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Department of Chemistry, P.O. Box 23346, University of Puerto Rico, Rı́o Piedras, San Juan 00931–3346, Puerto Rico
Received 13 June 2006; received in revised form 16 August 2006; accepted 16 August 2006
Available online 20 September 2006
Abstract
The photophysical properties of 1,1 0 -dimethyl-4,4 0 dipyridinium (methyl viologen, MV2+) intercalated within zirconium phosphate
(ZrP) were investigated. The intercalation of MV2+ within ZrP was achieved by ion-exchange using a hydrated form of ZrP with six
water molecules per formula unit and an interlayer distance of 10.3 Å. The intercalation yields a new phase with an interlayer distance
up to 10.6 Å. The MV2+-exchanged ZrP material was characterized using elemental analysis, XRPD and IR data. The MV2+-exchanged
ZrP materials show a red shift in the UV–Vis spectra in contrast with solution. The photoexcitation of nitrogen purged, MV2+-
exchanged ZrP water suspensions with UV light leads to fluorescence emission with a maximum at 337 nm. The photoexcitation of
MV2+-exchanged ZrP suspensions without nitrogen purging yields two fluorescence emissions with maxima at 337 and 450 nm. The
emission in the visible region can be attributed to a photodecomposition product. The fluorescence quantum yields indicate that the emis-
sion of MV2+-exchanged ZrP is of the same order of magnitude as that of MV2+ in water indicating a strong deactivation of the excited
state by non-radiative pathways.
2006 Elsevier B.V. All rights reserved.
Keywords: Methyl viologen; Zirconium phosphate; Ion-exchange; Intercalation; Photophysics; Inorganic layered materials
0020-1693/$ - see front matter 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.ica.2006.08.052
1536 A.A. Martı́ et al. / Inorganica Chimica Acta 360 (2007) 1535–1542
the solid material exciting at 390 nm and with the sample at where / is the quantum yield of the molecule of interest,
45 with respect to excitation and emission monochroma- /R is the quantum yield of the reference standard, I and
tors. UV–Vis absorption measurements were performed IR are the integrated intensities for the luminescent mole-
on a HP-8453 diode array spectrophotometer. cule and the standard, respectively, and OD and ODR
Steady state luminescence measurements were per- are the optical densities for the luminescent molecule and
formed on a SE-900 spectrofluorometer (Photon Technol- the standard, respectively. For this experiment, the absor-
ogy International, PTI) using a 150 W xenon lamp as the bance of the samples were kept below 0.1 (a.u.). The
excitation source and a PTI Model 710 photon counting amount of light scattered out of the cell in the absorbance
detector with a Hamamatsu R1527P photomultiplier. measurements was corrected by subtracting the offset from
The bandpass of the emission and excitation monochro- zero at 600 nm. Band broadening in the UV due to particle
mator was 7.50 nm. For the photolysis experiment the scattering within the measurement cell was not corrected
emission and excitation bandpass were 5 and 12.5 nm, because the scattered light at 255 nm is relatively small in
respectively. Time domain luminescence measurements comparison with the absorption and also any scattered
were performed using a PTI GL-3300 N2 pulsed laser, light out of the straight path of the light beam inside the
coupled to a dye laser, PTI GL-302 (rhodamine 6G dye, cell is likely to be absorbed and must also contribute to
580 nm) and a frequency doubler, PTI GL-301 to produce the emission. The errors reported are the standard devia-
a laser output at 290 nm (full width at half maximum, tion of three different determinations and constitute ca.
fwhm < 2 ns). Time dependent luminescence was mea- 20% of the values.
sured by a PTI 5020-ELT stroboscopic detector with a The radiative (kr) and non-radiative (knr) rate constants
Hamamatsu R1527P photomultiplier. The excitation were determined using the following equations [32]:
wavelength was 290 nm and the emission intensity was /
monitored at 337 nm. Iterative reconvolution of the scat- kr ¼ ;
s
ter and the experimental transient (when required) was
ð1 /Þ
performed with the Time Master software v1.2 provided k nr ¼ ;
s
with the PTI equipment. Time domain experiments on
0.008% (w/v) suspensions gave no appreciable fluores- where / is the luminescence quantum yield and s is the
cence transients. luminescence lifetime.
To observe fluorescence in the time domain modality the
luminescence of very concentrated suspensions with the 3. Results and discussion
sample at 45 relative to both excitation and detection
(using a triangular fluorescence cell) was measured. 3.1. Structural characterization of MV2+-exchanged ZrP
Because the suspensions were very concentrated, all the
light was absorbed near the face of the cell and immediately The attempt to directly intercalate MV2+ into a-ZrP
emitted out of the cell to the detector. This method allowed (synthesized by the direct precipitation method [33]) was
the use of highly concentrated samples while avoiding at unfruitful. With the purpose of achieving direct intercala-
the same time the dispersion of light that should be created tion of MV2+ within a ZrP framework we used 10.3 Å-
by the suspension if the light beam passed through the cen- ZrP in the intercalation reaction with MV2+. The XRPD
ter of the cell (this method was used only for the time patterns for the dry materials resulting from intercalation
domain studies). Nevertheless, the time domain transients are presented in Fig. 1. Each material is identified by the
were not very intense (Supporting Information, Figure 1). concentration of MV2+ within ZrP (loading) determined
To confirm that the observed emission was not due to scat- from elemental analysis (Supporting Information, Table
tered light or other instrument factors, a scatter sample (an 1). The first order diffraction peaks show an interlayer
unintercalated a-ZrP suspension) was measured at 337 nm, expansion from 10.3 Å in the unintercalated material up
the emission wavelength of MV2+-exchanged ZrP. The to 10.6 Å in the intercalated materials. Although the
scatter monitored at 337 nm gave no measurable intensity increase in interlayer distance is not very different with
in contrast with the scatter monitored at 290 nm, which respect to the interlayer distance of the base material
corresponds to the excitation laser pulse. This confirms (10.3 Å-ZrP), this increased distance is for the dry interca-
that the observed emission is indeed due to the fluorescence lated material. Unintercalated 10.3 Å-ZrP collapses to the
of MV2+ within the layers. Both steady-state and time 7.6 Å phase (a-ZrP) upon drying (Fig. 1) [8], indicating that
domain luminescence measurements, were performed in the interlayer expansion observed in the intercalated dry
samples purged with N2 (99.999%) for 15 min. materials is due to ion-exchanged MV2+ molecules keeping
Quantum yields were determined with 255 nm excita- apart the layers framework.
tion, using L-tyrosine in water (/ = 0.14) [30] as a standard Considering that the width of a ZrP layer is 6.6 Å [7],
using the following formula [31]: then from a 10.6 Å interlayer distance we have a remaining
free interlayer distance of 4 Å. The crystal structure of
I ODR MV2+ shows that its dimensions are 13.4 Å ·
/ ¼ /R ;
I R OD 6.8 Å · 4.2 Å (Supporting Information, Figure 2) [21].
1538 A.A. Martı́ et al. / Inorganica Chimica Acta 360 (2007) 1535–1542
Fig. 2. Idealized representation of the MV2+ molecules within ZrP with: (a) MV2+ parallel to the ZrP plane, (b) MV2+ at an angle with respect to the ZrP
layer, (c) MV2+ at an angle with respect to the ZrP layer and rotated through its C–C bond resulting in a torsion angle of 68 (2.07 M loading). The
hydrogen atoms are excluded for clarity.
A.A. Martı́ et al. / Inorganica Chimica Acta 360 (2007) 1535–1542 1539
the decrease in the crystallinity observed for low loading antisymmetric CH3 vibrations and is also present in the
level materials arise because the amount of MV2+ mole- MV2+-exchanged ZrP materials. The small signal at
cules is not enough to maintain the whole layer framework 1357 cm1 is almost inexistent in the intercalated materials
apart. Because under low loading level conditions, on aver- and is attributed to ring vibration. The disappearance of
age, the MV2+ molecules are far from one another, the lay- this band has been attributed to rotation of the methylpy-
ers collapse in some places giving rise to a low crystalline ridinium groups of MV2+ relative to each other [36,40].
material. This effect is especially observed as a broadening Because the cross-sectional area over the ZrP plane will
in the first diffraction peak due to the variety of interlayer be the same as for the case of MV2+ with coplanar meth-
distances. ylpyridinium groups, the angle between the pyridinium
rings and the ZrP layers will still be 34 but with pyridi-
3.2. Spectroscopic characterization of MV2+-exchanged ZrP nium rings rotated relative to each other by an angle of
68 (Fig. 2c). The MV2+ vibrational bands at energies
To determine if any chemical change has occurred to smaller than 1500 cm1 are mainly overlapped with phos-
MV2+ during or after the intercalation process, FT-IR phate bands. One observation about the phosphate bands
measurements of the intercalated materials were per- is that their intensities are slightly different in the
formed. Fig. 3 shows the FT-IR spectra of MV2+- exchanged material. This behavior is completely expected
exchanged ZrP at different loading levels as well as that and, as can be seen from Fig. 3, it also occurs when
of MVCl2. The IR spectrum of MVCl2 agrees with that 10.3 Å-ZrP becomes dry.
previously reported, which showed bands at ca. 1640, With the purpose of probing the excited state properties
1562, 1507 and 1467 cm1 that correspond to ring vibra- of MV2+ when it is encapsulated in ZrP, different spectro-
tions [36,40]. Fig. 3 shows that these vibrational bands scopic studies were performed. Fig. 4 shows UV–Vis
are present in the MVCl2 spectrum as well as in the absorption spectra of MV2+-exchanged ZrP at different
MV2+-exchanged ZrP materials spectra but with slight dis- loading levels. The absorption spectra of MV2+-exchanged
placements to higher wavenumbers. The band at ZrP shows an absorption band in the UV region that is
1440 cm1 in the MVCl2 IR spectrum corresponds to the clearly red shifted with respect to the spectrum in aqueous
solution. This red shift is consistent with the UV–Vis
absorption spectra of MV2+ immobilized in clay and zeo-
lite systems [24,37,42]. From Fig. 4 it can be seen that the
red shift increases with an increase in the MV2+ loading
concentration. This red shift can be attributed to a decrease
in the S0–S1 energy gap due to interactions between the
pyridine aromatic rings of neighboring MV2+ molecules
as the distances between them decrease. However, previous
studies of MV2+ in aqueous solution showed that the
UV–Vis spectrum of MV2+ does not change at high
concentrations, which would support the clustering
hypothesis [38].2 Alternatively, the red shift can be attrib-
uted to a change in the diffraction index and dielectric
constant of the media as more MV2+ is intercalated [39].
Fig. 5 shows the luminescence spectra of MV2+-
exchanged ZrP at different loading levels. Peon et al. con-
cluded that the emission of MV2+ in acetonitrile arises
from relaxation of the singlet excited state [25]. Since the
ground state is also singlet in character, the transition is
completely ‘‘allowed’’ and can be identified as fluorescence.
The fluorescence spectra shown in Fig. 5 indicate that the
excitation of MV2+-exchanged ZrP materials at the absorp-
tion kmax results in a measurable fluorescence with a max-
2
The quantum yield of MV2+ in solution can be estimated by the
measurements of Villemure et al. [23] which showed that the emission of
MV2+ is 40 times more intense than in montmorillonite. Because the
concentration in both cases was 5 · 106 M and the quantum yield of
MV2+ in montmorillonite is 0.014 we estimate a quantum yield of
3.5 · 104 M in solution. Although this is only an estimate, it indicates
Fig. 3. FT-IR spectra of MVCl2, 10.3 Å-ZrP, 10.3 Å-ZrP after drying and that the quantum yield of MV2+ in solution is of the same magnitude than
MV2+-exchanged ZrP at different loading levels. our measurements in ZrP.
1540 A.A. Martı́ et al. / Inorganica Chimica Acta 360 (2007) 1535–1542
4. Conclusions
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