Templating Porphyrin Anisotropy via Magnetically Aligned Carbon Nanotubes

Article abstract of DOI:10.1002/cplu.201800623

The preparation and characterisation of a novel three-dimensional organic material consisting of porphyrin arrays on carbon nanotubes embedded in an organogel is reported. Firstly, the porphyrin array was prepared through metal-ligand coordination of a ditopic ligand (1,2-bis(4-pyridyl)ethane) and two bis-Zn(II) porphyrins, linked through a pyrene core, and was studied through UV-Vis, NMR and diffusion spectroscopies. Secondly, the porphyrin supramolecular architecture was adsorbed on pristine carbon nanotubes, greatly improving the dispersibility of the latter in organic solvents. The hybrid material was characterised by means of UV-Vis spectroscopy, microscopic techniques and thermogravimetric analysis. Finally, by exploiting the anisotropic magnetic susceptibility of carbon nanotubes, the hybrid material was aligned under a magnetic field, the organisation of which could be maintained by in situ gelation. The resultant hybrid organogel exhibited notable optical anisotropy, suggesting an anisotropic arrangement of the porphyrin-CNTs architectures in the macroscopic material.

Full text of DOI:10.1002/cplu.201800623

Accepted Article
Title: Templating porphyrin anisotropy via magnetically-aligned carbon
nanotubes
Authors: Luka Đorđević, Tomas Marangoni, Mingjie Liu, Rita De
Zorzi, Silvano Geremia, Andrea Minoia, Roberto Lazzaroni,
Yasuhiro Ishida, and Davide Bonifazi
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Templating porphyrin anisotropy via magnetically aligned carbon
nanotubes
Luka Đorđević,a Tomas Marangoni,a Mingjie Liu,b Rita De Zorzi,a Silvano Geremia,a Andrea Minoia,c
Roberto Lazzaroni,c Yasuhiro Ishida,b and Davide Bonifazi*d
Dedication ((optional))
Abstract: We report the preparation and characterisation of a novel
three-dimensional organic material consisting of porphyrin arrays on
carbon nanotubes embedded in an organogel. Firstly, the porphyrin
array was prepared through metal–ligand coordination of a ditopic
ligand (1,2-bis(4-pyridyl)ethane) and two bis-Zn(II) porphyrins, linked
through a pyrene core, and was studied through UV-Vis, NMR and
diffusion spectroscopies. Secondly, the porphyrin supramolecular
architecture was adsorbed on pristine carbon nanotubes, greatly
improving the dispersibility of the latter in organic solvents. The hybrid
material was characterised by means of UV-Vis, microscopic
techniques and by thermogravimetric analysis. Finally, by exploiting
the anisotropic magnetic susceptibility of carbon nanotubes, the
hybrid material was aligned under a magnetic field, the organisation
of which could be permanently kept by in situ gelation. The resultant
hybrid organogel exhibited notable optical anisotropy, suggesting an
anisotropic arrangement of the porphyrin-CNTs architectures in the
macroscopic material.
been achieved either through non-templated or templated
methodologies.[27] In case of non-templated approaches, the
various non-covalent interactions (i.e., H-bonds, transition metal
coordination bonds, electrostatic interactions and others) have
been exploited to build complex organic architectures featuring
nanoscale precision and long-range order.[28–31] The templated
method, on the other hand, is based on exploiting interactions with
substrates such as zeolites[32,33] and carbonaceous materials,[34–
37]
and has also been extremely useful in creating functional
nanomaterials. Among the different chromophores, porphyrins,
square planar tetrapyrrolic macrocycles comprising of 18π
electrons, have arguably been the most exploited chromophores
across different research disciplines.[38–45] Some of their
advantageous properties include structural robustness, strong
absorption properties in the UV-Vis spectral region and vast
supramolecular chemistry.[46–53] Moreover, porphyrin chemistry
has become extremely rich and diverse and the electronic and
optical properties can be fine-tuned by shaping their periphery.[54–
58]
While a number of efforts in constructing nanostructures
through the organization of porphyrins have been achieved, their
organisation over multiple scales (from the nanoscale to the
microscale) remains of great interest owing to their potentials in
light-harvesting applications.[59–63] Although one- or two-
dimensional supramolecular porphyrin systems are now easily
Introduction
Ordered and controlled nanostructures are one of the major
routes towards new materials with outstanding properties. For
example, just as Nature seamlessly arranges the light harvesting
(LH) antenna complex in order to accomplish its unique
functions,[1–3] chemists have devoted efforts in supramolecular
association of fundamental molecular modules into functional
materials.[4–13] In fact, the controlled organization of photoactive
molecules is playing a crucial role in the research and future
development of devices, such as solar cells,[14,15] organic
transistors,[16,17] chemical and bio-sensors.[18–26] The organization
into functional nano-architectures of chromophoric modules has
[a]
Dr. L. Đorđević, Dr. T. Marangoni, Dr. R. De Zorzi, Prof. S. Geremia
Department of Chemical and Pharmaceutical Sciences, University of
Trieste
Via L. Giorgieri 1, 34127 Trieste, Italy
Dr. M. Liu and Prof. Y. Ishida
[b]
[c]
RIKEN Center for Emergent Matter Science
2-1 Hirosawa, Wako, Saitama 351-0198, Japan
Dr. A. Minoia and Prof. R. Lazzaroni
Laboratory for Chemistry of Novel Materials, CIRMAP, Université de
Mons-UMONS
Place du Parc 20, B-7000 Mons, Belgium
Prof. D. Bonifazi
[d]
School of Chemistry, Cardiff University
Park Place Main Building, CF10 3AT. E-mail:
bonifazid@cardiff.ac.uk
Figure 1. (a) Compounds 1, 2, Picoline (Pic) and 1,2-bis(4-pyridyl)ethane (BPE)
used in this study and (b) preparation of the [1∙BPE]2 and the subsequent
dispersion of MWCNTs.
Supporting information for this article is given via a link at the end of
the document.
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prepared, the construction of three-dimensional assemblies
remains a challenge.[64–66] While porphyrin low-dimensional
oligomers have already been prepared, both by the templated[67–
71]
and non-templated approaches,[72,73] we strived to
macroscopically
magnetically
arrange
aligned
porphyrin
multi-walled
structures
through
Figure 2. X-ray structure of compound 1. With two methanol molecules
coordinated to the Zn centres. Hydrogens atoms are omitted for clarity. Color
coding: C (gray), N (purple), O (red).
carbon-nanotubes
(MWCNTs).[74–77] CNTs appear to be the ideal platform due to
their versatility in interacting with organic molecules, such as
porphyrins,[78–83] OPEs,[84–87] TTFs,[88,89] perylene bisimides,[90,91]
alkylated
fullerenes[92–95]
and
various
supramolecular
avoid additional π-π interactions with the MWCNTs and self-
aggregation (Figure S1, Supporting Information). The two
synthons were prepared following literature procedures[110–112]
architectures.[96–103] The supramolecular porphyrin array used in
this study was prepared by preparing a 1:1 mixture of bis-
tetrapyrrolic macrocycle 1 and the ditopic ligand 1,2-bis(4-
pyridyl)ethane (BPE), through metal-ligand complexation (N∙∙∙Zn),
in a CHCl3 solution (Figure 1). Compound 1 was designed to bear
a central pyrene unit, which could act as anchoring moiety to form
known pyrene-CNTs π-π interactions that, in turn, can aid with
the dispersion of CNTs.[104–108] This hybrid material
[1∙BPE]2⊙MWCNT resulted in a very stable suspension that could
be aligned under a magnetic field. Aiming at preserving the
alignment after the stimulus was removed, hybrid
[1∙BPE]2⊙MWCNT was mixed with poly(hydroxybutyrate-co-
hydroxyvalerate) (PHBV, 4 mol % PHV content), an organic
biodegradable polymer that is known to form organogels.[109]
and were connected exploiting
a Pd(0)-catalysed Cu-free
Sonogashira cross-coupling reaction[113] in 62% yield. Suitable
crystals for X-ray crystallography were grown by vapour diffusion
of MeOH into a CHCl3 solution of 1, with the structure being shown
in Figure 2. Monotopic porphyrin 2 was analogously prepared,
through Pd(0)-catalysed cross-coupling reaction, between
porphyrin 6 and trimethylsilylacetylene in 83% yield.
Porphyrin Array Formation. First of all, we set to study the
formation of the porphyrin array [1∙BPE]2 in a CHCl3 solution.
While the coordination chemistry of Zn(II) porphyrins has been
studied in detail,[46,114] we first investigated the influence of mesityl
peripheral groups on the metal coordination (N∙∙∙Zn). In order to
appreciate the impact of the substituted phenyl groups on the
axial coordination, we performed UV-Vis titration (c = 3.0 × 10-6 M,
CHCl3, 298 K) of porphyrin 2 with 4-picoline (Pic) (Figure 3a and
S2, Supporting Information). The progressive addition of Pic into
a solution of 2, resulted in a bathochromic shift of the Soret band
from 421 to 431 nm. Non-linear global regression analysis,[115]
gave a microscopic binding constant Km = 1.8 × 104 M-1. This is in
Results and Discussion
Syntheses. The synthetic pathway undertaken to obtain
compounds 1 and 2 is reported in Scheme 1. Compound 1 is
comprised of a central aromatic core, 1,6-disubstituted pyrene,
and two peripheral Zn(II)-porphyrin units. Moreover, the Zn(II)-
porphyrin bears three mesityl units around its core in order to
1
great agreement with the value obtained by H-NMR titration for
the same system (Km = 1.6 × 104 M-1, Figure S3, Supporting
Information). Subsequently, we performed UV-Vis titration (c = 1.8
× 10-5 M, CHCl3, 298 K) experiments to prove the interaction
between compound 1 and BPE (Figure 3b). A bathochromic shift
of the Q bands was observed (from 550 and 590 nm to 565 and
605 nm, respectively), thus confirming the N∙∙∙Zn coordination.
To gain further insights into the structural changes upon binding
of the ligand to compound 1, 1H-NMR of a 1:1 mixture (c = 1.1 ×
10-3 M, CHCl3, 298 K) was performed (Figure 3c). The clearest
change upon addition of one equivalent (eq.) of BPE is the
appearance of three additional peaks at 5.05, 3.05 and 1.25 ppm,
attributed to the bis-pyridyl protons that show a significant upfield
shift (compared to the free BPE). Changes were also observed in
the chemical shift and multiplicity of the porphyrin protons, namely
an upfield shift for all β-pyrrolic signals of around 0.15 ppm was
1
observed. These observations prompted us to perform H-NMR
titrations (c = 1.1 × 10-3 M, CHCl3, 298 K, Figures 3d and S4,
Supporting Information) to elucidate the dynamic and structural
evolution occurring upon the binding of the ligand. The addition
from zero to one eq. of BPE showed the upfield shift of the α, β
and –(CH2)2– signals of the ditopic pyridine ligand at 5.05, 3.05
and 1.25 ppm. Addition of more than one eq. of ligand showed the
progressive downfield shift of the ligand signals toward those of
the free species, indicating a fast equilibrium. More useful
Scheme 1. Synthetic route to obtain compounds 1 and 2: (a) Br2, CCl4, rt; (b)
TMSA, [Pd(PPh3)2Cl2], PPh3, CuI, THF/Tol/Et3N, 120 °C, 1 h, µW irradiation; (c)
K2CO3, CHCl3/MeOH, rt; (d) 1. BF3∙Et2O, CHCl3, 1 h, rt; 2. DDQ,1 h, rt; 3. Et3N,
15 min, rt; 4. Zn(OAc)2∙2H2O, CHCl3/MeOH; (e) [Pd2(dba)3], AsPh3, Tol/Et3N, rt,;
(f) TMSA, [Pd2(dba)3], AsPh3, Tol/Et3N, rt. Abbreviations: TMSA,
trimethylsilylacetylene; THF, tetrahydrofuran; Tol, toluene; DDQ, 2,3-dichloro-
5,6-dicyanobenzoquinone.
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Figure 4. DOSY investigation (a) stack plot showing the signal decays as a
function of gradient strength (G) for compounds 1 and [1∙BPE]2; (b) overlay of
three 2D-DOSY experiments – BPE (black), compound 1 (blue) and [1∙BPE]2
(red); (c) normalised signal decays (ln(I/I0)) versus the diffusion weighing (b
values) of representative peaks of BPE (black), 1 (blue) and [1∙BPE]2 (red) with
the corresponding linear fits; (d) graphical analysis of Dexp values for different
molecules used in this study; the dotted lines represent the calculated
correlation of diffusion coefficients and molecular weights assuming that the
diffusion coefficients for two different molecular species (D1/D2) is inversely
proportional to the square root of the ratio of their molecular weights M2/M1 for
rod-like species.
Figure 3. Selected spectroscopic investigations: (a) UV-Vis titration data
(CHCl3, 298K) of compound 2 (c = 3.0 × 10-6 M) with different molar amounts of
Pic (from 0 to 150 equivalents); inset shows the variation in absorbance at 421
nm (red circles) and 431 nm (black circles) plotted against the molar ratio with
the corresponding 1:1 non-linear least-square fitting; (b) UV-Vis titration data
(CHCl3, 298 K) of compound 1 (c = 1.8 × 10-5 M) with different molar amounts
of BPE (from 0 to 36 equivalents); (c) 1H-NMR (CDCl3, 298 K, c = 1.1 × 10-3 M)
of BPE (top), compound 1 (bottom) and their 1:1 mixture (middle), α, β and –
(CH2)2– indicate the signals of complexed BPE; (d) 1H-NMR (CDCl3, 298K)
titration of compound 1 (c = 1.1 × 10-3 M) with BPE, experimental data for β-
pyrrole protons ppm shift against BPE eq.; the grey dotted line is intended as
guide for the eye; inset shows a 1.1 × 10-3 M solution of 1 before (left) and after
(12 h, right) titration experiment.
molecular weights (MW). For rod-like species, such as those
considered here, the ratio of the diffusion coefficients for two
different molecular species (D1/D2) is inversely proportional to the
square root of the ratio of their molecular weights (M2/M1): D1/D2
structural information was obtained by observing the evolution of
the β-pyrrolic signals upon addition of the ligand. From zero to one
eq. of BPE, the β-pyrrolic protons showed a progressive upfield
shift and an increased multiplicity due to the diminished symmetry
of compound 1 upon coordination. Addition of more than one eq.
of the ligand maintained the increased multiplicity of the β-pyrrolic
signals, but a downfield shift was observed. The experimental
data in Figure 3d are diagnostic of a closed 2:2 sandwich that
progressively moves toward the [1∙(BPE)2] complex.[116,117]
Unfortunately, the precipitation of the complex, which occurs upon
progressive addition of ligand to the solution (Figure 3d inset,
Figure S4, Supporting Information, note the baseline changes
even if n scans remains constant) made it impossible to obtain a
precise fit. To further characterise the structure of the coordination
complex, Diffusion-Order Spectroscopy (DOSY) measurements
of solutions containing the single components or the 1:1 mixture
were performed (Figure 4). This powerful technique has become
the method of choice for multi-component systems in order to gain
the structural insights of their effective size and shape.[118,119] In
this context, diffusion NMR spectroscopy would help us to
determine the species in solution, even if some precipitate is
formed. The self-diffusion translational coefficient (Df) of the
species showed a slight decrease of the Dexp of a 1:1 mixture,
when compared to compound 1 alone (Figures 4b,c). This
observation alone would exclude the formation of
oligomeric/polymeric species in solution. Additional analysis of
the DOSY data allowed us to compare the Df with the respective
= (M2/M1)1/2 [120,121]
Thus, by comparing these ratios (Table 1 and
.
Figure 4d) we could confirm the formation of [1∙BPE]2 in solution.
Table 1. Diffusion coefficients (Dexp) determined by DOSY experiments.
Molecular weights (MW) and the relation between diffusion coefficients and
molecular weights (compared to BPE) for rod-like species are reported.
Complete information is found in Supporting Information (Figures S5-7 and
Table S1).
Diff. Coeff.
(×10-6 / cm2 s-1)
MW
(g/mol)
DBPE
Dn
/
(MWn /
Sample
½
MWBPE
)
BPE
1
10.59
3.31
2.57
184.24
1854.94
4078.36
1.00
0.31
0.24
1.00
0.32
[1∙BPE]2
0.21
Dispersion of MWCNTs. Adapting a recently reported procedure
for the non-covalent functionalization of CNTs with organic
molecules,[99] it was possible to functionalise and disperse
MWCNTs with [1∙BPE]2 (Figure 5), by means of multiple cycles of
dispersion/centrifugation steps. Samples of [1∙BPE]2⊙MWCNT
were prepared by sonication (rt, 30 min) of 1.0 mg of pristine
MWCNTs into a 1:1 molar ratio solution of 1 and BPE in CHCl3 (c
= 4.9 × 10-5 M). The resulting black suspension was then
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Figure 5. (a) Protocol adopted for the non-covalent dispersion of CNTs: to a suspension of MWCNTs in CHCl3 (1.0 mg in 10.0 mL) was pre-sonicated and organic
material was added (c = 4.9 × 10-5 M). This suspension was sonicated for 30 minutes, centrifuged for 30 minutes, then the dispersed nanotubes were taken from
the supernatant and this solution was filtered to remove the excess organic material. The solid was redisolved in 10.0 mL CHCl3 and sonicated for 5 minutes to
obtain a stable suspension. This process was repeated until UV-Vis absorption showed no excess organic material in the filtrate; (b) enlarged photograph of the
dispersions obtained from the non-covalent dispersion protocol; (c,d) topography and phase TM-AFM images of the [1∙BPE]2⊙MWCNT; (e) thermogravimetric
analysis of the [1∙BPE]2⊙MWCNT (black line) in comparison to the pristine MWCNTs (grey line) showing a weight loss of 6% at 450 °C; (f) UV-Vis spectra of the
[1∙BPE]2⊙MWCNT (black), 1⊙MWCNT (grey) and 4⊙MWCNT (dashed), the inset shows the normalised absorption of the 3 hybrids.
centrifuged (at 5 krpm) for 30 min in order to separate the
unfunctionalised and aggregated fraction of carbonaceous
material from the dispersed nanotubes. Finally, the supernatant
solution was separated, filtered, and washed with CHCl3 to
remove the excess of the organic material. Multiple cycles were
performed until the filtrate showed no UV-Vis absorption profiles.
The same procedure was used in order to determine whether
other compounds used in this study could disperse the MWCNTs.
With compounds 1, 2 and 4 only traces (< 5%) of the hybrid
material were detected; in contrast, complex [1∙BPE]2 gave a high
dispersibility of the carbon nanomaterial. The dispersibility was
also confirmed by means of tapping mode atomic force
which could be ascribed to the adsorption of organic material
possessing different viscoelastic properties than that of the
graphitic CNTs.
The presence of the organic compound on the nanotubes was
also investigated by recording the UV-Vis absorption and
emission profiles. The UV-Vis spectra of [1∙BPE]2⊙MWCNT
showed the characteristic absorption profiles of dispersed
nanotubes, along with the typical electronic Soret and Q
transitions originating from the porphyrin macrocycle (Figures 5f
and S9, Supporting Information). Fluorescence spectroscopy
(Figure S10, Supporting Information) showed a weak emission
profile suggesting that, as expected, was strongly quenched upon
adsorption on the nanotube framework. Final evidence of the
formation of the hybrid material was obtained through
thermogravimetric analysis (TGA). At 450 °C the hybrid material
presents a 6% loss in weight when compared to the pristine
MWCNTs (Figure 5e), with the weight loss attributed to the
presence of the organic material. Finally, we proved that the
functionalisation of the MWCNTs[99,100,122] is reversible (Figure
S11, Supporting Information) by employing a strong acid
(trifluoroacetic acid, TFA, capable of protonating both the
porphyrin and the ligand) or by heating.
microscopy (TM-AFM). Indeed,
a drop-casted solution of
[1∙BPE]2⊙MWCNT showed only the presence of individualised
CNT structures (Figures 5c,d), indicating the efficient de-bundling
action triggered by [1∙BPE]2.
A closer analysis of the
[1∙BPE]2⊙MWCNT material clearly showed the presence of
tubular structures having lumps along the nanotubes (Figure 4d),
which were not present in the case of the pristine MWCNTs
(Figure S11, Supporting Information). These periodic structures
can be possibly attributed to the sandwiched [1∙BPE]2 complexes,
which are adsorbed around the MWCNTs thus enhancing their
dispersibility. Furthermore, the presence of soft organic material
onto the CNT surface was observed by phase imaging of
[1∙BPE]2⊙MWCNT (Figure 5d). Indeed, phase analysis revealed
the presence of areas of the sample possessing different contrast
Molecular Modelling. Molecular modelling simulations have
been performed in order to gain some understanding on the
morphology
of
the
[1∙BPE]2/CNT
interface
in the
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[1∙BPE]2⊙MWCNT hybrid material (Figure 6). The Biovia
molecular modelling package Materials Studio 7 has been used
to perform such modelling,[123] using its implementation of the
COMPASS force field.[124] Only the outermost tube of the
MWCNTs has been considered for the modelling, assuming that
the main contribution to the stability of the [1∙BPE]2⊙MWCNT
interface is coming from the adsorption on the MWCNTs external
wall, which we represent as an infinite, rigid carbon nanotube
having a diameter of about 10 nm. The first step in building the
molecular model for the [1∙BPE]2/CNT interface was to compare
the interaction between the nanotube wall and compound 1 when
adsorbed in flat and edge-on geometries. The 1⊙MWCNT
Figure 6. (a) Front and side view of compound 1 adsorbed flat (top) and edge-on (bottom) on the nanotube; (b) most stable conformations for [1∙BPE]2⊙MWCNT
complex adsorbed flat and (c) edge-on on the nanotube; Figures b,c left show the full system where the fixed molecules are shown in red. Figures b,c right show
the top views of the adsorbed geometries.
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interaction energy, E(1⊙MWCNT), is calculated as the sum of the
electrostatic and dispersion (vdW) energies between compound
1 and the nanotube and the results show that compound 1 is
about 67 kcal mol-1 more stable when adsorbed flat on the
nanotube (Figure 6a top) than when it is adsorbed in an edge-on
orientation (Figure 6a bottom). This is due to the fact that when
compound 1 is adsorbed flat, (i) favourable π-π interactions can
be formed between its pyrene fragment and the nanotube wall,
and (ii) less torsional stress is present in its molecular structure.
The much higher stability of the flat orientation is also reflected in
the observation that when initially set in the edge-on orientation,
compound 1 will spontaneously go flat on the nanotube in just a
few ps of MD simulation. Next, we built the [1∙BPE]2 complex and
made it interact with the surface of the nanotube in a bath of
CHCl3. The adsorption on the CNT surface of the [1∙BPE]2
complex was investigated during 100-ps long molecular dynamic
simulations, both in the flat (Figure 6b left) and edge-on (Figure
6c left) geometries. Finally, an iterative MD/Quench scheme[125]
consisting in a series of short (20-ps) MD, followed by a geometry
optimization of the system, is used to obtain the most stable
conformations of the [1∙BPE]2 complex in the flat and edge-on
geometries (Figure 6b,c right). The stability of the interfaces is
then estimated by comparing the [1∙BPE]2⊙MWCNT interaction
energies, and the results show that the interface where the
[1∙BPE]2 complex is adsorbed flat on the nanotube is about 42
kcal mol-1 more stable than that where the complex is adsorbed
edge-on. This difference can be rationalised considering the
complete adsorption of one pyrene unit on the nanotube, whereas
in the edge-on geometry the only interactions between the
complex and the carbon surface are present through some methyl
groups on the mesityl arms. These results indicate that the
[1∙BPE]2 complex prefers to interact with the nanotube by having
one porphyrin fully adsorbed on the surface and the other one
solvated.
Figure 7. (a) Steps adopted in the preparation of the aligned hybrid organogel
containing [1∙BPE]2⊙MWCNT; (b) photograph of the PHVB-alone organogel
(left) and aligned hybrid organogel (right); (c) POM images of the “side-wall”
face of the aligned hybrid organogel; (d,e) UV-Vis absorption profiles recorded
at different polarised angles (θ = from 0° ➝ 90° by 15° steps) of the “side-wall”
face (d) and the “tip” face (e).
Magnetic alignment. At this point, the CNTs, through their
magnetic susceptibility,[126] could be used for the templated
alignment of the adsorbed organic material as a top-down
approach.[127–131] However, the alignment can hold only when a
magnetic field is applied, thus using only a solution of hybrid
material would be unpractical. To this end, we used an organic
perpendicular to B. The first evidence of anisotropic absorption
was observed with the polarised optical microscope (POM) under
a crossed Nicols (Figure 7c). The microscope displayed very
different image brightness depending on the rotation of the
sample. When the “side-wall” face of the aligned hybrid organogel
was rotated in an in-plane manner, its POM showed a contrast
every 45°, giving a dark image when the light polarization angle
with respect the applied magnetic field was either 0° or 90°. When
performing measurements on the “tip” edge of the aligned hybrid
organogel no difference in brightness was perceived (Figure S12,
Supporting Information). In order to assess whether the goal of
building a three-dimensional templated porphyrin hybrid was
successful, we performed polarised UV-Vis absorption
spectroscopy (Figure 7d,e). When rotating the “side-wall” face
and measuring the absorption spectra every θ = 15° (Figure 7d),
a stepwise reduction in the overall absorbance (including the
Soret and Q-bands, centred at 429 and 553 nm) was observed
biodegradable
polymer
(poly(hydroxybutyrate-co-
hydroxyvalerate, PHBV, with a PHV content 4 mol %) that, in the
presence of organic solvent, would swell and gel relatively fast
(Figure 7). By employing different amounts of organogel, one can
tune the gelation time, the optical transparencies and the
manifestation of the magnetic behaviour.[132] The best results
were obtained for 10.0 mg of 4% PHBV and applying the magnetic
field for 60 minutes. The optimised procedure for the formation of
the aligned hybrid material is depicted in Figure 7a: to 10.0 mg
solid was added a solution of hybrid [1∙BPE]2⊙MWCNT (1.0 mL)
and the mixture was briefly heated to solubilise the organogel. At
this point, toluene (2.0 mL) was added to the heated solution and
the solution (final concentration of 3.3 mg mL-1) was placed under
a magnetic field (B, 10 T) and left until gelation was complete.
Considering the direction of the magnetic field, one could imagine
a “side-wall” face of the hybrid gel is parallel to B and a “tip”
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from θ = 0° (maximum absorbance) to θ = 90° (minimum
absorbance). This further proved the alignment of the porphyrin
organisation exerted by the CNT template. Additional
experiments at the “tip” face (Figure 7e) showed an optical
isotropic behaviour, namely no changes in the absorption
intensity were detected at different incident angles (θ = from 0° ➝
90° by 15° steps). In parallel, reference materials, containing
either PHBV alone or PHBV with only the [1∙BPE]2 complex were
also prepared to pinpoint the templating effect of the CNT
framework. Isotropic optical behaviour was obtained when
performing UV-Vis absorption measurements on both the PHBV-
alone organogel and the hybrid material containing only
Elmer 2000 spectrometer. (HR)-MALDI-MS mass spectrometry
was performed by the Centre de spectrométrie de masse at the
Université de Mons in Belgium recorded using a Waters QToF
Premier mass spectrometer. Teflon(JH)Millipore® (0.45 μm)
filters were used in order to recover functionalised carbon
nanotubes from a chloroform solution. Tapping-mode AFM
measurements were carried out in air at 293 K by using a
Nanoscope IIIa (Digital Instruments Metrology Group, USA)
instrument, model MMAFMLN. Sonication was performed using a
Branson 2510 Ultrasonic Bath. TGA analyses were performed
using a TA Instruments TGA Q500 with a ramp of 10 °C/min under
N2 from 100 to 800 °C. Magnetic alignment was performed on a
superconducting magnet JASTEC 10T100 with a vertical bore of
chromophore [1∙BPE]2 (in both cases with
a
polymer
concentration at 3.3 mg mL-1, Figure S13, Supporting Information), 100 mm was used for magneto-induced orientation of MWCNTs.
thus further confirming the templating efficacy exercised by the
tubular carbon framework.
Polarised optical microscopy (POM) was performed on a Nikon
model Eclipse LV100POL optical polarizing microscope.
Polarised UV-Vis spectra were recorded on a JASCO V-670
UV/Vis/NIR spectrophotometer.
Chemicals were purchased from Aldrich, Fluka, and Acros and
used as received. Solvents were purchased from JT Baker,
Aldrich and VWR, and deuterated solvents from Aldrich and
Cambridge Isotope Laboratories. Thin layer chromatography
(TLC) was conducted on pre-coated aluminium sheets with 0.20
mm Machevery-Nagel Alugram SIL G/UV254 with fluorescent
indicator UV254. Column chromatography was carried out using
Merck Gerduran silica gel 60 (particle size 15-40 and 40-63 μm).
MWCNTs are Nanocyl 7000, batch 318-25. Characterization
spectra of compound 1 are in the Supporting Information (Figures
S14-S18). CCDC 1432475 (1) contains the supplementary
crystallographic data for this paper - these data can be obtained
free of charge from The Cambridge Crystallographic Data Centre.
Conclusions
We report the development of a novel hybrid material comprising
a chromophore array adsorbed on carbon nanotubes and
embedded in an organogel. The chromophores are made of a
supramolecular porphyrin array built by metal-ligand coordination
and was thoroughly characterized in solution before being
adsorbed on carbon nanotubes. The hybrid material was then
characterized, and molecular modelling used in order to gain
insight in the interaction. Finally, magnetic manipulation of the
hybrid material, and the subsequent locking of the orientation in
an organogel, showed optical anisotropy, suggesting anisotropic
arrangement of the porphyrin arrays due to the templating effect
of the carbon nanotubes. This paves the way for new applications
of these functional materials since the information, partitioned by
the magnetic field on the templated chromophore, could be
preserved over time. Such hybrid materials could be used to
fabricate field-effect transistors,[133] solar cells[134] and tailoring
charge-transfer processes.[135] Further efforts could be also
directed in preparing anisotropic hydrogels and exploiting the
mechanical toughness, actuating and electroconductive
properties.[131]
Syntheses.
1,6-Bis-[(Zn(II)-5-(1-phen-4-yl)-10,15,20-
trimesitylporphyryl)ethynyl]pyrene (1): To a Schlenk tube, a
solution
of
Zn(II)-5-(4-iodophenyl)-10,15,20-
trimesitylporphyrin[110] (50.0 mg, 53.7 μmol) in toluene/Et3N (5:1,
15.0 mL) was added and the whole was degassed with a freeze-
pump-thaw cycle. After this, [Pd2(dba)3] (12.3 mg, 13.4 μmol) and
AsPh3 (16.4 mg, 53.6 μmol) were added and the suspension was
subjected to another degassing cycle. Finally, 1,6-
diethynylpyrene 5[111] (5.0 mg, 24.4 μmol) was added and all was
degassed for the last time. All was stirred at room temperature
overnight, under argon atmosphere. The reaction mixture was
filtered over celite (with the aid of CH2Cl2), evaporated, purified by
column chromatography (CHX/CH2Cl2, 85:15 v/v) and further
purified by precipitation from CH2Cl2 with cold petroleum ether to
obtain the pure product as dark red solid (62% yield, 28.0 mg).
Crystals suitable for X-ray were obtained from CHCl3/MeOH.
m.p. > 300 °C. 1H-NMR (500 MHz, CDCl3): δ 8.97-8.93 (m, 6 H,
Ar-H + β-pyrrole), 8.82 (d, J = 4.6, 4 H, β-pyrrole), 8.74 (s, 8 H, β-
pyrrole), 8.43 (d, J = 7.7 Hz, 2H, Pyr-H), 8.35-8.30 (m, 8 H, Ar-H
+ β-pyrrole), 8.14 (AA′BB′, d, J = 7.4, 4 H, Ar-H), 7.30 (s, 12 H, Ar-
H), 2.65 (s, 18 H, Ar-CH3), 1.88 (s, 36 H, Ar-CH3). 13C-NMR (126
MHz, CDCl3): δ 150.23, 150.20, 150.04, 149.90, 143.69, 139.54,
139.29, 139.20, 137.69, 137.67, 134.87, 132.52, 132.15, 131.65,
131.48, 131.41, 131.08, 130.46, 130.18, 128.63, 127.91, 126.80,
Experimental Section
1
Materials and Methods. Melting points are uncorrected. H and
13C NMR spectra were measured using
a Varian Inova
spectrometer at 500 and 125 MHz, respectively. Chemical shifts
are reported in parts per million (ppm) and are referenced to the
residual solvent peak. Coupling constants (J) are given in hertz
(Hz). The Self-diffusion coefficient evaluations were carried out
using Varian Inova (500 MHz) NMR spectrometer equipped with
Performa II-Z gradient coils with a cc_BPPSTE pulse sequence.
Microwave irradiation was performed using CEM Discovery
Reactor, using a dynamic mode of 200 W maximum power. UV-
Vis spectra were recorded on a Varian Cary 5000 spectrometer.
Fluorescence spectra were recorded with a Varian Cary Eclipse
spectrophotometer. IR spectra (KBr) were recorded on a Perkin
This article is protected by copyright. All rights reserved.

10.1002/cplu.201800623
ChemPlusChem
FULL PAPER
125.63, 124.70, 122.74, 119.43, 119.26, 119.06, 118.92, 96.08,
the ideal model with the following system: the solvent box
89.78, 22.03, 21.96, 21.74. IR (KBr): cm-1 3446, 2921, 2851, 2337, containing the solvated [1∙BPE]2 complex, has been placed in
2030, 1952, 1639, 1432, 1384, 1112, 1061, 876, 616. MS (HR-
MALDI, DCTAB) found 1850.6505 (M+), C126H98N8Zn2 requires
1850.6497.
contact with a portion of the original nanotube wall having a
surface area of about 140 nm2. This slab of the nanotube wall is
kept rigid during the simulations. Also, all the solvent molecules
defining the edge of the solvent box have been frozen, to avoid
their dispersion in the non-periodic modelling box. A few solvent
molecules have been removed to reduce the liquid density and
favour the diffusion.
Zinc(II)
(trimethylsilyl)ethynyl]phenyl}-porphyrin (2): To a Schlenk
tube, solution of Zn(II)-5-(4-iodophenyl)-10,15,20,-
5,10,15-Trimesityl-20-{4-[2-
a
trimesitylporphyrin[110] (50.0 mg, 53.7 μmol) in toluene/Et3N (5:1,
15.0 mL) was added and the whole was degassed with a freeze-
pump-thaw cycle. After this, [Pd2(dba)3] (6.2 mg, 6.7 μmol) and
AsPh3 (8.2 mg, 26.7 μmol) were added and the suspension was
subjected to another degassing cycle. Finally, TMSA (7.3 μL,
107.4 μmol) was added and all was degassed for the last time. All
was stirred at room temperature overnight, under argon
atmosphere. The reaction mixture was filtered over celite (with the
aid of CH2Cl2), evaporated and purified by column
chromatography (CHX/CH2Cl2, 85:15) to afford a dark purple solid
which was further purified by precipitation from CH2Cl2 with cold
petroleum ether to obtain the pure product (83% yield, 41.0 mg).
Characterizations were in accordance with literature.[110] m.p. >
300 °C. 1H-NMR (500 MHz, CD2Cl2): δ 8.86 (d, J = 4.6 Hz, 2H, β-
pyrrole), 8.76 (d, J = 4.6 Hz, 2H, β-pyrrole), 8.72 (s, 4 H, β-pyrrole),
8.20 (AA′BB′, d, J = 7.6 Hz, 2H, Ar-H), 7.86 (AA′BB′, d, J = 7.6 Hz,
2H, Ar-H), 7.31 (s, 6 H, Ar-H), 2.64 (s, 9 H, Ar-CH3), 1.85 (s, 6 H,
Ar-CH3), 0.39 (s, 9 H, Si-CH3). 13C-NMR (126 MHz, CD2Cl2): δ
151.83, 151.78, 151.64, 151.51, 145.26, 141.06, 141.02, 140.84,
140.79, 139.44, 136.27, 133.69, 132.97, 132.87, 132.49, 131.91,
129.57, 129.49, 124.09, 121.04, 120.80, 120.72, 106.98, 97.01,
23.31, 23.24, 23.05, 1.62. MS (HR-MS) found 899.3469 (M+),
C58H54N4SiZn requires 898.3409.
Acknowledgements
D.B. gratefully acknowledges the EU through the ERC Starting
Grant “COLORLANDS” project, the MIUR through the FIRB
(“SUPRACARBON”, contract n° RBFR10DAK6). Research in
Mons is also supported by the FNRS-FRFC through the EOS
program (2Dto3D project; contract O005018F) and the
‘Consortium des Équipements de Calcul Intensif – CECI’ program
(grant number 2.5020.11). We thank Professor C. Hunter
(University of Cambridge) for the help in trying to unravel the
equilibria ruling the [1∙(BPE)2] complex formation.
Keywords: Anisotropy • Carbon Nanotubes • Magnetic Field •
Porphyrins • Supramolecular Chemistry
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Entry for the Table of Contents (Please choose one layout)
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A three-dimensional organogel,
which consists of porphyrin arrays
adsorbed on carbon nanotubes, is
prepared and characterized.
Luka Đorđević, Tomas Marangoni,
Mingjie Liu, Rita De Zorzi, Silvano
Geremia, Andrea Minoia, Roberto
Lazzaroni, Yasuhiro Ishida, and Davide
Bonifazi*
Furthermore, the magnetic
susceptibility of the nanotubes was
exploited to prepare an organogel
with notable optical anisotropy.
Page No. – Page No.
Templating porphyrin anisotropy via
magnetically aligned carbon
nanotubes
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