(
Figure S15a). The pore size distribution obtained by the non-local
density functional theory (NLDFT) method showed only a single
peak at 1.67 nm (Figure S16), which is close to the pore size of
P L observed in the crystal structure (Figure 2c).
3 3
Figure 3. (a) Powder X-ray diffraction profiles of as-synthesized (black),
desolvated (red) crystals of P
crystal structure of P (blue). (b) N
sorption isotherms for P at 195 K (black) and 273 K (red). (d) CO
CO (green stars) and N (magenta squares) for P at 273 K. (solid symbols:
L
3 3
and simulation data obtained from single
sorption isotherm for P at 77 K. (c) CO
(red circles),
3
L
3
2
L
3 3
2
L
3 3
2
2
3 3
L
adsorption; open symbols: desorption)
Conclusion
We report the facile synthesis of the shape-persistent triangular
porphyrinic macrocycle P via imine condensation of 5,10-bis(4-
3 3
L
aminophenyl)-15,20-diphenylporphyrin (P) and bent-shaped 5-
bromo-2-hydroxy-1,3-benzedicarboxyaldehyde linker (L) as
building blocks. The porphyrinic macrocycle with a truncated cone
shape self-assembled into 1D columns in the solid state through
π⋯π and CH⋯π interactions between porphyrin–porphyrin and
porphyrin–phenyl units. This assembly produced a porous
architecture containing 1.7 nm wide hollow 1D channels.
Permanent porosity of the material was confirmed by several gas
sorption experiments and powder X-ray diffraction analysis.
Besides the porosity, the macrocyclic assembly can be exploited
for various applications by tuning the interior or exterior of the
macrocycle through post-synthetic modification of the inner
hydroxy group or outer bromine group on the linker. Furthermore,
we believe that the approach presented here is applicable to the
synthesis of other macrocycles of various sizes by tuning the
angle of the bent linker. Work is in progress along these lines.
3 3
Figure 2. (a) X-ray crystal structure of P L macrocycle depicts two different
conformational isomers A and B (anti- : green, the imine nitrogen is directed
away from the hydroxy group; syn- : magenta, the imine nitrogen is directed
3 3
towards the hydroxy group) and (b) their side views. (c) Crystal packing of P L
showing a 1.7 nm wide hollow column along [4 1 1] and [0 -2 2] directions (gray:
C; blue: N; red: O; orange: Br). Solvent molecules and hydrogen atoms are
omitted for clarity.
Next, CO
crystals. A CO
revealed a typical type I sorption behavior and produced a SBET
value of 360 m2g-1 (CO uptake of 154 cm3g-1 at 1 bar), which is
higher than that estimated from the N sorption isotherm (Figures
c and S15b). Furthermore, gas sorption experiments at 273 K
2
gas sorption experiments were performed for the
P
3
L
3
2
adsorption isotherm recorded at 195 K
2
2
3
showed that the CO
to N
cm g at 1 bar) (Figure 3d). These results may be due to one of
2
uptake (27.5 cm3g-1 at 1 bar) was superior
uptake (2.67 cm3g-1 at 1 bar) as well as CO uptake (3.93
2
-1
3
Acknowledgements
the following reasons or both: (i) acidic CO
relatively basic imine sites in P packing structure or (ii) CO
with a small kinetic diameter (3.3 Å) is readily adsorbed in
unexplored narrow sites compared to N (3.64 Å) or CO (3.76
The isosteric heat of adsorption for CO was calculated
to be around 36.6 kJmol-1 (at 10.6 cm3g-1 uptake of CO
) by fitting
2
interacts well with
3
L
3
2
This work was supported by the Institute for Basic Science (IBS)
[
IBS-R007-D1]. X-ray crystallography experiments with
2
synchrotron radiation were performed at the Pohang Accelerator
Laboratory (PLS-II BL2D SMC).
[
15c,16]
Å).
2
2
the adsorption data at 195 K and 273 K to the Clausius-Clapeyron
equation (Figure S17).
Keywords: Macrocycle • Porous architectures • self-assembly •
Imine condensation • permanent porosity
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Chemistry - An Asian Journal
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One-pot imine condensation of a cis-diaminophenylporphyrin and a bent dialdehyde-based linker as building units produce a shape-
persistent truncated cone-shaped macrocycle, which self-assembles into a 1D porous material with 1.7 nm wide hollow channels in the
solid state.
5
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