Supramolecular assemblies of phenolic metalloporphyrins: Structures and electrochemical studies

Article abstract of DOI:10.1142/S108842461950007X

The reactivity of two phenolic porphyrins bearing respectively catechol and gallol-derived meso substituents (5,10,15,20-Tetrakis(3,4-dihydroxyphenyl)porphyrin and 5,10,15,20-Tetrakis(3,4,5-Trihydroxyphenyl)porphyrin) with trivalent metallic ions (Fe, Mn,

Full text of DOI:10.1142/S108842461950007X

Journal of Porphyrins and Phthalocyanines
J. Porphyrins Phthalocyanines 2019; 23: 103–116
DOI: 10.1142/S108842461950007X
Published at http://www.worldscinet.com/jpp/
Supramolecular assemblies of phenolic metalloporphyrins:
Structures and electrochemical studies
Gia Co Quana, Morgane Denisb, Brian Abeykoona, Jean-Bernard Tommasinoa,
Erwann Jeanneaua, Catherine Journeta, Thomas Devic*b and Alexandra Fateeva*a
aUniversité Claude Bernard Lyon 1, Laboratoire des Multimatériaux et Interfaces (LMI), UMR CNRS 5615,
F-69622 Villeurbanne, France
bInstitut des Matériaux Jean Rouxel (IMN), UMR 6502, Université de Nantes, CNRS, 2 rue de la Houssinière,
BP32229, 44322 Nantes Cedex 3, France
This paper is part of the 2019 Women in Porphyrin Science special issue.
Received 20 December 2018
Accepted 15 January 2019
ABSTRACT: The reactivity of two phenolic porphyrins bearing respectively catechol and gallol-derived
meso substituents (5,10,15,20-tetrakis(3,4-dihydroxyphenyl)porphyrin and 5,10,15,20-tetrakis(3,4,5-
trihydroxyphenyl)porphyrin) with trivalent metallic ions (Fe, Mn, In) was studied. Six supramolecular
compounds were obtained and structurally characterized by single crystal X-ray diffraction. In each
compound, the supramolecular assembly was based on the axial coordination of a phenolate function
to the metallic ion lying in the porphyrinic core. A great diversity of supramolecular architectures was
accessible through such simple arrangements, and objects ranging from dimers to one-dimensional
polymers were isolated. Some of these assemblies were further investigated in solution by mass
spectrometry and by UV-vis absorption spectroscopy. For the iron-based materials, the redox behavior
was studied in solution through cyclic voltammetry experiments in inert conditions and under air.
KEYWORDS: supramolecular assembly, axial coordination, crystallography, structural studies,
electrochemistry.
MOFs are built up using polycarboxylic acids such as
INTRODUCTION
terephthalic acid as organic linkers, it appears natural that
Hybrid porphyrin and metal-based crystalline
TCPP (5,10,15,20-tetrakis(4-carboxyphenyl)porphyrin)-
assemblies trigger interest in numerous areas such as
based MOFs have been the most studied examples [15].
materials chemistry [1–3], photophysics [4–6], sensor
Still, many such materials suffer from a lack of stability
design [7–9] and catalyst development [10], the key point
towards hydrolysis [16]. Therefore we recently focused
being that the structural control on a supramolecular
on developing porphyrin-based hybrid frameworks built
level allows rationalization of the properties in such
up from phenolate-cation rather than carboxylate-cations
architectures. In our work on porphyrin-based porous
bonds. Interestingly, an unprecedented chemical stability
metal-organic frameworks, we have aimed to develop
was demonstrated for MOFs based on trioxobenzene
coordination polymers with enough chemical stability to
ligands [17–19]. More specifically, we recently repor-
be considered for applications in catalysis [11–13] and
ted a particularly stable MOF, MIL-173, based on
electrocatalysis [14]. Given that the wide majority of
5,10,15,20-tetrakis(3,4,5-trihydroxyphenyl)porphyrin
(H14TGP) and Zr4+ or RE3+ (RE: rare earth), which
demonstrated catalytic activity for the aerobic oxidation
of hydrocarbons [13]. In our quest to discover new
coordination polymers based on oxyphenylporphyrins,
*Correspondence to: Alexandra Fateeva, email: alexandra.
fateeva@univ-lyon1.fr; Thomas Devic, email: thomas.devic@
cnrs-imn.fr.
Copyright © 2019 World Scientific Publishing Company

104
G. CO QUAN ET AL.
we further explored the reactivity of both (H14TGP)
and 5,10,15,20-tetrakis(3,4-dihydroxyphenyl)porphyrin
(H10TCatP) with trivalent metals such as Fe, Mn and In.
It is of interest to consider the different possibilities
of assembling porphyrinic ligands with metallic ions and
specifically to differentiate two types of supramolecular
structures based on whether they are built up from a
unique building unit or two different components. In
open-framework structures, external units are linked to
the porphyrins or metalloporphyrins by coordination
functions at the aryl meso positions. In this case the
material is made up from two distinct building units:
an inorganic one (metal site) and a ligand (porphyrin or
metalloporphyrin), where each porphyrin is acting like
a bridging unit between external inorganic units (Fig. 1,
top). Another possibility to obtain supramolecular
porphyrinic assemblies is through axial binding of one
metalloporphyrin to the central metal ion of another; this
waytheresultingarchitectureconsistsofasupramolecular
assembly of a single building unit (Fig. 1, bottom). Note
that the dimensionality or the porosity of the resulting
compound is not an inherent property of one or another
type of coordination assemblies. In fact, discrete, 1D, 2D
or 3D structures, as well as cage-like porous structures,
can be obtained with either assembly mode, although
better stability towards desolvation and the highest
specific surface areas have always been achieved through
the external coordination mode.
coordination mode was through axial binding of one
metalloporphyrin to another, and four distinct crystalline
arrangements ranging from dimers to polymers were
obtained. Herein we report the synthesis and structural
characterizations in the solid state, and spectroscopic
data in solution for self-assembled materials based
on hydroxophenyl porphyrins. To the best of our
knowledge, with the exception of 5,10,15,20-tetrakis(4-
hydroxyphenyl)porphyrin-manganese(III)
[20],
no
related structures have so far been reported. Nonetheless,
phenolic porphyrins have been of interest in a number
of studies regarding properties such as electrochemical
behavior for catechol-functionalized porphyrins, [21, 22]
supercapacitive catechol-porphyrin-derived materials
[23], thin film assemblies of gallol-porphyrins [24] and
other phenolic porphyrins have been studied for solar
energy conversion [25]. In all these studies the exact
structure of the molecular material is unknown; therefore
our work paves a way to more precise knowledge about
supramolecular arrangements of phenolic porphyrins,
aiming to promote further fruitful studies in these fields.
EXPERIMENTAL
Synthesis
General methods. All reagents were purchased from
Sigma–Aldrich® and used without further purification.
1H NMR spectroscopy was performed on an AVS 300
Bruker spectrometer at the Centre Commun de RMN at
the University of Claude Bernard Lyon 1.
As stated earlier, the metal organic framework MIL-
173 built up from H14TGP and Zr or RE was first
obtained in solvothermal conditions in a DMF/water
mixture. When switching to lighter trivalent cations
(Mn, Fe, In), formation of crystalline phases was again
observed in solvothermal conditions but only using
DMF/water mixtures with much higher water content,
for both H10TCatP and H14TGP porphyrinic ligands.
Unlike MIL-173, in the current study the observed
Synthesis of porphyrins
5,10,15,20-tetrakis(3,4,5-trihydroxyphenyl)porphyrin
(H14TGP). (H14TGP) was synthesized as previously
Fig. 1. Schematic representation of two possible types of coordination compounds built up from a porphyrin and a metallic center.
Top: assemblies through external coordination based on two building units. Down: assemblies through axial ligation based on one
building unit
Copyright © 2019 World Scientific Publishing Company
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SUPRAMOLECULAR ASSEMBLIES OF PHENOLIC METALLOPORPHYRINS
105
reported [24]. The porphyrin is isolated in solid state
0.05 mmol) was combined with pyrocatechol (200 mg,
as a protonated product with bromide counter-ions.
The overall yield of the synthesis was 15%. NMR H
1.82 mmol) in a 5 ml mixture of H2O/DMF (v/v =
1
.
4:1) in a 12 mL glass vial. A FeCl3 6H2O (30 mg
(DMSO-d6, 300 MHz) d/ppm: -0.11 (s, 4H, NH), 7.61 (s,
8H, phenyl H), 8.58 (s, 8H, porphyrin b–H), 9.72 (broad s,
12H, OH); ESI-MS (m/z): 807.2 [M–H]+ 887.1 [M–2H–
Br]+ UV-vis (DMF) λmax/nm: 430 (Soret), 522, 560, 598,
655 (Q bands).
0.11 mmol) was added and then the mixture was
sonicated for 5 min at room temperature. Afterwards,
the suspension was heated at 120°C for 48 h, where the
temperature was increased over 4 h and then cooled down
to room temperature over 4 h. The solid was recovered
by filtration, washed thoroughly with deionized water
until the washed solution was colorless. After drying, the
MOF was obtained as a dark crystalline solid in a 90%
yield (36 mg of product).
5,10,15,20-tetrakis(3,4-dihydroxyphenyl)por-
phyrin (H10TCatP). The synthesis of H10TCatP was
inspired by previously reported procedures [22, 23]
and can be achieved from demethylation of either
5,10,15,20-tetrakis(3-methoxy-4-hydroxyphenyl)
porphyrin or 5,10,15,20-tetrakis(3,4-dimethoxyphenyl)
porphyrin by boron tribromide in anhydrous conditions.
In a typical procedure, (0.925 g, 1.16 mmol) of
5,10,15,20-tetrakis(3-methoxy-4-hydroxyphenyl)por-
phyrin was dissolved in anhydrous dichloromethane
(100 mL) in a round bottom flask and an inert atmosphere
was established. Then boron tribromide (20.0 mL of 1M
solution, 20.0 mmol) was slowly added at -70°C and the
reaction mixture was maintained at this temperature for
1 h. Then the reaction was left to reach room temperature
and allowed to proceed for 20 h. Then the reaction
was quenched by adding ice-cooled water. Saturated
NaHCO3 solution was added to the greenish reaction
mixture followed by ethyl acetate, and the organic layer
was separated and dried with anhydrous sodium sulfate.
The solid obtained from evaporating the organic layer
was washed with dichloromethane. The purple colored
product was obtained via filtration (560 mg, 0.755 mmol,
.
Compound 3 [In(H7TCatP)]n xH2O. 5,10,15,20-tetrakis-
(3,4-dihydroxyphenyl)porphyrin (H10TCatP) (40 mg,
0.05 mmol) was combined with pyrocatechol (500 mg,
.
4.5 mmol) and InCl3 6H2O (70 mg, 0.2 mmol) in a 5 ml
mixture of H2O/DMF (v/v = 4:1) in a 20 mL Teflon reactor
that was inserted into an autoclave. The reaction mixture
was heated at 160°C for 48 h with 6 h heating and cooling
time. The solid was recovered by filtration under vacuum.
Due to the presence of indium hydroxide as impurity the
final yield was not determined for this solid.
.
Compound 4 [Mn(H11TGP)]n xH2O. 5,10,15,20-
tetrakis(3,4,5-trihydroxyphenyl)porphyrin (H14TGP)
.
(40 mg, 0.05 mmol) was combined with MnCl2 4H2O
(30 mg, 0.15 mmol) in a 4 mL mixture of H2O/DMF
(v/v = 4:1) in a 8 mL glass vial. The mixture was sonicated
for 5 min and was heated at 120°C for 48 h with 3 h
heating and cooling time. The solid was recovered by
filtration, washed with deionized water then ethanol. The
compound was obtained as a dark crystalline solid in a
1
65% yield). NMR H (DMSO-d6, 300 MHz) d/ppm:
58% yield (25 mg of product).
.
-2.91 (s, 2H, NH), 7.18 (d, 4H, phenyl H, J = 7.9 Hz),
7.46 (d, 4H, phenyl H, J = 8.5 Hz), 7.59 (s, 4H, phenyl
H), 8.90 (s, 8H, porphyrin b–H), 9.40 (d, 8H, OH, J =
10.4 Hz); ESI-MS (m/z): 743.2 [M–H]+ 372.1 [M–2H]2+
UV-vis (DMF); λmax/nm: 427 (Soret), 520 561, 596, 654
(Q bands).
Compound
5
[Fe(H11TGP)]n xH2O. 5,10,15,20-
tetrakis(3,4,5-trihydroxyphenyl)porphyrin (H14TGP)
.
(40 mg, 0.05 mmol) was combined with FeCl2 4H2O
(30 mg, 0.15 mmol) in a 4 mL mixture of H2O/DMF
(v/v = 4:1) in a 8 mL glass vial. The mixture was sonicated
for 5 min and was heated at 120°C for 48 h with 3 h
heating and cooling time. The solid was recovered by
filtration, washed with deionized water then ethanol. The
compound was obtained as a dark crystalline solid in a
62% yield (27 mg of product).
Synthesis of supramolecular compounds
.
Compound 1 [FeH7CatP]2 xH2O. 5,10,15,20-tetrakis-
.
(3,4-dihydroxyphenyl)porphyrin (H10TCatP) (40 mg,
0.05 mmol) was dissolved in a 5 mL mixture of H2O/
DMF (v/v = 4:1) in a 12 mL glass vial. To the resultant
Compound 6 [In(H11TGP)]n xH2O. 5,10,15,20-
tetrakis(3,4,5-trihydroxyphenyl)porphyrin (H14TGP)
(40 mg, 0.05 mmol) was combined with InCl3 (39.8 mg,
0.18 mmol) in a 5 mL mixture of H2O/DMF (v/v =
4.5:0.5) in a 20 mL Teflon reactor that was inserted
into an autoclave. The mixture was heated at 120°C for
48 h with 6 h heating and cooling time. The solid was
recovered by filtration under vacuum.
.
mixture, FeCl3 6H2O (30 mg 0.11 mmol) was added and
the mixture was sonicated for 5 min at room temperature.
Afterwards, the suspension was heated at 120°C for 48 h,
where the temperature was increased over 4 h and then
cooled down to room temperature over 4 h. The solid was
recovered by vacuum filtration, washed thoroughly with
deionized water until the washed solution was colorless.
After drying, compound 1 was obtained as a dark
crystalline solid in 82.5% yield based on the chemical
formula (33 mg of product).
Single crystal diffraction
For compounds 1, 2, 3 and 6, suitable crystals
were selected and mounted on a Geminini Oxford
Diffractometer equipped with an Atlas CCD detector
and using Mo radiation (λ = 0.71069 Å) for 1, 2 and 3
.
Compound 2 [FeH7CatP]4 xH2O. 5,10,15,20-tetrakis-
(3,4-dihydroxyphenyl)porphyrin (H10TCatP) (40 mg,
Copyright © 2019 World Scientific Publishing Company
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106
G. CO QUAN ET AL.
and using Cu radiation (λ = 1.54056 Å) for compound
6. Intensities were collected at room temperature for
compounds 1 and 2 and at 100K for compound 3, by
means of the CrysalisPro software [26]. Reflection
indexing, unit-cell parameters refinement, Lorentz-
polarization correction, peak integration and background
determination were carried out with the CrysalisPro
software [26]. An analytical absorption correction was
applied using the modeled faces of the crystals. All the
structuresweresolvedbydirectmethodsusingSIR97[27]
and the least-squares refinement on F2 was achieved with
the CRYSTALS software [28]. All non-hydrogen atoms
were refined anisotropically. The hydrogen atoms were
initially refined with soft restraints on the bond lengths
and angles to regularize their geometry (C---H in the range
0.93–0.98Å and O---H = 0.82Å) and Uiso(H) (in the range
1.2–1.5 times Ueq of the parent atom), after which the
positions were refined with riding constraints. Residual
electronic density between the metalloporphyrins was
located but could not be modelled. The contribution of
the disordered solvent molecules was removed using the
SQUEEZE algorithm [29].
UV-vis measurements
UV-vis absorption spectra were recorded with a Perkin
Elmer Lambda 1050 spectrophotometer with a 3D WB
detector module with DMF solutions of compounds 1–5
-4
-5
-1
.
with a concentration range of 4.10 to 4.10 mol L .
Mass spectrometry
Mass spectrometry was performed on a Bruker
MicrOTOFQ II in electrospray ionization mode (ESI) at
the Centre Commun de Spectrométrie de Masse at the
University Claude Bernard Lyon 1.
Electrochemistry
Solventsandreagentswereavailablecommerciallyand
were used without further purification. Electrochemical
measurements were performed using an Origalys all-
in-one potentiostat and a standard three-electrode setup
with a glassy carbon electrode GCE (diameter: 3 mm),
platinum wire auxiliary electrode and a SCE (Saturated
Calomel Electrode) as reference electrode. DMF solution
concentrations of the compound during the study were
between 1.0 to 2.0 mM and n-Bu4NPF6 0.1 M was used
Crystal data of compound 5 was analyzed at room
temperature using
a Bruker–Nonius Kappa CCD
as supporting electrolyte. The voltage scan rate ranged
diffractometer working at the Mo Ka radiation. The
Bruker AXS “Collect” suite was used to integrate and
scale intensities, and a semi-empirical absorption correc-
tion (SADABS) was applied on the basis of multiple
scans of equivalent reflections. For compound 4, only
microcrystals could be obtained. Data were thus collected
on the CRISTAL beamline at Synchroton Soleil, using
a set-up adapted for small crystals at 100 (2) K on an
Xcalibur, Atlas four-circle diffractometer and equipped
with a CCD plate detector. Data reduction was performed
using CrysAlis. An empirical absorption correction was
applied using spherical harmonics on the basis of multiple
scans of equivalent reflections, implemented in SCALE3
ABSPACK scaling algorithm. Both structures of 4 and 5
were solved by direct methods using SHELXS-97 and
refined with the full-matrix least-squares routine SHELXL
[30]. Free solvent molecules were discarded using the
SQUEEZE procedure [29]. Non H-atoms were refined
anisotropically, whereas H atoms were added as rigid
bodies. In compound 5, Fe cations were found disordered
over two positions related by an inversion center.
-1
.
from 0.1 to 0.5 V s . Considering these experimental
conditions, the ferrocene/ferricinium couple, used as
internal reference for potential measurements, was
located at E1/2 = 0.445 V.
RESULTS AND DISCUSSION
Synthesis and structure analysis
Reactions with porphyrins bearing catechol coordi-
nating functions (H10TCatP) were attempted with Fe3+
and In3+ salts in DMF/water solvent mixtures at 120°C,
both with and without the addition of pyrocatechol.
Small monotopic ligands such as pyrocatechol can be
used in the synthesis of coordination assemblies as
coordination modulators. In fact, they can be seen as
competing additives that would slow down the reaction
between the metal ions and the multitopic ligands and
therefore favor single crystal growth or preferential
growth orientations allowing to tune crystal morphology.
This approach proved to be effective in the synthesis
of crystalline carboxylate-based MOFs [31–34]. In the
present case, single crystals were obtained both with
and without the addition of pyrocatechol, but the crystal
structures differed. In fact, reacting only the porphyrin
with an excess of iron salt led to the crystallization of
iron-porphyrin dimers (compound 1) while the same
reaction in the presence of an excess of pyrocatechol
resulted in the formation of tetrameric metalloporphyrin
assemblies (compound 2, see below). When In3+ was
used instead of Fe3+ in the presence of pyrocatechol
Powder diffraction
Powder X-Ray diffraction (PXRD) for compounds 1,
2, 3, and 6 was performed on a PANanlytical XpertPro
MRD diffractometer with Cu Ka1 radiation (λ =
1.540598 Å) used with 40 kV and 30 mA settings in q/q
mode, reflection geometry. PXRD data of compounds
4 and 5 were collected at 293 K on a Siemens D5000
diffractometer using CuKa radiation (λ = 1.5418 Å).
The patterns were scanned over the angular range 5–30°
(2 theta) with a step length of 0.02° (2 theta).
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SUPRAMOLECULAR ASSEMBLIES OF PHENOLIC METALLOPORPHYRINS
107
Scheme 1. Chemical structures of the phenolic porphyrins H10TCatP (left) and H14TGP (right) used in this work
Fig. 2. PXRD patterns for compounds 1 (a), 2 (b), 4 (c) and 5 (d). Black: calculated pattern from single crystal structure; grey:
experimental pattern
a polymeric phase was obtained instead of discrete
assemblies (compound 3).
bulk samples (Fig. 2) and on a scale that allowed
further investigations of their spectroscopic and redox
properties (see below).
Similar reaction conditions (solvents, temperature)
were applied to H14TGP, this time employing pyrogallol
as a modulator. Using both Mn2+ and Fe2+ salts as
reactants, almost identical polymeric chains based on
M3+ were obtained (compounds 4 and 5 respectively).
Finally, a similar structure (compound 6) was obtained
when using InCl3 as a precursor.
In case of In-based compounds (3 and 6), very low
yields were obtained, along with co-crystallization
of In(OH)3, and the synthesis was poorly repeatable,
hence precluding their full characterization. On
the opposite, all iron and manganese-containing
solids (1, 2, 4 and 5) were obtained in a pure form
as confirmed by powder X-Ray diffraction of the
Structures of compounds 1–6 were solved from
single crystal X-ray diffraction. These solids all contain
solvent molecules which were discarded using the
SQUEEZE procedure [29]. The cif files for the structures
of compounds 1–6 can be obtained from the Cambridge
Structural Database with reference numbers respectively:
CCDC 1886722, CCDC 1886720, CCDC 1886719,
CCDC 1886617, CCDC 1886616 and CCDC 1886721.
All solids present common features, notably the same
stoichiometry, namely one M3+ cation for one porphyrin
.
core, corresponding to the formula M(H7TCatP) xH2O
.
(compounds 1–3) and M(H11TGP) xH2O (compounds
4–6), whatever the metal: ligand ratio used in the course
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G. CO QUAN ET AL.
Fig. 3. The metallo(III)porphyrins in compounds 1 (top) to 6 (bottom), with the mean plane defined by the four nitrogen atoms
shown in green. For compounds 2 and 3, the two crystallographically independent molecules are pictured
of the synthesis. The metallic ion was exclusively inserted
inside the porphyrinic core and the supramolecular
architectures were built through axial coordination of
a phenolate substituent of one metalloporphyrin to the
metallic center of another. The exact position of the
cation depends on the nature of M (Fig. 3). For the solids
built up from Fe (compounds 1, 2 and 5), the cation
lies slightly outside of the porphyrinic ring (distances
from the mean plane defined by the four N atoms are
equal to 0.3977 (9) (1), 0.3879 (3) and 0.4258 (3) (2),
and 0.320 (2) Å (5)). Its coordination is completed by
a phenolate group arising from a neighboring molecule,
leading to a square pyramidal coordination environment.
In compound 4, the Mn ion adopts the same coordination
geometry, although lying that time almost perfectly in the
porphyrinic plane (distance from the mean plane defined
by the four N atoms is equal to 0.0889 (4) Å). In all cases,
M–O and M–N bond distances are in the expected range,
and in accordance with a +3 oxidation state, as confirmed
by bond valence calculations (see Table 1 for bond
distances and bond valence calculations). One can also
mention the presence of another oxygen atom occupying
the second axial position in compounds 4 and 5, but at a
distance too long (>2.5 Å) to correspond to an anionic
ligand; hence, this oxygen arises from a neutral phenolic
group, again in line with the bond valence calculations
(see Table 1). When increasing the size of the cation (In),
a truly octahedral coordination is sometimes observed.
This is the case for compound 6, as well as for half of the
porphyrins in compound 3 (see Fig. 3 and Table 1). Here
again, In–N and In–O bond distances are in agreement
with those found in the literature for indium porphyrin,
although bond valence calculations overestimate the
charge of the cation. With a single exception (half of
the molecules are fully planar in compound 3), the
porphyrin cores present nonplanar deformations (Fig. 3).
In catecholate-based compounds, porphyrins display a
mainly saddle type deformation, with a more marked
deformation in Fe-based (compounds 1 and 2) than
In-based (compound 3) solids. For the gallate-based
porphyrinic assemblies, only a wave-type deformation
is observed (compounds 4–6). In compounds 2–6,
C–O bond distances typical of the phenolic moieties
are observed (1.34–1.40 Å), confirming that catechol
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SUPRAMOLECULAR ASSEMBLIES OF PHENOLIC METALLOPORPHYRINS
109
Table 1. M–N and M–O bond lengths and corresponding bond valences (calculated from [35])
Compound
Distances M–N (Å)
Distances M–O (Å)
Total bond valence for Mn+
Bond valence
Bond valence
1 (Fe)
2 (Fe)
2.034 (5) 2.039 (4) 2.059 (4) 2.061 (5)
1.882 (4)
>3
3.1
3.1
3.1
4.0
3.6
3.3
3.1
3.8
0.6
2.053 (2) 2.053 (2) 2.057 (2) 2.059 (2)
0.6 0.6 0.6 0.6
2.035 (2) 2.047 (2) 2.050 (2) 2.052 (2)
0.6 0.6 0.6 0.6
2.109 (4) 2.109 (4) 2.117 (4) 2.117 (4)
0.8 0.8 0.8 0.8
2.119 (4) 2.124 (4) 2.131 (4) 2.144 (4)
0.8 0.8 0.8 0.7
1.998 (3) 1.998 (3) 2.003 (3) 2.011 (3)
0.7 0.7 0.7 0.7
2.026 (3) 2.033 (3) 2.039 (3) 2.047 (3)
0.6 0.6 0.6 0.6
2.081 (8) 2.081 (8) 2.114 (8) 2.114 (8)
0.9 0.9 0.8 0.8
0.6
0.6
0.5
0.7
1.875 (2)
>3
>3
0.7
1.916 (1)
0.7
3 (In)
2.255 (3)
2.255 (3)
0.4
0.4
2.095 (4)
>3
0.6
4 (Mn)
5 (Fe)
6 (In)
2.159 (3)
2.528 (3)
0.3
0.1
2.023 (4)
2.660 (4)
0.5
0.1
2.416 (8)
2.416 (8)
0.3
0.3
and gallol functionalities are not oxidized into quinone
during the course of synthesis. For compound 1, shorter
C–O bond distances (1.25–1.27 Å) occur in one fourth of
the catechol substituents, suggesting a partial oxidation.
Nevertheless, such an oxidized compound was not
detected by mass spectrometry (see below).
(Fig. 5). The case of compound 5 is more complex: the
iron cation is disordered over two positions lying on both
sides of the porphyrinic core. Hence, depending on the
sequence of occupied positions, an infinite variety of
motifs is defined, ranging from isolated dimers (similar
to compound 1), oligomers of various lengths, to infinite
chains (identical to compound 4).
Although the way the metalloporphyrins interact with
each other in the solid state through M–O bonds strongly
depends on the nature of the cation and functional groups
(catechol vs. gallol), as well as on the conditions of
crystallization, again common features can be found.
Note here that only anionic O atoms giving rise to
short M–O distances (<2.5 Å) are taken into account.
All structures built up from H7TCatP are made of the
same centrosymmetric dimer, constructed from doubly
connected porphyrins (pictured in blue and pink in
Fig. 4). In compound 1, these dimers remain isolated
from each other (Figs 4–1), whereas in compound 2,
both metalloporphyrins from one dimer connect to a
new molecule (green and yellow) through a phenolate
group, defining a tetramer (Figs 4–2). Eventually,
when moving to compound 4, thanks to the octahedral
coordination of In inserted in these extra porphyrins,
they bind again to another dimer, giving rise to a chain-
like coordination polymer (Figs 4–3). For the H11TGP-
based solids, all compounds crystalize in the same unit
cell and define very similar chain-like motifs built up
from a single type of metalloporphyrin, reminiscent
of those observed with the related ether-functionalized
5,10,15,20-tetrakis(3,4,5-trimethoxyphenyl)porphyrin-
magnesium and zinc [36]. Depending on the nature of
the cation, these metalloporphyrins are either singly
(compound 4) or doubly (compound 6) connected
As already mentioned, the catechol and gallol moieties
are only partially deprotonated. For the structures built
up from H7TCatP (compounds 1–3), the aforementioned
dimer involves oxygen atoms in meta position of the
porphyrin ring, whereas the most acidic group, namely
the oxygen atoms in para position, are deprotonated
only in compounds 2 and 3 to further form the tetramer
and chain-like motifs. Similarly, the most acidic proton
in the gallol moieties is the one located in para position
[37], and this is the first being deprotonated in previously
reported MOFs [18, 19, 38]. In the present work, the
deprotonation only occurred in the meta position. Hence,
the protonation state in the final structure of compounds
1–6 is not governed by the relative values of the pKa, but
more likely by an optimization of the molecular packing.
Indeed, connection through the oxygen atoms in para
position would lead to perpendicular porphyrin rings and
thus very open structures, while the connection through
the oxygen atoms in meta position affords closer contacts
between adjacent porphyrins.
Characterizations in solution
As described above, compounds 1, 2, 4 and 5 were
obtained in good yield as pure phase crystalline materials.
It was nevertheless found that these solids could
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110
G. CO QUAN ET AL.
Fig. 4. Assemblies of MH7TCatP in compounds 1 (dimer), 2 (tetramer) and 3 (chain). Left: atomic structures (for the sake of clarity,
H atoms are omitted, and only one position is shown for the disordered catechol groups). Right: corresponding coordination paths
Fig. 5. Chain-like assemblies of MH11TGP in compounds 4 to 6. Left: atomic structures (for the sake of clarity, H atoms are omitted,
and only one position is shown for the disordered cation in compound 5). Right: corresponding coordination paths
Copyright © 2019 World Scientific Publishing Company
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SUPRAMOLECULAR ASSEMBLIES OF PHENOLIC METALLOPORPHYRINS
111
redissolve in DMF. Unsurprisingly, discrete compounds
with a Soret band at 427 and 430 nm respectively (Figs 6a
and 6b). As reported before [22] this slightly red-shifted
values of the Soret band wavelength (compared to the
tetraphenyl porphyrin) is characteristic of the electron-
donating effect of the hydroxo substituents on the phenyl
rings [39]. In the visible region, as expected, 4 Q bands
are distinguished at 520, 561, 596, 654 nm for H10TCatP
and 516, 552, 592, 648 nm for H14TGP.
The UV-vis absorption spectra of supramolecular
compounds derived from iron and H10TCatP (1 and 2),
and from H14TGP (5) are presented Fig. 6). For all of
these iron containing compounds, very similar spectra
are obtained. The reduction of the number of Q bands
confirms the metal insertion into the porphyrin core and
in each case, two Q bands are visible at 510 and 670 nm.
The generally broad bands obtained for 1, 2 and 5 are
indicative of supramolecular interactions in solution
as bands broadening is commonly observed in case of
porphyrin aggregation [40], supporting the presence of
oligomers or polymers in solution as established by mass
spectrometry.
1 and 2 were more readily dissolved than the polymeric
assemblies 4 and 5, however, with time all the above cited
materials appear soluble in DMF. Discrete compounds 1
and 2 could be analyzed by mass spectrometry, whereas
the polymeric compounds 4 and 5 did not give any usable
spectra, presumably due to the difficulty of ionizing
polymeric assemblies. The spectroscopic properties of
all samples were assessed by UV-vis absorption and the
redox properties of iron-containing architectures were
evaluated by cyclic voltammetry.
Mass spectrometry
Discrete assemblies based on iron and catecholate
porphyrin 1 and 2 could be analyzed by electrospray
ionization mass spectrometry (MS). The data obtained
for the tetrameric compound 2 display a distribution of
mass to charge m/z signals corresponding to the parent
doubly charged tetrameric molecular ion ([2 – H + Na]2+
at 1603 m/z, [2]2+ at 1591.7 m/z) and additional signals
corresponding to m/z of trimeric ([C132H83Fe3N12O24]2+ at
1194 m/z), dimeric ([C88H54Fe2N8O16]2+ at 1592.2 m/z and
monomeric (m/z at 796.1) compounds (see ESI Sec. 2).
Although it cannot be clearly concluded at the current
stage whether these latter complexes are originating from
the fragmentation of the tetramer during the electrospray
or are already present in equilibrium in solution, this
proves that the supramolecular assembly 2 observed
in solid state does exist in DMF solution. Therefore,
intermolecular interactions are strong enough to be at
least partially preserved when the solid is dissolved even
at high dilution. In case of compound 1, the observations
were similar. At first sight, the main signals originated
from the monomer and dimer singly charged molecular
ions at 796.1 and 1592.2 m/z respectively. When the
compound at 1592.2 m/z was selected for the MS/MS
experiment, the resulting product ion corresponded as
expected to the monomeric form with the signal at 796.1.
More importantly, a closer look at the m/z region around
the dimeric molecular ion revealed the presence of signals
originating from the doubly charged tetrameric assembly
at 1591.7 m/z as described previously. Therefore the MS
analysis implies that when dissolved in DMF, compounds
1 and 2 are hardly distinguishable and a dynamic
equilibrium between monomeric and oligomeric forms
is established. Moreover, for both samples, signals
corresponding to species with a loss of one or more Fe
atoms are observed. Metalloporphyrins demetallation
has already been observed to happen during the analysis
and therefore cannot be considered representative of the
sample. Further UV-vis data presented below indeed
strongly support a quantitative metal insertion.
UV-vis spectroscopy
Catechol and gallol free-base porphyrins display simi-
lar features in their absorption spectra in DMF solution,
Fig. 6. Normalized UV-vis absorption spectra of free-base
porphyrins and iron-based compounds 1, 2 and 5
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112
G. CO QUAN ET AL.
but dramatically modified the absorption properties
of 4, it was concluded that the absorption signal at
430 nm did not originate from the presence of metal-
free compound but is proper to the Mn-based compound
4. Given its pKa (3.75), formic acid is strong enough
to protonate the phenolate function in 4, and then favor
the decomplexation of the axial gallate ligand. For this
reason we believe that the absorption observed at 430 nm
originates from the particular coordination of Mn by the
redox-active gallate ligand that might induce a charge
transfer giving rise to this intense band. Considering this,
the data in Fig. 7a indicate that in solution an equilibrium
of this axial ligation is reached with time. Still, this axial
ligation appears quite stable as diluting a solution of 4
by a factor 100 does not induce any immediate changes
(Fig. S12). An absorption band at 430 nm in the case of
Mn-porphyrins can also be attributed to the presence of
reduced (Mn(II)) or oxidized (Mn(IV)) species. Although
this hypothesis seemed very unlikely given that these
species are expected to be unstable in air, we wanted to
ensure that no redox reaction took place that could reduce
a Mn(IV) compound to Mn(III), as formic acid could be
oxidized into CO2. For that purpose, formic acid was
replaced by propionic acid, and the same observations
were made (see Fig. S13). In light of these combined
data we concluded that the absorption band at 430 nm
originates from the charge transfer due to the particular
axial coordination of the phenolate group to Mn(III).
Fig. 7. Normalized UV-vis spectra of 4 in the course of time
(a) and upon addition of formic acid (b)
Electrochemical studies
H7TCatP-based compounds 1 and 2 were dissolved in
DMF and studied by cyclic voltammetry (CV) at variable
-1
-1
.
.
.
The case of compound 4 appeared to be more
complex when the UV-vis spectrum was recorded
in DMF solution. In fact, a fresh sample displayed a
spectrum with two intense absorption bands at 430 and
476 nm along with three less intense bands at 520, 572
and 615 nm (Fig. 7a). Moreover, an evolution of the
absorption spectrum was observed when the sample
was left in DMF in aerobic conditions: the signal at
430 nm decreased, whereas the band at 476 nm became
predominant. As the intense absorption band at 430 nm
seemed quite surprising for a Mn(III) porphyrinic
compound we first aimed to check whether this could be
due to the presence of free-base porphyrin arising from a
partial metal insertion in the bulk sample. To check this,
formic acid was added to the DMF solution of the free
base porphyrin and to a solution of 4. In the former case,
no spectral changes were noticed (Fig. S14), while in the
latter a sharp decrease of the absorption at 430 nm was
observed, leading to a characteristic spectrum of Mn(III)
porphyrin with an intense Soret band at 476 nm and two
Q bands at 570 and 608 nm along with charge transfer
bands at higher energies (430, 404, 385 and 345 nm)
(see Fig. 7b). Given that the addition of formic acid did
not induce any changes on the absorption of H14TGP
scanning rates from 0.1V s to 0.5V s (all the data
-1
presented below are plotted at a 0.1V s scanning rate
unless specified) using an SCE reference electrode. Both
compounds display a characteristic irreversible oxidation
peak at 1.18 V associated to an irreversible reduction
peak at 0.15 V in reverse voltage scan (Fig. S17). The
pattern of these voltammograms corresponds to the well-
known oxidation of the catechol moiety in a non-aqueous
solvent [41–43] and was observed in case of the free-
base H10CatP (see Fig. S17). For these two complexes,
the voltammograms also remain similar in the reduction
region, as shown in Fig. 8.
Indeed, both compounds display the following signals:
a quasi-reversible electrochemical process centered
around -0.5 V, a reversible reduction at -1.25 V and an
irreversible reduction at -1.9V. Therefore, 1 and 2 present
the same redox properties and cannot be distinguished
by cyclic voltammetry in solution, in line with the result
of the mass spectrometry data. For this reason, only the
data associated with compound 1 will be presented.
Given the values of the redox potentials, the first redox
process is assigned to the metal-centered redox process
when the other two are assigned to the macrocycle-
centered electrochemical reactions (see Fig. 8b). Quite
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SUPRAMOLECULAR ASSEMBLIES OF PHENOLIC METALLOPORPHYRINS
113
10
(a)
15
5
A2
5
A1
I(µA)
-5
0
I(µA)
C1
C2
-15
-25
-5
C1
-3
-2
-1
E(V) vs SCE
0
1
-10
-1.2
-0.6
0
0.6
E(V) vs SCE
(b)
-1
10
.
Fig. 9. Cyclic voltammetry of 1 at GC electrode at 0.1 V s in
DMF under inert atmosphere. C1: first cathodic peak, A1 first
anodic peak relating to the C1/A1 redox system; A2: second
anodic peak, C2 second cathodic peak relating to the A2/C2
redox system
0
I(µA)
-10
-20
C1
10
-3
-2
-1
0
1
E(V) vs SCE
0
-1
.
Fig. 8. Cyclic voltammetry at 0.1 V s in DMF at GC electrode
for (a): 1 (black) and 2 (grey); (b): for 1 (black) and the
corresponding free-base porphyrin (grey)
I(µA)
-10
-20
low potentials for [Fe(III) → Fe(II)] redox processes
are usually observed in the presence of an axial ligand
that is strongly coordinated, stabilizing the trivalent
state [44]. Therefore this observation corroborates what
is observed by mass spectrometry, i.e. the retention of
supramolecular architectures in solution through a strong
M–O axial ligation and quite short bond length.
-1
-0.4
0.2
E(V) vs SCE
0.8
-1
.
Fig. 10. Cyclic voltammetry of 1 at GC electrode at 0.1 V s in
Then, we focused our attention on this metal-centered
monoelectronic reduction (see the cathodic peak C1 on
Fig. 8b). This process is not fully reversible since after
the reduction, part of the Fe(II) entities undergo an
oxidation at a much higher potential of 0.25 V (see A1
vs. A2, Fig. 9) which is itself related to the new reduction
peak observed around -0.15 V (C2 on Fig. 9). This result
indicates the presence of a general electrochemical-
chemical-electrochemical (ECE) process as shown in
DMF, both under inert atmosphere (grey) and under air (black)
aFeIII + e- à aFeII Electrochemical reduction E = -0.5V,
C1 with redox system C1/A1
aFeII à bFeII Chemical reaction
bFeII à bFeIII Electrochemical oxidation E = 0.25V,
A2 with redox system C2/A2
a
the equations below, where the FeIII is first reduced to
a
the FeII complex and the later undergoes a chemical
When air was bubbled in the electrochemical cell, the
reduction peak intensity at -0.5V rose by approximately
a factor of 2.5 (Fig. 10) and the oxidation signal was lost,
which points to a catalytic activation of oxygen reduction
at the potential where Fe(III) is reduced to Fe(II). Given
that oxygen reduction in DMF at the GC electrode occurs
at -0.77V, compounds 1 and 2 are active electrocatalysts
b
transformation into the FeII complex which is oxidized
at 0.25V. Although the exact nature of the ECE process
was not elucidated in this case, one can stipulate that the
probable change in the axial ligation of the generated FeII
compound would be at least partly responsible for the
irreversibility we observe here.
Copyright © 2019 World Scientific Publishing Company
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114
G. CO QUAN ET AL.
(a)
at 0.98 V (Fig. S16) [47, 48]. In the reduction scan, two
signals are observed: first an almost irreversible peak at
-0.51V ascribed to Fe(III) reduction and a second wave at
-1.25 V (Fig. 11a). This second reduction is associated to
a thin and intense oxidation peak at -1.18 V characteristic
of a redissolution. As previously, we focused on the first
reduction process; here, the system appears practically
irreversible (Fig. S15). In the presence of atmospheric
oxygen, a large reduction peak appears close to -0.51 V,
characteristic of a catalytic oxygen activation (Fig. 11b),
as observed for compounds 1–2. However, upon multi-
4
0
I(µA)
-4
-8
ple cycling, the intensity of the oxidation peak at
-1
.
0.1 V s dramatically decreases, probably because of the
deposition of an insulating film on the electrode surface.
To summarize, the electrochemical behaviors in solution
of all Fe-based compounds appear to be very similar
under inert atmosphere. Under oxygen atmosphere, even
if a catalytic activation of oxygen is observed for all
compounds, this complicated mechanism seems to lead
to opposite results upon multiple cycling, namely the
deposition of a conducting film for compounds 1 and 2,
and an insulating one for compound 5.
-2
-1
0
1
E(V) vs SCE
(b)
10
5
0
I(µA)
-5
-10
-15
CONCLUSION
In conclusion, six new supramolecular assemblies
based on phenolic porphyrins were synthesized and
structurally characterized. Their arrangements in the
solid state and their behaviors in solution were studied
and redox active iron-based compounds were electro-
chemically investigated. By tuning synthesis conditions,
the nature of the trivalent metallic cation and the
number of hydroxo functionalities on the phenyl meso
positions, a broad diversity of structural arrangements
was obtained, even if all of them are based on one only
metalloporphyrin as a building unit. We believe that
coordination assemblies based on phenolic porphyrins
should be further explored for a deeper understanding of
the reactions mechanisms and physico-chemical (notably
redox) behaviors of these non-innocent ligands.
-1.5
-0.5
0.5
E(V) vs SCE
-1
.
Fig. 11. Cyclic voltammetry of 5 at GC electrode at 0. 1V s
in DMF. Left: under inert atmosphere. Right: under inert
atmosphere (black) and under air (grey)
for oxygen reduction in DMF. Such catalytic activity
is widely known for Fe-based metalloporphyrins [45].
Interestingly, the O2·- generated by the electroreduction
catalysis process seems to react with the FeII compound
to give a new entity, which is oxidized at 0.3V. This is not
surprising as oxygen activation by iron porphyrins was
often described as an irreversible process, for example
leading to Fe–O–O–Fe dimers after oxygen binding to the
metallic center [46]. Moreover, the cyclic voltammetry
Acknowledgments
The authors thank the Centre Commun de Spectro-
metrie Masse and the Centre Commun de RMN of the
University Lyon 1, the French Ministry of National
Education, Research and Technology, the University
Lyon 1, the ANR (project STREAM) and the CNRS for
financial support. The authors also thank Synchrotron
Soleil for providing access to the beamline CRISTAL,
as well as the network Reciprocs. P. Fertey is thanked
for his help during the measurement. The authors thank
G. Mouchaham for initial experiments and fruitful
discussions. The Pays de la Loire Region is acknowledged
for the Ph.D. fellowship of M. Denis (project PSR
‘MatHySE2’).
-1
.
at 0.1 V s exhibits a continuous increase of all of the
current density upon cycling; this is presumably due to
an increase of the electrode conductivity originating from
the deposition of a conductive material on the electrode
surface, as visually observed during the experiment. The
mechanism associated to the oxygen activation appears
to be complex and is currently under investigation in our
laboratory.
When the gallol-based polymeric compound 5 was
studied by CV at a 0.1V s scanning rate in DMF, two
irreversible oxidation waves characteristic of gallol
moiety oxidation in non-aqueous solvents were observed
-1
.
Copyright © 2019 World Scientific Publishing Company
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SUPRAMOLECULAR ASSEMBLIES OF PHENOLIC METALLOPORPHYRINS
115
Supporting information
14. Lions M, Tommasino JB, Chattot R, Abeykoon B,
Guillou N, Devic T, Demessence A, Cardenas L,
Single crystal X-Ray diffraction, mass spectrometry,
UV-vis spectroscopy and electrochemistry for the
examined compounds are given in the supplementary
material. This material is available free of charge via the
Internet at http://www.worldscinet.com/jpp/jpp.shtml.
Crystallographic data have been deposited at the
Cambridge Crystallographic Data Centre (CCDC) under
numbers CCDC-1886722, CCDC-1886720, CCDC-
1886719, CCDC-1886617, CCDC-1886616 and CCDC-
1886721. Copies can be obtained on request, free of
charge, via http://www.ccdc.cam.ac.uk/data_request/cif
or from the Cambridge Crystallographic Data Centre, 12
Union Road, Cambridge CB2 1EZ, UK (fax: +44 1223-
336-033 or email: deposit@ccdc.cam.ac.uk)
Maillard F and Fateeva A. Chem. Commun. 2017;
53: 6496–6499.
15. Gao W-Y, Chrzanowski M and Ma S. Chem. Soc.
Rev. 2014; 43: 5841–5866.
16. Fateeva A, Clarisse J, Pilet G, Greneche JM, Nouar
F, Abeykoon BK, Guegan F, Goutaudier C, Luneau
D, Warren JE, Rosseinsky MJ and Devic T. Cryst.
Growth Des. 2015; 15: 1819–1826.
17. Chen E-X, Qiu M, Zhang Y-F, Zhu Y-S, Liu L-Y,
Sun Y-Y, Bu X, Zhang J and Lin Q. Adv. Mater.
2018; 30: 1704388.
18. Mouchaham G, Cooper L, Guillou N, Martineau C,
Elkaïm E, Bourrelly S, Llewellyn PL, Allain C, Cla-
vier G, Serre C and Devic T. Angew. Chem., Int. Ed.
2015; 54: 13297–13301.
19. Cooper L, Guillou N, Martineau C, Elkaim E,
Taulelle F, Serre C and Devic T. Eur. J. Inorg. Chem.
2014; 2014: 6281–6289.
20. Yang J-W, Zhang J, Yan Y, Huang X-C and Tong
S-L. Solid State Sciences 2010; 12: 1242–1247.
21. Osati S, Davarani SSH, Safari N and Banitaba MH.
Electrochim. Acta 2011; 56: 9426–9432.
22. Jamaat PR, Davarani SSH, Fumani NS, Masoumi L
and Safari N. J. Porphyrins Phthalocyanines 2008;
12: 85–93.
23. Jin S, Hill JP, Ji Q, Shrestha LK and Ariga K.
J. Mater. Chem. A 2016; 4: 5737–5744.
24. Jiang L, Lu F, Li H, Chang Q, Li Y, Liu H, Wang S,
Song Y, Cui G, Wang N, He X and Zhu D. J. Phys.
Chem. B 2005; 109: 6311–6315.
REFERENCES
1. Elemans JAAW, vanHameren R, Nolte RJM and
Rowan AE. Adv. Mater. 2006; 18: 1251–1266.
2. Meshkov IN, Zvyagina AI, Shiryaev AA, Nickolsky
MS, Baranchikov AE, Ezhov AA, Nugmanova AG,
Enakieva YY, Gorbunova YG, Arslanov VV and
Kalinina MA. Langmuir 2018; 34: 5184–5192.
3. Hu R-H, Yi C, Li Y, Zhang Z-X, Lin L-Z and Chen
W-T. J. Porphyrins Phthalocyanines 2018; 22:
325–330.
4. ShiY, Sánchez-Molina I, Cao C, Cook TR and Stang
PJ. Proc. Natl. Acad. Sci. 2014; 111: 9390–9395.
5. Lee CY, Farha OK, Hong BJ, Sarjeant AA, Nguyen
ST and Hupp JT. J. Am. Chem. Soc. 2011; 133:
15858–15861.
6. Son HJ, Jin SY, Patwardhan S, Wezenberg SJ, Jeong
NC, So M, Wilmer CE, Sarjeant AA, Schatz GC,
Snurr RQ, Farha OK, Wiederrecht GP and Hupp JT.
J. Am. Chem. Soc. 2013; 135: 862–869.
7. Guo PP, Zhao GY, Chen PL, Lei B, Jiang L, Zhang
HT, Hu WP and Liu MH. ACS Nano 2014; 8:
3402–3411.
25. Milgrom LR. J. Chem. Soc., Perkin Trans. 1 1983:
2535–2539.
26. CrysAlisPRO ODATUL, Yarnton, England.
27. Altomare A, Burla MC, Camalli M, Cascarano GL,
Giacovazzo C, Guagliardi A, Moliterni AGG, Poli-
dori G and Spagna R. J. Appl. Crystallogr. 1999; 32:
115–119.
28. Betteridge PW, Carruthers JR, Cooper RI, Prout
K and Watkin DJ. J. Appl. Crystallogr. 2003; 36:
1487.
8. He WL, Fang F, Ma DM, Chen M, Qian DJ and Liu
MH. Appl. Surf. Sci. 2018; 427: 1003–1010.
9. Zhang W, Rozniecka E, Malinowska E, Par-
zuchowski P and Meyerhoff ME. Anal. Chem.
2002; 74: 4548–4557.
29. Spek A. Acta Crystallogr. Sect. C 2015; 71: 9–18.
30. Sheldrick G. Acta Crystallogr. Sect. C 2015; 71:
3–8.
31. Hu S, Liu M, Guo X, Li K, Han Y, Song C and
Zhang G. Cryst. Growth Des. 2017; 17: 6586–6595.
32. Schaate A, Roy P, Godt A, Lippke J, Waltz F,
Wiebcke M and Behrens P. Chem. — Eur. J. 2011;
17: 6643–6651.
10. Nakagaki S, Ferreira GKB, Ucoski GM and Castro
K. Molecules 2013; 18: 7279–7308.
11. Abeykoon B, Devic T, Greneche JM, Fateeva
A and Sorokin AB. Chem. Commun. 2018; 54:
10308–10311.
33. Umemura A, Diring S, Furukawa S, Uehara H, Tsu-
ruoka T and Kitagawa S. J. Am. Chem. Soc. 2011;
133: 15506–15513.
34. Diring S, Furukawa S, TakashimaY, Tsuruoka T and
Kitagawa S. Chem. Mater. 2010; 22: 4531–4538.
35. Brese NE and O’Keeffe M. Acta Crystallogr. Sect.
B 1991; 47: 192–197.
12. Fateeva A, Chater PA, Ireland CP, Tahir AA, Khi-
myak YZ, Wiper PV, Darwent JR and Rosseinsky
MJ. Angew. Chem., Int. Ed. 2012; 51: 7440–7444.
13. Mouchaham G, Abeykoon B, Gimenez-Marquez M,
Navalon S, Santiago-Portillo A, Affram M, Guillou
N, Martineau C, Garcia H, Fateeva A and Devic T.
Chem. Commun. 2017; 53: 7661–7664.
Copyright © 2019 World Scientific Publishing Company
J. Porphyrins Phthalocyanines 2019; 23: 115–116

116
G. CO QUAN ET AL.
36. Bhuyan J and Sarkar S. Cryst. Growth Des. 2011;
11: 5410–5414.
43. Weibel N, Mishchenko A, Wandlowski T, Neu-
burger M, Leroux Y and Mayor M. Eur. J. Org.
Chem. 2009; 2009: 6140–6150.
44. Bottomley LA, Olson L and Kadish KM. In Elec-
trochemical and Spectrochemical Studies of Biolog-
ical Redox Components, Kadish K. (Ed.). Vol. 201,
American Chemical Society, 1982; pp. 279–311.
45. Huang X and Groves JT. Chem. Rev. 2018; 118:
2491–2553.
46. Latos-Grazynski L, Cheng RJ, La Mar GN and
BalchAL. J. Am. Chem. Soc. 1982; 104: 5992–6000.
47. Nasr B, Hsen T and Abdellatif G. J. Environ.
Manage. 2009; 90: 523–530.
37. Huguenin J, Ould Saad Hamady S and Bourson P.
J. Raman Spectrosc. 2015; 46: 1062–1066.
38. Saines PJ, Yeung HHM, Hester JR, Lennie AR and
Cheetham AK. Dalton Trans. 2011; 40: 6401–6410.
39. Dalton J, Milgrom LR and Pemberton SM. J. Chem.
Soc., Perkin Trans. 2 1980: 370–372.
40. Chen D-M, Zhang Y-H, He T-J and Liu F-C. Spec-
trochim. Acta Part A: 2002; 58: 2291–2297.
41. Giovanelli D, Buzzeo MC, Lawrence NS, Hardacre
C, Seddon KR and Compton RG. Talanta 2004; 62:
904–911.
42. Stallings MD, Morrison MM and Sawyer DT. Inorg.
Chem. 1981; 20: 2655–2660.
48. Yang B, Kotani A, Arai K and Kusu F. Anal. Sci.
2001; 17: 599–604.
Copyright © 2019 World Scientific Publishing Company
J. Porphyrins Phthalocyanines 2019; 23: 116–116