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Procedia Chemistry 12 (2014) 41 – 46

New Processes and Materials Based on Electrochemical Concepts at the Microscopic Level
Symposium, MicroEchem 2013

Electrochemical characterization of spiropyran structures

Georgina Armendáriz-Vidalesa, Eduardo Martínez-Gonzáleza, Denhy Hernández-Melob,
Jorge Tiburciob and Carlos Frontanaa*
a
Centro de Investigación y Desarrollo Tecnológico en Electroquímica, S.C., Parque Tecnológico Sanfandila, Pedro Escobedo, 76703, Mexico
b
Centro de Investigación y Estudios Avanzados del Instituto Politécnico Nacional, Departamento de Química, Av. IPN 2508, Zacatenco, Mexico
D.F., 07360, Mexico

Abstract

Spiropyran (SP) is a type of photochromic molecules widely studied because of their interesting physical and chemical
properties. Irradiation of spiropyrans with near UV-light induces heterolytic cleavage of the spiro bond, resulting in the
possibility of their application in electro-optical molecular devices and electronic data storage. Although some reports conclude
that the opening process also occurs upon electrochemical oxidation of the indolic nitrogen, a complete description of both
oxidation and reduction processes, is yet unavailable. In this work, cyclic voltammetry was employed for characterizing
nitrospiropyran structures. After oxidation of SP, a reduction signal at a potential value less negative than the original closed
compound appeared when successive voltammetric cycles were performed. Based on the results obtained, possible mechanistic
pathways are discussed.
© 2014
© 2014TheTheAuthors.
Authors. Published
Published by Elsevier
by Elsevier B.V. B.V.
This is an open access article under the CC BY-NC-ND license
Selection and peer-review under responsibility of the Sociedad Mexicana de Electroquimica.
(http://creativecommons.org/licenses/by-nc-nd/3.0/).
Peer-review under responsibility of the Sociedad Mexicana de Electroquimica
Keywords:Spiropyrans; cyclic voltammetry; ring opening.

1. Introduction

Photochromism, defined as a reversible transformation of a molecular species between two forms having different
absorption spectra by absorption of electromagnetic radiation1, is a well-studied phenomenon that has found

* Corresponding author. Tel.: +52 442 2116000x7849; fax: +52 442 2116001.
E-mail address: ultrabuho@yahoo.com.mx, cfrontana@cideteq.mx

1876-6196 © 2014 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/by-nc-nd/3.0/).
Peer-review under responsibility of the Sociedad Mexicana de Electroquimica
doi:10.1016/j.proche.2014.12.039
42 Georgina Armendáriz-Vidales et al. / Procedia Chemistry 12 (2014) 41 – 46

widespread applications in many fields, such as light sensitive sunglasses, electronic data storage and other electro-
optical devices2-4.
Recently, much effort has been made to investigate a variety of photoswitchable molecules: azobenzenes,
stilbenes, diarylethenes, spiropyrans, among others5. The latter type of compounds, with the unique feature of having
its two isomers possessing different properties, is composed of an indoline and a chromene moiety linked by a spiro
carbon atom, oriented perpendicular to each other5,6. When the parent closed-ring isomer of spiropyran (SP, Fig. 1)
is irradiated with near UV-light, the heterolytic cleavage of the C spiro – O bond is produced, giving rise to two
open-ring unstable isomer species (MC, Fig. 1), represented as the zwitterionic or merocyanine-like structure and the
other quinoidal;4,5,7 At room temperature, the open form reverts thermally or with irradiation with visible light to the
closed structure.2,7 It is known that a solution containing the SP closed form is colorless; as soon as the molecule is
forced to open up, the system adopts a planar form stabilized by ʌ-conjugation over the entire molecule and
switching the colorless SP solution to the purple MC.2,7 Also, it has been reported that the presence of a nitro-
substituent enhances its photochromic activity;2,8 hence, investigation is being done on synthesizing compounds with
some other derivatization, leading to higher quantum yields and a more slowly ring-closing process.2

Fig. 1. Spiropyran (SP) closed-ring structure and its stimuli-induced open-ring zwitterionic and quinoidal isomers (MC).4.7

Although the majority of publications highlight the photochemical features of spiro compounds, less attention has
been paid on their electrochemical behavior. Some reports conclude that the ring-opening process can be achieved
and monitor via electrochemistry, although Ivashenko and co-workers conclude that oxidation of spiro compounds
does not lead to open-ring structures9. In this work, cyclic voltammetry was employed for characterizing
nitrospiropyran structures and preliminary obtained results along with possible mechanistic pathways are briefly
discussed.
Nomenclature

Ru Uncompensated Resistance, ȍ
E0 Standard potential, V
Epa/c Anodic/cathodic peak potential, V
GC Glassy Carbon
SP Spiropyran, closed-ring isomer
 Georgina Armendáriz-Vidales et al. / Procedia Chemistry 12 (2014) 41 – 46 43

MC Merocyanine, open-ring isomer

SP-Ox Spiropyran oxidized form

2. Experimental

2.1. Chemicals

1-(2-hydroxyethyl)-3,3-dimethylindoline-6’-nitrobenzospiropyran and derivatives (1-3, Fig. 2) were obtained

from previous synthesis10 0.4 mM solutions of compounds 1-3 were dissolved in acetonitrile (extra dry over
molecular sieve), containing 0.1 M tetrabutylammonium hexafluorophosphate (for electrochemical analysis •99%,
dried the night before use at 105 °C). All solutions were maintained under an inert atmosphere by saturation with
high-purity nitrogen at room temperature (approx. 20 °C).

Fig. 2. Structures of the nitrospiropyrans studied

2.2. Instrumentation

Cyclic voltammetry experiments were performed using a potentiostat/galvanostat, at a scan rate of 0.1 V s-1 and
applying IR drop compensation with Ru values determined from positive feedback measurements (average Ru = 550
ȍ). A glassy carbon disk electrode (0.0079 cm2), polished with 0.05ȝm diamond suspension and rinsed with acetone
before each voltammetric run, was used as working electrode. A platinum wire and a non-aqueous electrode of
Ag|Ag+ 0.01 mol dm-3 [n-Bu4N]ClO4, were used as auxiliary and reference electrodes, respectively.
44 Georgina Armendáriz-Vidales et al. / Procedia Chemistry 12 (2014) 41 – 46

3. Results and discussion

Cyclic voltammograms for solutions of the studied compounds were obtained in acetonitrile (Figure 3). A
monoelectronic reduction process was observed in all compounds at -1.52 V (E0I for compounds 1 and 2 Fig. 3A,
and E0II for 3, Fig. 3B), associated to the reversible reduction reaction of the nitro group. Compound 3 presented an
additional reversible process possibly related to the reduction of the bipyridinium moiety, E0I = -1.22 V (Figure 3B).

Fig. 3. Cyclic voltammograms of solutions of compounds (A) 1 and 2 and (B) 3 in CH3CN / 0.1 mol dm-3 n-Bu4NPF6, v = 0.1 Vs-1, c = 0.0004 mol
dm-3; WE: GC (0.0079 cm2).

Oxidation of spirocompounds is characterized by an irreversible oxidation of the indoline moiety, whose reaction
mechanism has been scarcely discussed. Cyclic voltammograms presented in Fig. 4 show an oxidation peak at
different potential values (Epa), demonstrating its dependence on the substituent. Compound 3, bearing a
bipyridinium moiety with a positive charge, become more difficult to oxidize (Epa = 0.98 V), compared to 1 (Epa =
0.73 V) and 2 (Epa = 0.84 V).

Fig. 4. Cyclic voltammograms of 1 (ņņ), 2 (- - -) and 3 (···) in CH3CN / 0.1 mol dm-3 n-Bu4NPF6, v = 0.1 Vs-1, c = 0.0004 mol dm-3; WE: GC
(0.0079 cm2).

Also, it was observed that upon oxidizing and performing successive voltammetric cycles at low scan rates (less
than 0.1 Vs-1) to compounds 1 and 2, an additional process appeared (Fig. 5A and 5B, peaks IIc – IIa) in the
reduction scan and no significant diminishment in current of the second reduction process (IIIc / IIIa) is observed
(Fig. 5C). These results suggest that the spiropyran oxidized form (SP-Ox), generated in peak Ia, undergo a coupled
 Georgina Armendáriz-Vidales et al. / Procedia Chemistry 12 (2014) 41 – 46 45

chemical reaction that causes a new chemical species either with an additional reacting site, or this latter species
reduces more easily and thus, a shift in the reduction potential is observed, followed by the reduction of the nitrogen
moiety of the original compound.

Fig. 5. Cyclic voltammogram of 1, (A) one cycle, (B) five succesive cyclic voltammograms until process IIa-IIc is obtained at v = 0.1 Vs-1, and
(C) cyclic voltammogram before (···) and after five cycles (ņņ) , indicating that current of peaks IIIc – IIa does not diminish.

As reported by Wagner4, Preigh11 and co-workers, initial oxidation of the indoline nitrogen to give SP-Ox
followed by rearrangement, affords the formation of the MC radical cation, although no concluding electrochemical
evidence of such process has been proved yet. Wagner and colleagues proposed that the cathodic signals in the
reverse scan once the SP closed-form is oxidized, are due to reduction of stereoisomers of the MC radical
cation.4Also, it has been suggested that once the MC species is generated, ʌ-radical cation dimers are obtained6. On
the other hand, recent experiments made by Ivashenko and co-workers showed that oxidation of spiropyrans results
in the formation of covalent SP-SP dimers, as a product of a carbon-carbon bond formation.9 It is noteworthy that
contrary to the results presented in this report, neither a diminishment in the oxidation voltammetric signal (Ia) upon
successive cycles, nor the appearance of other oxidation peaks were observed. These reports, along with the
voltammetric characterization suggest that the electrochemical ring-opening of the SP structure after indoline
nitrogen oxidation does occur, although spectroelectrochemical evidence is desirable in order to confirm this
proposal.

4. Conclusions

In this work, cyclic voltammetry was employed for characterizing nitrospiropyran derivatives. It was observed
that oxidation potential depends on the substituent present in the structure. After irreversible oxidation, a reduction
signal at a potential value less negative than the original closed compound appeared when successive voltammetric
cycles were performed. Based on the results obtained, possible mechanistic pathways were discussed.

Acknowledgements

G. Armendáriz – Vidales and E. Martínez – González thank CONACYT for their studies support through
Projects SEP – CONACYT 107037 and 128419, and scholarships 351995 and 270926.

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