Article

pubs.acs.org/Langmuir

Unveiling the Structure of Polytetraruthenated Nickel Porphyrin by

Raman Spectroelectrochemistry
Luís M. C. Ferreira,† Daniel Grasseschi,† Mauro S. F. Santos,† Paulo R. Martins,‡ Ivano G. R. Gutz,†
Ana Maria C. Ferreira,† Koiti Araki,*,† Henrique E. Toma,† and Lúcio Angnes*,†
†
Instituto de Química, Universidade de São Paulo, CEP 05508-000 Sao Paulo, SP, Brazil
‡
Instituto de Química, Universidade Federal de Goiás, CEP 74001970 Goiania, GO, Brazil
*
S Supporting Information

ABSTRACT: The structure of polytetraruthenated nickel porphyrin was

unveiled for the first time by electrochemistry, Raman spectroelectrochemistry,
and a hydroxyl radical trapping assay. The electrocatalytic active material,
precipitated on the electrode surface after successive cycling of [NiTPyP{Ru-
(bipy)2Cl}4]4+ species in strong aqueous alkaline solution (pH 13), was found to
be a peroxo-bridged coordination polymer. The electropolymerization process
involves hydroxyl radicals (as confirmed by the characteristic set of DMPO/•OH
adduct EPR peaks) as reaction intermediates, electrocatalytically generated in the
0.80−1.10 V range, that induce the formation of Ni−O−O−Ni coordination
polymers, as evidenced by Raman spectroelectrochemistry and molecular
modeling studies. The film growth is halted above 1.10 V due to the formation
of oxygen gas bubbles.

1. INTRODUCTION mediated by electrogenerated hydroxyl radicals.3 However, the

Electrocatalytically active modified electrodes can be easily
prepared by voltammetric cycling of nickel(II) macrocycle
complexes such as nickel(II) tetraazamacrocycles,1−5 Ni-
phtalocyanines,6−16 Ni-porphyrins,5,8,17−20 and Ni-Salen com-
plexes9,11 in strongly alkaline solutions (pH ≥13). Interesting
materials17,20−24 capable of promoting the oxidation of many
organic compounds are generated, including alcohols, at
relatively low overpotentials. Malinski et al.25,26 studied the
electropolymerization of tetrakis(3-methoxy-4-hydroxiphenyl)-
porphyrin and proposed the use of carbon-fiber ultra-
microelectrodes modified with the resultant material as
amperometric sensors for the determination of nitric oxide in
a single cell. The monomers were thought to be connected
through the meso-methoxyphenol substituents in the nickel
porphyrin meso positions.20,21 However, cationic [Ni-
TMPyP]4+ and anionic [Ni-TSPP]4− porphyrin complexes,20,27
where TMPyP4+ = meso-tetra(pyridyl)porphyrin and TSPP4− =
meso-tetra(4-sulfonatephenyl)porphyrin, were also shown to
exhibit electropolymerization properties generating similar
electroactive materials. More recently, Bedioui et al.28 prepared
hybrid materials based on carbon nanotubes and tetrasulfo-
nated nickel(II) phthalocyanine with similar electrochemical
properties.
The characteristic electrochemical behavior of polynickel
porphyrins and polynickel macrocycles is usually assigned to
the formation and subsequent deposition of coordination
polymers of the corresponding nickel complex on the electrode
surface, where polymerization takes place through axial μ-oxo
bridges connecting the nickel centers in a reaction that could be
similarity in the electrochemical behavior of all of those
polymeric materials among themselves and with that of nickel
hydroxide29−31 is intriguing, and the elucidation of their
structure may help to shed light on the mechanism of
stabilization of nickel hydroxide in the alpha phase.31,32 Thus,
the formation of nickel hydroxide after a kind of “electro-
chemically induced demetalation” of the starting Ni-TSPP
complex generating a TSPP/Ni(OH)2 conducting salt, where
the porphyrin is present as a radical cation, has also been
proposed.18 Nevertheless, the stability of such a reactive
porphyrin species in a strongly alkaline medium is questionable.
In fact, there are few reports showing unequivocal experimental
evidence to help elucidate their actual chemical structure, either
as hybrid materials containing Ni(OH)2 or as μ-oxo-bridged
nickel macrocycle coordination polymers. Also, no evidence of
possible intermediate species participating in the polymer
formation mechanism has been reported yet.3,5,8,14,33
Raman spectroelectrochemistry is a powerful technique for
the investigation of electrochemically generated intermediates
and products that can provide invaluable structural information
on both the species in solution and those adsorbed on the
electrode surface. In fact, pioneering work by Fleischmann,
Hendra, and MacQuilan34 on the anomalous intensification of
Raman scattering from pyridine molecules adsorbed on silver
and gold electrode surfaces culminated in the discovery of
Received: January 22, 2015
Revised: March 21, 2015
Published: March 26, 2015

© 2015 American Chemical Society 4351 DOI: 10.1021/acs.langmuir.5b00250

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Figure 1. Electronic spectrum of a 1 × 10−4 mol·L−1 [NiTPyP{Ru(bipy)2Cl}4](TFMS) solution in (a) methanol and (b) a 0.1 mol·L−1 aqueous
NaOH solution. The black and red lines correspond to the experimental and calculated spectra by deconvolution with Gaussian functions. Note that
no substitution of the chloro ligands is expected in the peripheral R = py-[Ru(bipy)2Cl]+ groups.
surface-enhanced Raman spectroscopy, SERS. Since then,
Raman spectroeletrochemistry has been used to characterize
different types of interfaces, such as those based on porphyrin
thin films obtained by interfacial polymerization35 as well as
graphene and semiconductor thin films.36,37
Tetraruthenated metalloporphyrins were extensively inves-
tigated as redox mediators for the oxidation of several
compounds for sensor applications, exploring the [Ru-
(bipy)2Cl]+ peripheral complexes as electrocatalytic active
sites in slightly acidic media.38−40 Interestingly, the tetrar-
uthenated nickel porphyrin, [NiTPyP{Ru(bipy)2Cl}4]4+, can
also be electropolymerized in pH 13 solution by redox cycling
in the 0.0 to 1.0 V vs Ag/AgCl(KCl sat.) range, despite the
presence of bulky [Ru(bipy)2Cl(pyP)]+ complexes at the meso
positions, thus making unlikely the formation of axial μ-oxo
polymers. As expected, the nickel center is electrochemically
active only in highly alkaline media, where the modified
electrode exhibits a very sharp couple of waves at around 0.4−
0.5 V, which are assigned to a Ni3+/Ni2+ process. Furthermore,
the peripheral ruthenium complexes seem to play an important
role in film growth because the electropolymerization process
was shown to be remarkably dependent on the limiting anodic
potential used in the redox cycling,19 providing new strategies
to investigate further the nature of that polymeric material.
Accordingly, the influence of hydroxide ions, the role played by
Ru and Ni sites in the electropolymerization process and film
growth, and the composition and structure of poly-[NiTPyP-
{Ru(bipy)2Cl}4] were elucidated by a detailed electronic and
Raman spectroelectrochemical study.
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2. EXPERIMENTAL SECTION
2.1. Chemicals and Reagents. Supermolecular complex μ-meso-
tetra(4-pyridyl)porphyrinatenickel(II)-tetrakis[bis(bipyridine)-
(chloro)ruthenium(II)](TFMS) 4 and sodium meso-tetra(4-
sulfonatephenyl)porphyrinate zinc(II), hereafter denoted respectively
as [NiTPyP{Ru(bipy)2Cl}4]4+ and [ZnTSPP]4−, were synthesized as
previously reported.31,38−41 Sodium hydroxide and methanol were
purchased from Merck (Darmstadt, Germany). 5,5-Dimethyl-1-
pyrroline N-oxide (DMPO) was acquired from Sigma-Aldrich Co.
and purified by distillation under reduced pressure, as recommended,
before its use as a spin scavenger.42 All aqueous solutions were
prepared using ultrapure water from a Millipore Milli-Q system
(resistivity ≥18.2 MΩ·cm).
2.2. Electrode Modification and Electrochemistry. The
electrochemical characterization was performed using a μ-Autolab
type III potentiostat/galvanostat (EcoChemie, The Netherlands). The
voltammetric measurements were carried out in a conventional 10 mL
cell using a (modified) glassy carbon disk working electrode
(geometric area: 0.071 cm2), Ag/AgCl(KCl sat.) reference electrode,
and a platinum wire as an auxiliary electrode. Electrodes were modified
as previously reported 19 by performing 5 or 50 successive
voltammetric cycles in a 1.0 × 10−4 mol·L−1 solution of [NiTPyP-
{Ru(bipy)2Cl}4]4+ species in 0.1 mol·L−1 NaOH supporting electro-
lyte in the 0.00 to 0.90 V range (scan rate = 0.1 V·s−1). The modified
electrodes were washed with the electrolyte solution and reserved for
further use. All potentials are referred to the Ag/AgCl(KCl sat.) reference
electrode.
The experimental conditions for electrode modification and
electrochemical assays were chosen after careful study by varying the
deposition pH and limiting the positive potential as shown respectively
in Figures S4 and S5. The polymeric material was not formed at pH 14
probably because of the shift in the oxygen gas evolution reaction to
lower potentials.
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2.3. Electronic Spectra. Electronic spectra in solution were
recorded in an HP 8453 diode array spectrophotometer using a 10.0
mm optical path quartz cuvette. The electronic reflectance spectra of
modified platinum electrodes were obtained using an Analytical
Spectral Devices (ASD) Field Spec fiber optics probe spectropho-
tometer equipped with a tungsten lamp. Platinum electrodes were
modified following the procedure previously described for the
modification of glassy carbon (GC) electrodes. The spectrum was
registered in reflectance mode and converted to the absorbance scale
using the ASD Field Spec equipment software.
2.4. Raman Spectra and Spectroelectrochemistry. Raman
spectra were recorded using a WITec Alpha 300R confocal Raman
microscope equipped with an EM-CCD analyzer and Ar (488 nm),
Nd:YAG (532 nm), and He−Ne (633 nm) lasers. The Raman
spectrum of solid [NiTPyP{Ru(bipy)2Cl}4](TFMS)4 was recorded at
488 and 532 nm (power = 0.15 and 2.00 mW) using an integration
time of 10 s. The Raman spectrum of a 1.0 × 10−3 mol·L−1 solution of
this supramolecular complex in aqueous 0.1 mol·L−1 NaOH was
recorded at 488 and 532 nm (power = 7.50 mW for both lasers) using
an integration time of 120 s.
Raman spectroelectrochemistry experiments were carried out using
a homemade three-electrode spectroelectrochemical cell (Figure S1 in
Supporting Information) and a PalmSens potentiostat/galvanostat.
The laser was focused on the GC electrode surface and three
successive Raman spectra (λ = 532 nm, power = 0.50 mW, integration
time = 10 s) recorded after surface modification with a poly-
[NiTPyP{Ru(bipy)2Cl}4] film while applying a potential in the 0.05 to
0.85 V range.
2.5. Electron Paramagnetic Resonance Spectroscopy. The
hypothesis of a radical species being the key intermediate species for
the formation of the poly-[NiTPyP{Ru(bipy)2Cl}4] film was
investigated using a GC electrode modified with an electrostatically
assembled [NiTPyP{Ru(bipy)2Cl}4]4+/[ZnTSPP]4− film39 polarized
at 0.90 V. The spin-trapping reaction for hydroxyl radical detection
was carried out in a specially designed electrochemical flow cell
(Figure S2 in Supporting Information). A stream of a 0.1 mol·L−1
NaOH solution was continuously passed over the modified GC surface
and merged with a 2.0 × 10−4 mol·L−1 DMPO solution at a confluence
point placed immediately after the working electrode. A peristaltic
pump was used to propel both solutions at 0.6 mL·min−1. The
resultant effluent solution was collected in an appropriate flask and
injected into a 200 μL flat quartz cell placed in the cavity of a Bruker
EMX EPR spectrometer operating at the X band (9.5 GHz). Spectra
were registered at room temperature using the following parameters:
modulation frequency = 100 kHz, modulation amplitude = 1 G, and
microwave power = 20.21 mW.
2.6. Molecular Modeling. The ground-state geometry optimiza-
tion and the Raman spectra calculation for the target species were
carried out using the Gaussian 09W software employing density
functional theory (DFT)43,44 and the B3LYP hybrid functional45
(Becke’s gradient-corrected exchange correlation46 in conjunction with
the Lee−Yang−Parr correlation functional with three parameters47).
The 6-311G++(d,p) basis set for C, N, and H atoms and the
LANL2DZ basis set for the nickel atom, with their respective
pseudopotentials for the inner shell, were employed in the calculations.
The assignment of the vibrational spectra was carried out by
comparison with literature data using GaussView 05 and Gabedit
2.4.0 software.
3. RESULTS AND DISCUSSION
3.1. Electronic Spectroscopy. The electronic spectrum of
[NiTPyP{Ru(bipy)2Cl}4](TFMS)4 in methanol solution (Fig-
ure 1a) shows absorption bands at 209, 244, 291, 355, 408, 434,
486, 526, and 558 nm, consistent with the presence of two
chromophores, the nickel(II) porphyrin and the peripheral
ruthenium complexes.41 The bands at 291, 355, 434, and 486
nm were assigned to the Ru complexes, where the 291 nm band
was assigned to characteristic π → π* internal transitions of the
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bipy ligands. The Ru(II) ligand field transitions were found at
355 nm whereas the bands at 434 and 486 nm were assigned to
Ru(II) → bipy and dπ → pπ* metal-to-ligand charge-transfer
transitions (MLCT). The changes observed in the MLCT
bands in methanol and NaOH aqueous solution can be
attributed to solvatochromic effects. The characteristic
porphyrin ring bands at 408, 526, and 558 nm were assigned
to the Soret, β, and α transitions, respectively.
According to the four frontier orbitals model48 for the
porphyrin electronic states, the Soret band is marked by a
transition from the HOMO (with a2u symmetry) to the LUMO
(eg) orbital. The a2u orbital exhibits a lower electronic density
on the pyrrolic carbons, being more sensitive to the nature of
substituents at the meso positions and the coordinated metal
ion and respective axial ligands. Therefore, changes in the
electronic properties of the peripheral ruthenium complexes
and the coordination of hydroxide anions to the nickel
porphyrin axial positions should cause a blue shift and decrease
in the intensity of the Soret band, as observed in Figure 1b.
Accordingly, one can assume that [Ni(OH)2TPyP{Ru-
(bipy)2Cl}4]2+ is the predominant species in the 0.1 mol·L−1
NaOH aqueous solution.
After 50 voltammetric cycles in the 0.00 to 0.90 V range in
aqueous NaOH solution (0.1 mol·L−1), a thin film of poly-
[NiTPyP{Ru(bipy)2Cl}4] is deposited on the platinum disk
electrode surface. This exhibits red-shifted porphyrin transitions
(Soret, β and α) consistent with formation of a π-stacked
porphyrin material (Figure 2), whereas the MLCT bands of the
peripheral ruthenium complexes exhibited only a slight red shift
and broadening indicating a much lower degree of
intermolecular interactions.
Figure 2. Electronic spectra of poly-[NiTPyP{Ru(bipy)2Cl}4]
deposited on a platinum disk electrode surface after successive cycling
(50 times) in a pH 13 aqueous 1.0 × 10−4 mol·L−1 [NiTPyP{Ru-
(bipy)2Cl}4]4+ solution in the 0.00 to 0.90 V range (black line).
Calculated absorption spectrum (red line) and set of bands obtained
by deconvolution of the actual spectrum using Gaussian functions.
3.2. Electrochemical Behavior and Characterization.
The cyclic voltammograms (CVs) corresponding to 50
successive redox cycles of a platinum disk electrode in a pH
13 aqueous 1.0 × 10−4 mol·L−1 [NiTPyP{Ru(bipy)2Cl}4]-
(TFMS)4 solution, in the 0.0−0.9 V range, are presented in
Figure 3a. The precipitation of poly-[NiTPyP{Ru(bipy)2Cl}4]
on the electrode surface is confirmed by the rise of a couple of
sharp anodic and cathodic peaks respectively at 0.49 and 0.40
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Figure 3. (a) Successive 50 cyclic voltammograms recorded while
monitoring the growth of poly-[NiTPyP{Ru(bipy)2Cl}4] on a glassy
carbon electrode from an aqueous 1.0 × 10−4 mol·L−1 monomer
solution in 0.1 mol·L−1 NaOH solution (pH 13) at 0.100 V·s−1 and
(b) CVs corresponding to the first three cycles in the 0.0 to 0.9 V
range where the 0.0 to 0.7 V region is shown in detail in the inset. CV
in pure electrolyte solution (black line), first (red line), second (blue
line), and third (green line) scan in [NiTPyP{Ru(bipy)2Cl}4]-
(TFMS)4 solution.
V, assigned to the Ni3+/Ni2+ redox couple. In particular, the
first three cycles (Figure 3b) were found to be important in the
investigation of the mechanism of polymer formation.
The rise of an irreversible anodic peak at around 0.80 V,
starting from the very first cycle in the presence of the
tetraruthenated nickel porphyrin, is evident in all 50 voltammo-
grams, suggesting the possible contribution of the peripheral
ruthenium complexes to the mechanism of polymer formation.
Ru3+/Ru2+ is a reversible monoelectronic process38,39,49 such
that the intense irreversible wave can be assigned to an
electrocatalytic process. In fact, the electrolyte discharge is
anticipated in 0.4 V (Figure S3 in Supporting Information)
when the tetraruthenated nickel porphyrin is present in
solution, suggesting the key role of the peripheral ruthenium
complexes in that electrochemical reaction. Considering the
absence of any other species except those present in the
supporting electrolyte solution, it should involve the electro-
catalytic oxidation of hydroxide anions to hydrogen peroxide
anion, molecular oxygen, or hydroxyl radical. The last
hypothesis is particularly interesting because it may be involved
in the electropolymerization mechanism18 leading to the
formation of poly-[NiTPyP{Ru(bipy)2Cl}4] species.
The electrochemical generation of dioxygen on the electrode
surface at sufficiently positive potentials is well documented in
the literature, but the formation of the other two species is
much more scarce. Thus, the hypothesis of hydroxyl radical
formation mediated by peripheral Ru(III) complexes was
pursued by EPR. For this purpose, an especially designed flow
cell was constructed in order to trap the •OH species with
DMPO soon after being generated on a GC electrode modified
with a thin film of electrostatically assembled38 [NiTPyP{Ru-
(bipy)2Cl}4]4+/[ZnTSPP]4− material. This is quite insoluble
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and allows us to explore only the electrochemical properties of
the peripheral ruthenium complexes because the tetraanionic
porphyrin stacks on the top of the tetracationic porphyrin
species acting as a spacer, thus sterically hindering the
nickel(II) axial positions and inhibiting the formation of μ-
oxo or μ-peroxo bridges that may consume that radical species.
Interestingly, the EPR spectrum of the resulting solution
(Figure 4) clearly exhibited the typical signals of the
Figure 4. EPR spectrum of the solution generated in the electro-
chemical flow cell set with a GC electrode modified with a
[NiTPyP{Ru(bipy)2Cl}4]4+/[ZnTPPS]4− film and polarized at 0.90
V, showing the characteristic signals of the DMPO/•OH spin adduct.
DMPO/•OH adduct, with a hyperfine constant of 15.6 G,
consistent with the reference value of 15.01 G.50−53 This result
indicates the formation of significant numbers of hydroxyl
radicals at the GC electrode modified with electrostatically
assembled porphyrins and polarized at 0.9 V.
The oxidation of water to molecular oxygen by the
[RuIII(bipy)3] complex in alkaline media was previously
reported in the literature.54−58 A similar reaction probably
can be promoted by the [RuIII(bipy)2Cl(pyP)] species under
appropriated electrochemical conditions. Nevertheless, because
there was no gas evolution at the modified electrode polarized
at 0.90 V, that reaction should not be significant under our
experimental conditions. Instead, in a 0.1 mol·L−1 NaOH
solution, hydroxyl radicals seem to be generated as the major
oxidation product, suggesting that it may be the key
intermediate species involved in the electropolymerization
mechanism leading to the formation of poly-[NiTPyP{Ru-
(bipy)2Cl}4].
Thus, the [RuIII(bipy)2Cl(pyP)] species generated in alkaline
media at potentials above 0.80 V should be the active species
responsible for the formation of hydroxyl radicals, either by
direct electron transfer or involving an intermediate species as
proposed by Ledney et al.57 (Scheme 1). Direct electron
transfer is thermodynamically forbidden (OH• + e− = OH, E0 =
2.02 V vs SHE), but a reaction mechanism involving the
nucleophilic attack of OH− or H2O molecules on the para
position of one of the bipy ligands produced a protonated
Ru(III) adduct whose rapid deprotonation reaction leads to the
redistribution of the charge density corresponding to the pair of
electrons and the formation of a hydroxylated bipyridyl radical.
The deprotonation of the bipy N−H intermediate is facilitated
by the high hydroxide concentration in the electrolyte such that
the subsequent reduction of the peripheral complex to the
Ru(II) state leads to the homolysis of the C−OH bond,
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Scheme 1. Possible Mechanism for the Electrocatalytic Generation of Hydroxyl Radicals Mediated by Peripheral
[RuIII(bipy)Cl(pyP)] Complexes in Strong Aqueous Alkaline Solutiona
a
Adapted from Ledney et al.57
Figure 5. Normalized Raman spectra of [NiTPyP{Ru(bipy)2Cl}4](TFMS)4 powder (red line) and the [Ni(OH)2TPyP{Ru(bipy)2Cl}4]2+ complex
present in aqueous 0.1 mol·L−1 NaOH solution (black line), acquired using the (a) 488 and (b) 532 nm laser lines.
releasing a •OH radical species and regenerating the bipy
ligand. Then, the complex is rapidly oxidized back to the
Ru(III) state by the electrode, starting a new electrocatalytic
cycle.
The formation of poly-[NiTPyP{Ru(bipy)2Cl}4] is strongly
dependent on that electrochemical process because the
characteristic Ni3+/Ni2+ waves at 0.50 and 0.40 V (peaks III
and IV in Figure 3b) are not observed when the potential
sweep is limited to values lower than 0.80 V, and there is no
significant production of the [RuIII(bipy)2(pyP)Cl] complex.
Also, potentials higher than 1.10 V promote the formation of
molecular oxygen, and bubbles released at the modified
electrode surface inhibit the deposition of that polymeric
material. Thus, the above-described mechanism seems to
explain why the voltammetric pattern in alkaline media is
different from that obtained in acidic media39 as well as the
dependence of the film growth on pH and the limiting anodic
potential. The intensity of the reversible redox couple with Epa
= 0.31 and Epc = 0.24 V (peaks I and II in Figure 3B) does not
change significantly as a function of the number of scans and
can be assigned to a soluble species present in the electrolyte
solution.
In summary, the formation of poly-[NiTPyP{Ru(bipy)2Cl}4]
proceeds via an electrochemical−chemical−electrochemical
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(ECE) mechanism taking place in a narrow potential range
(0.80 V ≤ E < 1.10 V) and involving electrocatalytically
generated hydroxyl radicals. These highly reactive species
should trigger some sort of polymerization process leading to
the deposition of a slightly soluble material as a thin film on the
electrode surface. However, no clear evidence of what is
responsible for the polymerization process has been reported.
Accordingly, Raman spectroscopy and spectroelectrochemistry
studies were carried out to shed light on the structure of such a
polymeric material.
3.3. Raman Spectroscopy and Spectroelectrochemis-
try. Raman studies were carried out in order to characterize the
poly-[NiTPyP{Ru(bipy)2Cl}4] deposited on a glassy carbon
electrode surface by comparing the spectra of [NiTPyP{Ru-
(bipy)2Cl}4](TFMS)4 in the solid state, in an aqueous 0.1 mol·
L−1 NaOH solution (Figure 5), and as a polymeric film after 5
and 50 voltammetric redox cycles in the 0.0 to 0.9 V range
(Figure 6) at a scan rate of 0.10 V·s−1.
The characteristic porphyrin and bipyridine CC and C
N stretching modes can be seen in the 1450−1650 cm−1 range
using the 532 and 488 nm laser lines. The 532 nm laser is in
resonance with the nickel porphyrin β transition so that the
intensification of the corresponding normal modes can be
explained by the Herzberg−Teller mechanism,59 where the
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Table 1. Tentative Assignment of the Raman Spectrum of

the [NiTPyP{Ru(bipy)2Cl}4]4+ Species in Aqueous 0.1 mol·
L−1 NaOH Solution in Comparison to the Spectrum of the
Pure [NiTPyP{Ru(bipy)2Cl}4](TFMS)4 Powder Registered
Using the 488 nm Laser Line and Typical Vibrational Modes
of the Peripheral [Ru(bipy)2Cl]+ Complex60−62
theoret. exp: 488 nm (in
[NiP] Ru(bipy)2Cl [NiTRP] NaOH solution) tentative assignment
3133 νsiCβ−H
3117 νassCβ−H
3087
1632 1600 1609 1608 νassCmCα
νsi CC and νsi CN
(bipy)
1555 1558 1557 1565 νass CC and νass CN
(bipy)
νsiCmCα
Figure 6. Theoretical Raman spectra of the [NiP(O2)]1− species νsiCβCβ
(top), where P represents the porphyrin ring. Raman spectra of the 1493 1487 1491 1490 νassCβCβ
poly-[NiTPyP{Ru(bipy)2Cl}4] species on a glassy carbon electrode νassCC and
after 50 (middle) and 5 (bottom) voltammetric cycles in the 0.00 to νassCN(bipy)
0.90 V range, in 0.1 mol·L1 aqueous NaOH solution. 1447 1455 1438 νsiCβCβ + νsiCmCα
(out of phase)
1369 1379
1348 1352 1355 δsi,opNCC +
asymmetric modes should be more enhanced than the δsi,ipCαCmCα (out
of phase)
symmetric ones. Accordingly, the asymmetric CC and C
νNiN
N stretching modes at 1515 cm−1 and the asymmetric
1338 1321 1324 νassNC
porphyrin ring deformation modes at 454 and 116 cm−1 are
1319
the most enhanced ones.
1274 1271 ν(bipy)
The spectral profile and peak intensities of [NiTPyP{Ru-
1259 1252 νCm−py + δipNi−
(bipy)2Cl}4]4+ species in aqueous 0.1 mol·L−1 NaOH solution OH
closely resemble those obtained for the pure powder as 1217 1217 ν(py)
described above, confirming that no degradation takes place 1168 1170 1173 1177 δipCβH
when the tetraruthenated nickel porphyrin is dissolved in 1090 1094
strongly alkaline solution (pH 13). The intensity of the ν(Ru− 1052 1064 1070 1066 δsi,ipNNiN
Cl) stretching mode at 253 cm−1 (Table 1) decreased in NaOH 974 1027 1024 1021 ring breathing (P +
solution when probed with both 488 and 532 nm laser lines. bipy) + νsiNiN
This suggests that hydroxide anions may be substituting for the 1004 989
chloride ligand in the Ru coordination sphere, but no evidence 889 901
of such a reaction could be found electrochemically. The bands 843
assigned to the Ni−O stretching and Ni−O−H angle 807 δsi,ipCαCβCβ +
δsi,ipCαCmCα
deformation modes were found respectively at 405 and 1252
cm−1, indicating that hydroxo ligands are coordinated to the Ni 719 744
696
porphyrin axial positions. Accordingly, one can assume that
650 662 669 668 δsi,opCαCβH +
[Ni(OH)2TPyP{Ru(bipy)2Cl}4]2+ is the major species present δsi,opCH(py)
in aqueous 0.1 mol·L−1 aqueous NaOH solution, but the 601
presence of minor amounts of supramolecular nickel porphyrin 557
containing [Ru(bipy)2(pyP)(OH)]+ groups cannot be com- 447 459
pletely ruled out. The conventional electrochemical behavior of 409 405 νNiO + δsi,opP
a [NiTPyP{Ru(bipy)2Cl}4]4+ solution was recovered after the 389 381
pH was adjusted to 5. 371 371 370 νRuN
The tentative assignment of the Raman spectra shown in 348 320 325 νsiNiN
Table 1 was carried out in comparison to spectra of the 253 νRuCl
porphyrin and its derivatives60−62 found in the literature, in 216 230 214 νassNiN + δassNiN
addition to the theoretical Raman spectra of [NiP], [NiP- 116 δsi,opP + δsi,opNiN
(OH)]−1, and [NiP(O2)]−1 species, where P represents the a
[NiTRP] = [NiTPyP{Ru(bipy)2Cl}4]4+ complex; [NiP] = non-
porphyrin ring. These species were considered in the substituted Ni porphyrin.
theoretical calculations assuming the possibility that the
deposited material could be a coordination polymer where
nickel porphyrin units are connected through hydroxide or Poly-[NiTPyP{Ru(bipy)2Cl}4] was deposited as a thin film
peroxide bridges. The optimized structures and respective from an aqueous NaOH solution such that hydroxide anions
theoretical Raman spectra are shown in the Supporting are coordinated to the axial positions of the nickel(II)
Information (Figures S6 and S7). porphyrin. The electrochemical and Raman data suggest the
4356 DOI: 10.1021/acs.langmuir.5b00250
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Langmuir Article

formation of μ-hydroxo, μ-peroxo, or μ-oxo bridges connecting

adjacent nickel porphyrin units. And according to the radical
trapping assay, hydroxyl radicals should be involved in the
electropolymerization mechanism.
Thus, the formation of poly-[NiTPyP{Ru(bipy)2Cl}4] was
monitored by Raman spectroelectrochemistry in order to prove
that hypothesis and identify the most probable bridging group.
The spectrum of the material deposited on the GC electrode
surface after 5 and 50 voltammetric cycles is shown in Figure 6,
in comparison to the spectrum of [NiTPyP{Ru(bipy)2Cl}4]4+
species in NaOH solution, where it is apparent that the rise of
an intense band at 399 cm−1 is assigned to a Ni−O stretching
mode.
The O−O stretching generally appears as high-intensity
bands in the 800−1300 cm−1 range depending on its
oxidization state and bond order.63,64 According to the
theoretical Raman spectra of the [NiP(O2)]1− species (Figure
6, top), the O−O stretching mode should be found around
1370 cm−1 and the O−O bond length should be 1.31 Å, as
expected for the formation of a peroxo bridge with high charge
delocalization into the porphyrin ring. Comparing the
theoretical spectra with that of poly-[NiTPyP{Ru(bipy)2Cl}4]
obtained after 5 and 50 voltammetric cycles, one can see the
rise of new bands at 1382 and 1236 cm−1, which can be
assigned to a ν(O−O) mode with slightly higher bond order
than that theoretically predicted for a peroxide. Furthermore,
the bands at 249 and 209 cm−1 can be assigned to δ(NiOO)
angular deformation modes, reinforcing the hypothesis of a μ-
peroxo-bridged Ni porphyrin polymer. No additional bands
assignable to μ-hydroxo or μ-oxo bridged species could be
found in the characteristic 800 to 1300 cm−1 range.
A red shift and broadening of most of the Raman peaks were
observed in the polymeric material obtained after 50 cycles as
compared to 5 cycles, indicating that intermolecular inter-
actions become stronger as the electropolymerization process
proceeds in NaOH solution. This behavior can be rationalized
by a higher degree of π-stacking of nickel porphyrin rings due
to the formation of a more densely packed phase, as expected
for the film growth as a function of the number of voltammetric
cycles.
The negative charge density on the O−O bridge is
dependent on the charge delocalization to the nickel porphyrin
ring, thus changing its apparent oxidation state. For example,
the band at 810 cm−1 can be assigned to a ν(Ni3+−O)
vibrational mode, which presents a higher frequency than the
analogous ν(Ni2+−O) mode at 405 cm−1. The Ru4+O
stretching mode also can be found around 800 cm−1; however,
this was disregarded because the possibility of chloride ligand Figure 7. Raman spectroelectrochemistry of poly-[NiTPyP{Ru-
substitution by hydroxide was shown to be very low, according (bipy)2Cl}4] on a glassy carbon electrode in 0.1 mol·L−1 aqueous
to our electrochemical studies as a function of the pH of the NaOH solution in three complementary wavenumber ranges.
electrolyte solution.
Finally, poly-[NiTPyP{Ru(bipy)2Cl}4] was studied by formation of Ni−O−O−Ni peroxo bridges, involving hydroxyl
Raman spectroelectrochemistry (Figure 7) in the 0.00 to 0.70 radicals as an intermediate. This is confirmed by the rise of the
V range, making it possible to correlate the structural changes 1234 and 209 cm−1 bands assigned to the ν(O−O) and
associated with a given redox process and reinforce the δ(NiOO) modes, respectively. Additionally, the red shift of the
evidence supporting the proposed structure. The first point to porphyrin ν(CC) and ν(CN) modes at 1610 and 1560 cm−1
be highlighted here is the absence of a typical Ni(OH)2 band shows the π stacking of the nickel porphyrin rings as the
around 475 cm−1 considering the whole potential range (Figure electropolymerization process proceeds. These vibrational
7a−c), thus ruling out the hypothesis of electrochemically modes were not significantly influenced when higher potentials
induced decomposition of the NiP complex65 and the were applied, confirming the assignment of the anodic wave at
formation of authentic Ni(OH)2. The spectrum of the material 0.52 V to the Ni2+/Ni3+ process. This conclusion is reinforced
formed after five voltammetric cycles (Figure 5a) showed that by the saturation behavior of the intensity of the 810 cm−1
the oxidation of Ni2+ to Ni3+ around 0.50 V is coupled with the peak, assigned to the ν(Ni3+−O) mode, that reaches its
4357 DOI: 10.1021/acs.langmuir.5b00250
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Langmuir
maximum in the 0.45 to 0.55 V range. In summary, the Raman
spectroelectrochemistry studies confirmed the hypothesis that
poly-[NiTPyP{Ru(bipy)2Cl}4] is constituted by stacked nickel
macrocycles connected by μ-peroxo bridges instead of hybrid
composites of authentic Ni(OH)2 formed upon electrochemi-
cally induced decomposition of the nickel porphyrin complex.
This conclusion is also supported by the fact that the CV and
absorption spectral profile of the starting [NiTPyP{Ru-
(bipy)2Cl}4]4+ complex is recovered upon neutralization of
the polymeric material.
4. CONCLUSIONS
Spectroscopic and Raman spectroelectrochemical studies were
carried out, demonstrating for the first time that the polymeric
material, electrochemically deposited from strongly alkaline
solutions of the [NiTPyP{Ru(bipy)2Cl}4]4+ complex, is a μ-
peroxo-bridged coordination polymer. The electropolymeriza-
tion process involves the reaction of hydroxyl radicals, as
confirmed by EPR using DMPO as a spin-trapping agent, with
the hydroxide anions coordinated to the nickel porphyrin axial
positions. In fact, the oxidation of the peripheral ruthenium
complexes to Ru(III) leads to the electrocatalytic formation of
hydroxyl radicals in the 0.80−1.10 V range, inducing the
formation of Ni−O−O−Ni bridges. However, the film growth
is halted above 1.10 V because of the formation of oxygen gas
bubbles that disturb the electrode surface, precluding the
adhesion of poly-[NiTPyP{Ru(bipy)2Cl}4]. The presence of μ-
peroxo bridges was confirmed by the rise of Raman peaks
assigned to ν(O−O) and δ(NiOO) at 1234 and 206 cm−1 and
the enhancement of the 810 cm−1 peak assigned to the ν(Ni3+−
O) vibrational mode as Ni2+(O2−2) is oxidized to the respective
Ni3+ species. Our findings probably can be extended to other
nickel porphyrins.
■
ASSOCIATED CONTENT
*
S Supporting Information
Scheme of Raman spectroelectrochemical cell. CV of GCE in
NaOH in the presence and absence of nickel porphyrin.
Successive CVs as a function of pH. CVs as a function of anodic
limiting potential in NaOH. DFT-optimized structures and
calculated DFT Raman spectra of NiP, [NiP(OH)]−1, and
[NiP(O2)]−1. This material is available free of charge via the
Internet at http://pubs.acs.org.
■
AUTHOR INFORMATION
Corresponding Authors
*E-mail: koiaraki@iq.usp.br. Phone: ++ 55 11 3091 8513.
*E-mail: luangnes@iq.usp.br. Phone: ++ 55 11 3091 3828. Fax:
++ 55 11 3091 3781.
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
We thank Fundaçaõ de Amparo à Pesquisa do Estado de São
Paulo (FAPESP), Conselho Nacional de Desenvolvimento
́ Camacho, L. Anodic Electrodeposition of NiTSPP from Aqueous
Cientifico e Tecnológico (CNPq), and Coordenaçaõ de
Aperfeiçoamento de Pessoal de Ensino Superior (CAPES) for
financial support and a fellowship for D.G. (FAPESP 2011/
00037-6). We also thank Dr. Tiago Araujo Matias for helpful
discussions.
4358
Article
■ REFERENCES
(1) Azad, U. P.; Ganesan, V. Influence of Metal Nanoparticles on the
Electrocatalytic Oxidation of Glucose by Poly(NiIIteta) Modified
Electrodes. Electroanalysis 2010, 22, 575−583.
(2) Cataldi, T. R. I.; Centonze, D.; Ricciardi, G. Electrode
Modification with a Poly(NiII -tetramethyldibenzo-tetraaza[14]-
annulene) film. Electrochemical Behavior and Redox Catalysis in
Alkaline Solutions. Electroanalysis 1995, 7, 312−318.
(3) Roslonek, G.; Taraszewska, J. Electrocatalytic oxidation of
alcohols on glassy carbon electrodes electrochemically modified with
nickel tetraazamacrocyclic complexes: mechanism of film formation. J.
Electroanal. Chem. 1992, 325, 285−300.
(4) Taraszewska, J.; Roslonek, G. Voltammetric behaviour of Ni(II)
and Co(III) tetraazamacrocyclic complexes containing a pendant
amino group. J. Electroanal. Chem. 1991, 297, 245−255.
(5) Trevin, S.; Bedioui, F.; Villegas, M. G. G.; Bied-Charreton, C.
Electropolymerized nickel macrocyclic complex-based films: design
and electrocatalytic application. J. Mater. Chem. 1997, 7, 923−928.
(6) Agboola, B.; Nyokong, T. Electrocatalytic oxidation of
chlorophenols by electropolymerised nickel(II) tetrakis benzylmer-
capto and dodecylmercapto metallophthalocyanines complexes on
gold electrodes. Electrochim. Acta 2007, 52, 5039−5045.
(7) Altamar, L.; Fernández, L.; Borras, C.; Mostany, J.; Carrero, H.;
Scharifker, B. Electroreduction of chloroacetic acids (mono-, di- and
tri-) at poly-Ni(II)-tetrasulfonated phthalocyanine gold modified
electrode. Sens. Actuators, B 2010, 146, 103−110.
(8) Berríos, C.; Marco, J. F.; Gutiérrez, C.; Ureta-Zañartu, M. S.
Study by XPS and UV-Visible and DRIFT Spectroscopies of
Electropolymerized Films of Substituted Ni(II)-p-Phenylporphyrins
and -Phthalocyanines. J. Phys. Chem. B 2008, 112, 12644−12649.
(9) Berríos, C.; Ureta-Zañartu, M. S.; Gutiérrez, C. Impedance study
of electropolymerized films of polyNi(II)-macrocycles. Electrochim.
Acta 2007, 53, 792−802.
(10) Chauke, V.; Matemadombo, F.; Nyokong, T. Remarkable
sensitivity for detection of bisphenol A on a gold electrode modified
with nickel tetraamino phthalocyanine containing Ni−O−Ni bridges.
J. Hazard. Mater. 2010, 178, 180−186.
(11) Cortez, L.; Berríos, C.; Yáñez, M.; Cárdenas-Jirón, G. I.
Theoretical study of the binding nature of glassy carbon with
nickel(II) phthalocyanine complexes. Chem. Phys. 2009, 365, 164−
169.
(12) Khene, S.; Lobb, K.; Nyokong, T. Interaction between nickel
hydroxy phthalocyanine derivatives with p-chlorophenol: Linking
electrochemistry experiments with theory. Electrochim. Acta 2010, 56,
706−716.
(13) Mugadza, T.; Nyokong, T. Facile electrocatalytic oxidation of
diuron on polymerized nickel hydroxo tetraamino-phthalocyanine
modified glassy carbon electrodes. Talanta 2010, 81, 1373−1379.
(14) Obirai, J.; Bedioui, F.; Nyokong, T. Electro-oxidation of phenol
and its derivates on poly-Ni(OH)TPhPyPc modified vitreous carbon
electrodes. J. Electroanal. Chem. 2005, 576, 323−332.
(15) Pontié, M.; Gobin, C.; Pauporté, T.; Bedioui, F.; Devynck, J.
Electrochemical nitric oxide microsensors: sensitivity and selectivi-
tyvcharacterisation. Anal. Chim. Acta 2000, 441, 175−185.
(16) Ureta-Zañartu, M. S.; Alarcón, A.; Muñoz, G.; Gutiérrez, C.
Electrooxidation of methanol and ethylene glycol on gold and on gold
modified with an electrodeposited polyNiTSPc film. Electrochim. Acta
2007, 52, 7857−7864.
(17) Ciszewski, A.; Milczarek, G. Electrocatalytic oxidation of
alcohols on glassy carbon electrodes electrochemically modified by
conductive polymeric nickel(II) tetrakis(3-methoxy-4-hydroxyphenyl)
porphyrin film. J. Electroanal. Chem. 1996, 413, 137−142.
(18) Pérez-Morales, M.; Muñ oz, E.; Martín-Romero, M. T.;
Basic Media. Langmuir 2005, 21, 5468−5474.
(19) Quintino, M. d. S. M.; Winnischofer, H.; Nakamura, M.; Araki,
K.; Toma, H. E.; Angnes, L. Amperometric sensor for glucose based
on electrochemically polymerized tetraruthenated nickel-porphyrin.
Anal. Chim. Acta 2005, 539, 215−222.
DOI: 10.1021/acs.langmuir.5b00250
Langmuir 2015, 31, 4351−4360
Langmuir
(20) Trévin, S.; Bedioui, F.; Devynck, J. New electropolymerized
nickel porphyrin films. Application to the detection of nitric oxide in
aqueous solution. J. Electroanal. Chem. 1996, 408, 261−265.
(21) Ciszewski, A.; Milczarek, G. Glassy carbon electrode modified
by conductive, polymeric nickel(II) porphyrin complex as a 3D
homogeneous catalytic system for methanol oxidation in basic media.
J. Electroanal. Chem. 1997, 426, 125−130.
(22) Fish, J. R.; Kubaszewski, E.; Pea, A.; Malinski, T.; Kaczor, J.;
Kus, P.; Czuchajowski, L. Synthesis and Electrochemistry of
Conductive Copolymeric Porphyrins. Chem. Mater. 1992, 4, 795−803.
(23) Hrbác,̌ J.; Gregor, Č .; Machová, M.; Králová, J.; Bystroň, T.; Č íž,
M.; Lojek, A. Nitric oxide sensor based on carbon fiber covered with
nickel porphyrin layer deposited using optimized electropolymeriza-
tion procedure. Bioelectrochemistry 2007, 71, 46−53.
(24) Malinski, T.; Ciszewski, A.; Fish, J. R. Conductive Polymeric
Tetrakis(3-methoxy-4-hydroxyphenyl)porphyrin Film Electrode for
Trace Determination of Nickel. Anal. Chem. 1990, 62, 909−914.
(25) Bailey, F.; Malinski, T. Carbon-Fiber Ultramicroelectrodes
Modified with Conductive Polymeric Tetrakis(3-methoxy-4-
hydroxyphenyl)porphyrin for Determination of Nickel in Single
Biological Cells. Anal. Chem. 1991, 63, 395−398.
(26) Malinski, T.; Taha, Z. Nitric Oxide release from a Single Cell
Measured in Situ by a Porphyrinic-Based Microsensor. Nature 1992,
358, 676−678.
(27) Chen, S.-M.; Wang, C.-H. The electrocatalytic reactions of
adenine, guanine, H2O, H2O2, N2H4, and L-cysteine catalyzed by
poly(Ni(4-TMPyP)) film-modified electrodes. J. Solid State Electro-
chem. 2007, 11, 281−291.
(28) Porras Gutierrez, A.; Griveau, S.; Richard, C.; Pailleret, A.;
Gutierrez Granados, S.; Bedioui, F. Hybrid Materials from Carbon
Nanotubes, Nickel Tetrasulfonated Phthalocyanine and Thin Polymer
Layers for the Selective Electrochemical Activation of Nitric Oxide in
Solution. Electroanalysis 2009, 21, 2303−2310.
(29) Danczuk, M.; Nunes, C. V., Jr.; Araki, K.; Anaissi, F. J. Influence
of Alkaline Cation on the Electrochemical Behavior of Stabilized Alpha
Nickel Hydroxide. J. Solid State Electrochem. 2014, 18, 2279−2287.
(30) El-Shafei, A. A. Electrocatalytic oxidation of methanol at a nickel
hydroxide/glassy carbon modified electrode in alkaline medium. J.
Electroanal. Chem. 1999, 471, 89−95.
(31) Rocha, M. A.; Winnischofer, H.; Araki, K.; Anaissi, F. J.; Toma,
H. E. A New Insight on the Preparation of Stabilized Alpha-Nickel
Hydroxide Nanoparticles. J. Nanosci. Nanotechnol. 2011, 11, 3985−
3996.
(32) Martins, P. R.; Araújo Parussulo, A. L.; Toma, S. H.; Rocha, M.
A.; Toma, H. E.; Araki, K. Highly stabilized alpha-NiCo(OH)2
nanomaterials for high performance device application. J. Power
Sources 2012, 218, 1−4.
(33) Bukowska, J.; Rostonek, G.; Taraszewska, J. In-situ surface-
enhanced Raman spectroscopic study of gold electrodes modified with
nickel tetraazamacrocyclic complexes. J. Electroanal. Chem. 1996, 403,
47−52.
(34) Fleischmann, M.; Hendra, P. J.; McQuillan, A. J. Raman spectra
of pyridine adsorbed at a silver electrode. Chem. Phys. Lett. 1974, 26,
163−166.
(35) Czernuszewicz, R. S.; Macor, K. A. A Low-Temperature Bulk
Electrolysis Cell for in situ Resonance Raman Spectroelectrochemis-
try: Observation of the FeIVO Stretching Frequency for Electro-
generated Ferryl Tetramesitylporphyrin. J. Raman Spectrosc. 1988, 19,
553−557.
(36) Frank, O.; Dresselhaus, M. S.; Kalbac, M. Raman Spectroscopy
and in Situ Raman Spectroelectrochemistry of Isotopically Engineered
Graphene Systems. Acc. Chem. Res. 2015, 48, 111−118.
(37) Salvatierra, R. V.; Moura, L. G.; Oliveira, M. M.; Pimenta, M. A.;
Zarbin, A. J. G. Resonant Raman spectroscopy and spectroelec-
trochemistry characterization of carbon nanotubes/polyaniline thin
film obtained through interfacial polymerization. J. Raman Spectrosc.
2012, 43, 1094−1100.
(38) Angnes, L.; Azevedo, C. M. N.; Araki, K.; Toma, H. E.
Electrochemical detection of NADH and dopamine in flow analysis
4359
Article
based on tetraruthenated porphyrin modified electrodes. Anal. Chim.
Acta 1996, 329, 91−96.
(39) Azevedo, C. M. N.; Araki, K.; Angnes, L.; Toma, H. E.
Electrostatically Assembled Films for Improving the Properties of
Tetraruthenated Porphyrin Modified Electrodes. Electroanalysis 1998,
10, 467−471.
(40) Martins, P. R.; Popolim, W. D.; Nagato, L. A. F.; Takemoto, E.;
Araki, K.; Toma, H. E.; Angnes, L.; Penteado, M. D. V. C. Fast and
reliable analyses of sulphite in fruit juices using a supramolecular
amperometric detector encompassing in flow gas diffusion unit. Food
Chem. 2011, 127, 249−255.
(41) Toma, H. E.; Araki, K. Spectroelectrochemistry And Electro-
catalytic Properties of a Tetraruthenated Nickel Porphyrin. J. Chem.
Res. 1994, 1994, 1501−1515.
(42) Augusto, O. In CRC Handbook of Biomedicine of Free Radicals
and Antioxidants; Miguel, J., Ed.; CRC Press: Boca Raton, FL, 1989;
Vol. 3.
(43) Hohenberg, P. Inhomogeneous Electron Gas. Phys. Rev. 1964,
136, B864−B871.
(44) Kohn, W.; Sham, L. J. Self-Consistent Equations Including
Exchange and Correlation Effects. Phys. Rev. 1965, 140, A1133−
A1138.
(45) Becke, A. D. Density-functional thermochemistry. V. Systematic
optimization of exchange-correlation functionals. J. Chem. Phys. 1997,
107, 8554.
(46) Becke, A. D. Density-functional thermochemistry. III. The role
of exact exchange. J. Chem. Phys. 1993, 98, 5648.
(47) Hill, E. A Problem in the Quantum Mechanics of Crystals. Phys.
Rev. 1931, 37, 785−794.
(48) Gouterman, M. Spectra of Porphyrins. J. Mol. Spectrosc. 1961, 6,
138−163.
(49) Araki, K.; Wagner, M. J.; Wrighton, M. S. Layer-by-layer growth
of electrostatically assembled multilayer porphyrin films. Langmuir
1996, 12, 5393−5398.
(50) Buettner, G. R. Spin Trapping of the Hydroxyl Radical. In CRC
Handbook of Methods for Oxygen Radical Research; Greenwald, R. A.,
Ed.; CRC Press: Boca Raton, FL, 1985; pp 151−156.
(51) Buettner, G. R. Spin trapping: ESR parameters of spin adducts.
Free Radical Biol. Med. 1987, 3, 259−303.
(52) Buettner, G. R.; Mason, R. P. Spin-Trapping Methods for
Detecting Superoxide and Hydroxyl Free Radicals In Vitro and In
Vivo. In Critical Reviews of Oxidative Stress and Aging: Advances in Basic
Science, Diagnostics and Intervention; Rodriguez, R. G. C. a. H., Ed.;
World Scientific: Singapore, 2003; Vol. I, pp 27−38.
(53) Mottley, C.; Connor, H. D.; Mason, R. P. [17O] Oxygen
Hyperfine Structure for the Hydroxyl and Superoxide Radials Adducts
of Spin Traps DMPO, PBN AND 4-POBN. Biochem. Biophys. Res.
Commun. 1986, 141, 622−628.
(54) Creutz, C.; Sutin, N. Reaction of tris(bipyridine)ruthenium(III)
with hydroxide and its application in a solar energy storage system.
Proc. Natl. Acad. Sci. U.S.A. 1975, 72, 2858−2862.
(55) Das, S. K.; Dutta, P. K. Intrazeolitic Photoreactions of
Ru(bpy)33+ with Methyl Viologen. Langmuir 1998, 14, 5121−5126.
(56) Ghosh, P. K.; Brunschwig, B. S.; Chou, M.; Creutz, C.; Sutin, N.
Thermal and Light-Induced Reduction of Ru(bipy)3 Aqueous
Solution. J. Am. Chem. Soc. 1984, 106, 4772−4183.
(57) Ledney, M.; Dutta, P. K. Oxidation of Water to Dioxygen by
Intrazeolitic Ru(bpy)3. J. Am. Chem. Soc. 1995, 117, 7687−7695.
(58) Quayle, W. H.; Lunsford, J. H. Tris(2,2′-bipyridine)ruthenium-
(III) in Zeolite Y: Characterization and Reduction on Exposure to
Water. Inorg. Chem. 1982, 21, 97−103.
(59) Li, X.-Y.; Czernuszewicz, R. S.; Kincaid, J. R.; Su, O.; Spiro, T.
G. Consistent Porphyrin Force Field. 2. Nickel Octaethylporphyrin
Skeletal and Substituent Mode Assignments from 15N, Meso-d4, and
Methylene-d16, Raman and Infrared Isotope Shifts. J. Phys. Chem.
1990, 94, 47−61.
(60) Aydin, M. DFT and Raman spectroscopy of porphyrin
derivatives: Tetraphenylporphine (TPP). Vib. Spectrosc. 2013, 68,
141−152.
DOI: 10.1021/acs.langmuir.5b00250
Langmuir 2015, 31, 4351−4360
Langmuir Article

(61) Jiang, J.; Bao, M.; Rintoul, L.; Arnold, D. P. Vibrational

spectroscopy of phthalocyanine and naphthalocyanine in sandwich-
type (na)phthalocyaninato and porphyrinato rare earth complexes.
Coord. Chem. Rev. 2006, 250, 424−448.
(62) Li, X.-Y.; Czernuszewicz, R. S.; Kincaid, J. R.; Stein, P.; Spiro, T.
G. Consistent Porphyrin Force Field. 1. Normal-Mode Analysis for
Nickel Porphine and Nickel Tetraphenyiporphine from Resonance
Raman and Infrared Spectra and Isotope Shifts. J. Phys. Chem. 1990,
94, 31−47.
(63) Kieber-Emmons, M. T.; Annaraj, J.; Seo, M. S.; Heuvelen, K. M.
V.; Tosha, T.; Kitagawa, T.; Brunold, T. C.; Nam, W.; Riordan, C. G.
Identification of an “End-on” Nickel-Superoxo Adduct, [Ni(tmc)-
(O2)]+. J. Am. Chem. Soc. 2006, 128, 14230−14231.
(64) Reed, R. A.; Rodgers, K. R.; Kushmeider, K.; Spiro, T. G.; Su, Y.
O. Iron-Hydroxide Stretching Resonance Raman Bands of a Water-
Soluble Sterically Hindered Porphyrin. Inorg. Chem. 1990, 29, 2881−
2883.
(65) Yeo, B. S.; Bell, A. T. In Situ Raman Study of Nickel Oxide and
Gold-Supported Nickel Oxide Catalysts for the Electrochemical
Evolution of Oxygen. J. Phys. Chem. C 2012, 116, 8394−8400.

4360 DOI: 10.1021/acs.langmuir.5b00250

Langmuir 2015, 31, 4351−4360