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ATR spectroscopy applied to photochromic polymer analysis

Article in Materials Characterization · August 2007

DOI: 10.1016/j.matchar.2006.12.003

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 Materials Characterization 58 (2007) 771 – 775

ATR spectroscopy applied to photochromic polymer analysis

R. Delgado-Macuil ⁎, M. Rojas-López, V.L. Gayou, A. Orduña-Díaz, J. Díaz-Reyes
Centro de Investigación en Biotecnología Aplicada del IPN, Ex-Hacienda de San Juan Molino Km. 1.5,
Tepetitla de Lardizábal, Tlaxcala, C. P. 90700, México
Received 12 June 2006; received in revised form 17 October 2006; accepted 8 December 2006

Abstract

This work reports the use of infrared spectroscopy in the Attenuated Total Reflection (ATR) mode to analyze the interactions
between polymeric bases and the spiropyran. Infrared spectroscopy helps to understand the interactions between the different
molecules, spiropyran polymeric base and the solvent. Polymethyl methacrylate and cellulose acetate as polymeric base and the
spiropyran 1, 3, 3 trimethyl indoline-5-nitro benzopyrane were used. Thin films of different concentrations (0.25%, 0.5%, 1%, 2%
and 5%) of spiropyran were deposited in each type of polymeric base. The infrared spectra show the frequencies associated with
the chemical bonds of each molecule. A decrease in intensity of absorbance was observed for the C = O stretching mode of the
acetate group located at 1720 cm− 1 and for the C = C and C = N stretching modes at 1642 cm− 1 associated with spiropyran. A shift
in the intensity of the peaks was also observed due to solvent and polymeric base effects on the final film.
© 2006 Elsevier Inc. All rights reserved.

Keywords: Spiropyrans; Photochromic materials; Infrared spectroscopy; Structural analysis

1. Introduction molecular transformation. This process can be reversed

by visible illumination.
Photochromism is a phenomenon wherein, the Reversible photocoloration is attributed to an equi-
absorption spectrum of a single chemical species librium between the SP (closed, colorless) form and the
changes reversibly when it is irradiated by light of a merocyanine (open, colored) form, as shown in Fig. 1.
certain wavelength, inducing transformations between The cis-cisoid isomer is an intermediate product in this
molecular states, whose absorption spectra are different. molecular transformation and it is associated to the
One of the most studied photochromic materials is sample degradation [1]. Spiropyran-doped polymers
spiropyran (SP) which absorbs ultra violet (UV) light. have a great potential for applications in optoelectronic
On UV illumination the SP's colorless isomer undergoes devices, such as data storage films and waveguides
an heterolytic cleavage of the NO bond to form a [2,3], and in bioelectronic devices, like biosensors for
colored isomer (merocyanine), which absorbs light in medical purposes [4–6]. When the molecule is in the
the visible region. The change in coloration (colorless to open merocyanine state, a dipole is generated. By laser
blue) of the sample is a physical observation of the illumination or application of an external field, its
physical and chemical properties can be controlled. The
⁎ Corresponding author. Tel.: +52 248 4 87 07 65; fax: +52 248 4 87 radical group NO could be changed to generate shifts in
07 66. the absorption peaks for the merocyanine state. One of
E-mail address: [email protected] (R. Delgado-Macuil). the most notable features of these materials, is that
1044-5803/$ - see front matter © 2006 Elsevier Inc. All rights reserved.
doi:10.1016/j.matchar.2006.12.003
772 R. Delgado-Macuil et al. / Materials Characterization 58 (2007) 771–775

the CA films, the same weight concentrations of Spiro

were mixed with 0.2 g of CA and dissolved in 10 ml of
methylene chloride. All the solutions were deposited in
Petri covered boxes and dried at room temperature for
48 h. The samples present a good optical quality and
were optically defect-free.

2.2. ATR spectroscopy analysis

The infrared spectroscopy analysis was performed

Fig. 1. Schematic molecular structure of the sample before UV using a Brucker Infrared Spectrometer Vertex 70 in the
illumination (λ = 355 nm) and after isomerization. The process is Attenuated Total Reflection (ATR) mode. A ZnSe
reversible under visible illumination (λ = 633 nm). The X isomer is an crystal in a single reflection ATR plate was used; the
intermediate product in the conversion cycle between spiropyran and transmission percentage values of this kind of plate are
merocyanine.
greater than 25. Initially, ATR spectra were obtained for
CA and PMMA in the solid state or as a film, and for the
several cycles of conversion–reconversion process can SP in a powder. These three ATR spectra were used as
be done. Otherwise each cycle generates a degrading in references to compare the ATR spectra for the rest of the
the optical properties of the sample. samples.
To know and improve the optical properties, it is
important to analyze the molecular behavior of these 3. Results and discussion
types of structures. The vibrational spectroscopies, such
as Infrared and Raman techniques, help us to understand Fig. 2 corresponds to the ATR spectrum of CA and
the interactions between the molecules (SP, polymeric PMMA using the polymeric base in film and spiropyran
matrix and solvent). Infrared [1,3,7−9] and Raman [7,9] in powder form. The spectrum corresponds to the CA
spectrometry studies have been used to observe the polymeric base, shows intense peaks for the CH3 bond
conformational and intermolecular interactions between in two different assignments and for the acetate group at
the polymeric base and the spiropyran. Others studies 1720 cm− 1, which are the characteristics peaks for
have analyzed chemically the solvent polarity effects on cellulose acetate. For the PMMA polymeric base; the
the spiropyran molecules, using only the absorption spectrum shows intense peaks for CH3 and CH2 at two
spectrum of the structure [10–12]. different wavelengths and also for the acetate group at
This study reports on the use of infrared spectroscopy 1720 cm− 1. The infrared spectra show the associated
in the Attenuated Total Reflection (ATR) mode to
analyze the interactions between the polymeric base, the
solvent and the SP. Individual components were first
analyzed separately and later in a combinatory way
(Spiro plus solvent and Spiro plus polymeric base plus
solvent) to investigate the final molecular arrangement.

2. Experimental details

2.1. Fabrication of samples

The samples for investigation were fabricated using

the gravity-deposition technique, as this growth tech-
nique is simpler and cheaper. Polymethyl methacrylate
(PMMA) and cellulose acetate (CA) were used as
polymeric matrices and 1, 3-Dihydro-8-methoxy-1, 3, 3
trimethyl-6-nitrospyro were used as the Spiro. For the
PMMA films, 0.25%, 0.5%, 1%, 2% and 5% of
spiropyran in weight concentrations were mixed with Fig. 2. ATR spectra of fundamental vibration modes for: CA, PMMA
0.2 g of PMMA and dissolved in 10 ml of acetone. For and spiropyran in powder.
 R. Delgado-Macuil et al. / Materials Characterization 58 (2007) 771–775 773

frequencies to the chemical bonds of each molecule (CA Table 2

and PMMA). Spiropyran IR characteristics absorption frequencies
A structural analysis of the spiropyran in powder Assignment Wavenumber Assignment Wavenumber
form was performed, even though the characteristic (cm− 1) (cm− 1)
peaks present in the powder state were not the same as CH3 asymmetric 2969 C–N stretching 1297 and
those in the thin film state, the presence of other peaks stretching 1278
CH3 symmetric 2863 C–O stretching 1237
could give us an idea on the different molecules
stretching
associated to SP and these characteristic peaks are C = C stretching 1642 COCH3 stretching 1175
shown in Fig. 2. Aromatic ring 1610 and CH out of plane 1123 and
In Tables 1 and 2, the main IR frequencies for 1570 asymmetric 1090
polymeric bases and the spiropyran molecule are listed, stretching
NO2 stretching 1517 and CH out of plane 1026 and
which are determined from the ATR spectra in Fig. 2.
1332 symmetric stretching 1013
With the main bonds of each molecule (CA, PMMA and CH3 asymmetric 1466 O–C–N stretching 974
SP) identified, one can analyze the final arrangements. bending
First, the spiropyran interaction with the solvents, CH3 symmetric 1388 Benzene ring 910, 845,
methylene chloride and acetone, was analyzed using bending 794 and 748
ATR spectroscopy to observe the frequencies associated
with each molecule. The experiment conducted is as
follows: initially Spiro in powder was measured, after peaks of Spiro plus methylene spectrum (black line).
that, both solvent methylene chloride and acetone were Similarly, in Fig. 3b we can observe the spectral range in
measured. Finally, 0.5% of Spiro was dissolved in 3 ml the 750–1750 cm− 1 range, for acetone plus the Spiro
of methylene chloride and in 3 ml of acetone. mixture. The light gray line is assigned to acetone,
In Fig. 3a, one can observe the spectral region in the whereas the dark gray and black lines correspond to
750–1750 cm− 1, where the main spiropyran peaks are spiropyran in the powder and in the solution, respec-
observed. The light gray line is methylene chloride, tively. Additionally, vertical lines are added to show a
whereas the dark gray and black lines correspond to frequency shift in the peaks from 4 to 11 cm− 1, between
spiropyran in powder and in solution, respectively. the peaks of Spiro in the powder spectrum (dark gray
Vertical lines are added to show a frequency shift in line) and peaks of the Spiro plus acetone spectrum
several peaks, from 5 to 13 cm− 1, between the peaks of (black line). By the molecular arrangement, a frequency
Spiro in the powder spectrum (dark gray line) and the shift from 2 to 20 cm− 1 was observed with peak

Table 1
IR characteristic absorption frequencies for the polymeric bases used
CA PMMA
Assignment Wavenumber Assignment Wavenumber
(cm− 1) (cm− 1)
OH stretching 3400 CH3 symmetric 2995
stretching
CH3 asymmetric 2950 CH2 asymmetric 2958
stretching stretching
CH3 symmetric 2860 CH2 symmetric 2933
stretching stretching
Acetate C–C–O 1235 C = O carbonyl 1732
stretching stretching
C–O stretching 1050 C–O ester bond 1147
stretching
C = O stretching 1720 C–H bending Broad
band from
988–740
CH3 asymmetric 1432 Structural factor 490
deformation
CH3 symmetric 1370
Fig. 3. ATR of Spiro (dark gray line), solvent (light gray line) and
deformation
solvent plus Spiro (black line), to check the effects on the spiropyran
Structural factor 603
by the solvent. a) Methylene chloride and b) acetone.
774 R. Delgado-Macuil et al. / Materials Characterization 58 (2007) 771–775

Table 3
ATR characteristics absorption frequencies for spiropyran dissolved in
two different solvents
Methylene chloride Acetone
Stable Shifted Stable Shifted
Wavenumber Wavenumbers Wavenumber Wavenumbers
(cm− 1) (cm− 1) (cm− 1) (cm− 1)
797 813 shifted to 1024 811 shifted to
823 820
1023 914 shifted to 1268 971 shifted to
927 982
1118 1090 shifted to 1580 1281 shifted to
1095 1285
1337 1174 shifted to 1515 shifted to
1179 1523
1359 1297 shifted to 1610 shifted to
1306 1613
1390 1512 shifted to Fig. 4. ATR spectra for spiropyran deposited in CA and PMMA
1522 polymeric bases.
1485 1642 shifted to
1654
1581
1610 shift is now present associated to the solvent and
polymeric base effect, for example: the CH3 asymmetric
peak is shifted to lower frequencies and the symmetric
positions listed in Table 2, in comparison with the peak peak to higher frequencies, the C = C peak is very weak,
intensities showed in Fig. 3a and b. the peak associated with the benzene ring is shifted to
The shift to higher frequencies in some peaks are due 1642 cm− 1, only one peak is now present associated
to a solvent effect on the Spiro [10–12], low polarity with the NO2 bond, the asymmetric vibration bending
solvents do not cause a shift of the peaks, but when the for CH disappears and the O–C–N stretching peak as
polarity is increased, a major shift is expected. Although well, COCH3 stretching peak is now at 1160 cm− 1 and
the polarity of acetone is a little more compared to only two peaks of the benzene ring at 890 and 773 cm− 1
methylene chloride; the same displacement range were were identified.
observed for both solvents. Some peaks of the
spiropyran molecule are hidden by solvent molecule
peaks, for example, for the methylene plus Spiro
spectrum between 1200 and 1300 cm− 1 and for the
acetone plus Spiro between 1300 and 1500 cm− 1. This
is because of fewer frequency peaks reported to acetone
than for methylene.
Table 3 lists all the associated frequencies of the
spiropyran molecule (with and without a shift) observed
in the spectral range 750 cm− 1 and 1750 cm− 1. It is
observed that, there is an effect of solvent on the
spiropyran molecule and the next step was to determine
the effect of the polymeric base on the SP. ATR spectra
of spiropyran deposited in CA and the PMMA
polymeric base were also measured, as mentioned in
Section 2.2.
Fig. 4, shows CA and CA plus SP plots, from which
we can note that the CA peaks dominate the spectrum in
Fig. 5. Amplified plot of the ATR spectra for spiropyran deposited in
intensity. Even though the peak intensities are less, CA, to show the generation or increase of peaks associated to the
almost all fundamental vibration modes of the spir- presented spiropyran as its concentration is increased in the polymeric
opyran molecule are present (also see Fig. 2). A longer matrix.
 R. Delgado-Macuil et al. / Materials Characterization 58 (2007) 771–775 775

The polymeric base PMMA shows a similar the results reported will definitely help researchers in
behavior, in Fig. 4b, it can be noted that the PMMA future to precede their optical analysis based on our
peaks dominate the spectrum in intensity, as in the results.
acetone case, but even smaller, almost all fundamental
vibration modes of the spiropyran molecule are present Acknowledgement
(also see Fig. 2). The longer shift is associated to the
solvent and polymeric base effect, for example: peaks This work was supported by CONACyT grant 50022.
associated with CH3 asymmetric and symmetric vibra-
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