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Inorganica Chimica Acta 360 (2007) 1535–1542

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Photophysical characterization of methyl viologen ion-exchanged


within a zirconium phosphate framework
Angel A. Martı́ 1, Giovanni Paralitici, Lorena Maldonado, Jorge L. Colón *

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

1. Introduction Zirconium bis(monohydrogen orthophosphate) mono-


hydrate, Zr(HPO4)2 Æ H2O, also called a-zirconium phos-
Solid-state porous and layered materials have been phate (a-ZrP), possesses a lamellar structure where the
extensively used for inclusion chemistry, because they zirconium atoms are arranged in alternate positions
can take up molecular guests with appropriate dimensions around the mean plane joined by phosphate groups above
into their lattice frameworks [1–4]. Materials such as zeo- and below the plane [7]. Three of the phosphate oxygens
lites are supramolecular inorganic systems in which the join three different zirconium atoms and the fourth is
uptake of guest species is restrained by the channel size, bonded to a hydrogen atom and is pointing into the inter-
which results in a size/shape selective inclusion behavior lamellar region. The stacking of these layers forms the lay-
[5]. Layered materials such as zirconium phosphates are ered framework where the distance between the zirconium
composed of inorganic sheets that can expand the dis- atoms’ planes is 7.6 Å. Ion-exchange of the phosphate
tance between their layers to accommodate guest species hydrogens by small cations (e.g. Na+, K+) can be accom-
of different sizes [6]. plished leading to an increase in the interlamellar distance
[8]. Intercalation by acid/base reactions is possible using
alkylamines resulting in enlarged interlayer distances which
*
depend on the length of the alkyl chain [9]. Alkylamines
Corresponding author. Tel.: +787 764 0000x2371; fax: +787 756 8242.
have been used to enlarge the interlayer spacing of ZrP
E-mail address: jorgecr@caribe.net (J.L. Colón).
1
Present address: Department of Chemistry, Columbia University, New allowing large molecules such as 1-pyrenemethyl-
York, NY 10027, USA. amine (PYMA) to intercalate within the ZrP layers [10].

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

Furthermore, alkanols and glycols have been successfully 2. Experimental


intercalated within a-ZrP by regenerating ZrNaH(-
PO4)2 Æ 5H2O with HClO4 in the presence of the corre- 2.1. Materials
sponding alkanol or glycol [11]. The alkanol intercalated
materials have proven to be useful to intercalate other All chemicals were purchased from Aldrich Chemical
polar organic molecules (e.g. acetonitrile, urea, benzyl alco- Co. and used as received with the exception of MVCl2
hol) due to its enlarged interlayer space. Recently, we have which was recrystallized twice from ethanol.
proved that the direct ion-exchange of tris-(2,2 0 -bipyridi-
nium)ruthenium(II) ðRuðbpyÞ3 2þ Þ can be accomplished 2.2. Intercalation procedure
using a hydrated form of ZrP that instead of one water
molecule per formula unit possesses ca. 6 water molecules The synthesis of 10.3 Å-ZrP is reported elsewhere
per formula unit and an interlayer distance of 10.3 Å [12,28]. The intercalation procedure was performed sus-
(10.3 Å-ZrP) [12]. This swelled material can ion-exchange pending a predetermined amount of wet 10.3 Å-ZrP in
cations larger than 10 Å in diameter. MV2+ aqueous solutions with different concentrations.
1,1 0 -Dimethyl-4,4 0 dipyridinium (methyl viologen, MV2+) The 10.3 Å-ZrP was prepared fresh before the intercalation
has been extensively studied especially because of its utiliza- procedure and used wet in order to maintain the interlayer
tion as an electron acceptor in photoinduced electron trans- expansion (upon dehydration, the 10.3 Å phase turns into
fer reactions [13–20]. The structure of MV2+ can be described the a-ZrP phase). The suspensions were constantly stirred
as two methylpyridinium groups joined by a single covalent at room temperature for five days. After this time the sus-
bond through their 4 and 4 0 carbon atoms [21]. The absorp- pensions were filtered by vacuum using 0.22 lm filters (Mil-
tion spectrum of MV2+ occurs in the UV region. The lower lipore). The solids were washed with abundant nanopure
energy absorption band possesses a maximum at 257 nm water and dried at ambient temperature for seven days.
with a molar absorption coefficient of 1.4 · 104 M1 cm1, The intercalation loading level was controlled by changing
corresponding to a p–p* transition [22]. Photoexcitation of the MV2+:ZrP molar ratio in the intercalation suspension.
MV2+ to the lowest excited state in aqueous solution leads The range of MV2+:ZrP intercalation molar ratios used in
to the observance of very weak fluorescence with maximum our experiments was from 1:30 to 5:1.
intensity at 345 nm [23]. The low intensity of this fluores-
cence emission has been attributed to efficient deactivation 2.3. X-ray powder diffraction measurements
by very favorable non-radiative pathways (e.g., rotation of
the pyridinium rings through the C4–C4 0 bonds [24], ultra- XRPD experiments were performed from 2 to 45 (in
fast isomerization producing deactivation of the excited 2h) using a Siemens D5000 X-ray diffractometer system
state[25] and photoreaction between MV2+ and water [25]). with a copper anode source (Cu Ka, k = 1.5418 Å). The
Encapsulation of MV2+ in rigid matrices like zeolites, mont- slits used had the following width: divergence slit, 2 mm;
morillonite and hectorite produces intense emission at ca. receiving slit, 2 mm; scatter slit, 0.6 mm; detector slit,
330 nm [23,24]. Recently, Peon et al. reported the lumines- 2 mm. In ZrP materials the interlayer distance (dhkl) can
cence of MV2+ in acetonitrile solution at room temperature be determined from the first order diffraction peak follow-
with a quantum yield of 0.03 [25]. These authors reported the ing Bragg’s law [29].
fluorescence quenching between MV2+ and methanol, etha-
nol, 1,4-dioxane, H2O, 2,2,2-trifluoroethanol and NH4PF6 2.4. Elemental analysis
with bimolecular quenching rate constants ranging from
0.040 to 1.6 · 1010 M1 s1. Carbon and phosphorus elemental analyses were per-
The divalent nature of MV2+ promotes its adsorption by formed by Quantitative Technologies, Inc. (QTI) and used
negatively charged inorganic networks like clays [23,24], to determine the concentration of MV2+ within the layers
zeolites [17–20], silica gel [26] and host molecules like as described in Supporting Information, Table 1.
cucurbit [7]uril [27]. This property opens the possibility of
intercalation into zirconium phosphate materials. Here 2.5. Spectroscopic measurements
we report that MV2+ can be easily intercalated in 10.3 Å-
ZrP. In this paper, we present a detailed structural charac- IR spectra of the intercalated materials were recorded
terization of MV2+ within the layers of ZrP. To study the on KBr pellets (1%, w/w) with a Nicolet Magna 750 FTIR
photophysical properties of MV2+ within the ZrP layers a spectrometer while wet and dry 10.3 Å-ZrP spectra were
thorough spectroscopic characterization including UV– measured directly on the sample with a Bruker Tensor 27
Vis spectrophotometry, steady-state fluorescence and FTIR spectrometer. UV–Vis spectrophotometric and
time-resolved fluorescence measurements was performed. steady state luminescence measurements were performed
The conclusions brought by these studies will show how suspending a determined amount of MV2+-exchanged
a rigid and polar microenvironment such as the ZrP ZrP material in water to make 0.008% (w/v) suspensions,
interlayer region affects the photophysical properties of unless otherwise stated. The luminescence spectra in Sup-
MV2+. porting Information, Figure 3 were obtained directly from
A.A. Martı́ et al. / Inorganica Chimica Acta 360 (2007) 1535–1542 1537

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

culated. This represents a difference of ca. 17 % from the


maximum loading obtained from experimental data
(2.07 M). Three different explanations can be proposed to
explain this discrepancy. First, poor crystallinity of the
intercalated material might increase the surface area of
the material, increasing the amount of MV2+ molecules
ion-exchanged in the material [35,41]. However, a tendency
to sharper and more defined peaks was observed in the
XRPD patterns as the loading increased, indicating a rela-
tively high crystallinity, which is inconsistent with this
explanation. The second explanation is that clustering of
MV2+ cations is occurring on the outer surface of ZrP.
However, this possibility appears to be unreasonable, since
the materials were washed with abundant deionized water
to remove any unintercalated MV2+ residue and it would
be an unprecedent phenomena for MV2+ ions. The third
hypothesis is that the two pyridinium rings of MV2+ are
not parallel to the ZrP layers but at an angle to them.
An angle larger than zero would decrease the cross sec-
tional area projected over the ZrP layers occupied by a
MV2+ molecule, allowing packing of more molecules.
The theoretical cross-sectional area that MV2+ should
project over the ZrP layer to obtain the highest experimen-
tal molarity (2.07 M) is calculated to be 75.7 Å2. Assuming
Fig. 1. XRPD patterns for the different MV2+-exchanged ZrP loadings that the planar structure dimensions of MV2+ do not
levels, 10.3 Å ZrP and 10.3 Å ZrP after drying for 5 days at room change and using trigonometry arguments we calculate
temperature. that such projection is given when the angle between the
MV2+ plane and the ZrP layer is 34, as shown in
The 4.2 Å dimension is in agreement with the interlayer dis- Fig. 2b. The perpendicular distance with respect to the
tance observed and is consistent with a configuration where ZrP layers plane occupied by MV2+ with its plane adopting
the two methylpyridinium rings in MV2+ lie parallel to the a 34 angle with the layers is ca. 4.7 Å. This distance is
ZrP layers (Fig. 2a). To determine the theoretical molarity 0.5 Å larger than the initial assumption (4.2 Å, with
of MV2+ in a completely ion-exchanged ZrP material MV2+ completely parallel to the layers). The theoretical
(maximum loading) where the intercalation process has interlayer distance would then be 6.6 Å + 4.7 Å = 11.3 Å,
been topotactic, we assumed that a MV2+ molecule lying which is 0.7 Å larger than the distance measured by XRPD
parallel to the ZrP layers occupies a cross sectional area (10.6 Å). However, as we previously observed for
of 13.4 Å · 6.8 Å or 91.1 Å2 (Supporting Information, Fig- RuðbpyÞ3 2þ -exchanged ZrP, ionic, hydrogen bonding, and
ure 2) [34]. Since the area of a ZrP formula unit is 24 Å2 other electrostatic interactions between the cations and
[5,6] a theoretical amount of 0.263 MV2+ molecules per the layers can cause the distances between them to become
ZrP formula unit is determined. Because the experimental smaller than those predicted by van der Waals distances
interlayer distance of 10.6 Å is equivalent to a volume of [12]. In addition, nothing precludes MV2+ to slightly inter-
2.55 · 1025 dm3 per ZrP formula unit, a theoretical maxi- penetrate the layers between the phosphate groups decreas-
mum molarity of 1.72 M for MV2+-exchanged ZrP is cal- ing further the interlayer distance. The smaller distance and

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

luminescence was attributed to coordination of MV2+ to


basic sites in the zeolitic framework [36,40]. More recently,
Peon et al. suggested that this luminescence must be due to
oxidation photoproducts, especially pyridones which can
be formed by viologen photolysis in the presence of oxygen
[25]. These pyridones are highly luminescent and can
account for these additional features [37,42]. Fig. 5 shows
that this 420 nm emission was not observed in MV2+-
exchanged ZrP. These materials were purged for 15 min
with ultrapure (99.999%) nitrogen prior to fluorescence
measurements, ruling out the possibility of a photochemi-
cal reaction involving molecular oxygen. The direct irradi-
ation at 290 nm of the MV2+-exchanged ZrP powders,
without a nitrogen purge, produced fluorescence bands
Fig. 4. UV–Vis absorption spectra of MV2+-exchanged ZrP at different between 400 and 550 nm for all the materials (Supporting
loadings and of a 1.0 · 104 M MV2+ aqueous solution. Information, Figure 3). The experiments showed that the
intensity of these bands increase with longer exposition
time to the 290 nm excitation light. These data lead us to
conclude that the emission band at k > 400 nm is due a
photodecomposition product of the sample and not to
MV2+ (i.e., a MV2+ oxidation photoproduct is produced
in the presence of oxygen). If instead of irradiating
MV2+-exchanged ZrP powders at 290 nm we irradiate at
260 nm a suspension (0.008%, m/v) of MV2+-exchanged
ZrP (1.918 M loading), without nitrogen purge, we produce
the spectra shown in Fig. 6. The spectra shows a decrease
in the band at 337 nm and an increase in the fluorescence
bands between 400 and 550 nm corresponding to the pho-
tolysis product. These results indicate that the photoprod-
uct(s) can be obtained not only in non-purged powders but
also in not purged water suspensions.
Fig. 5. Fluorescence spectra for the different MV2+-exchanged ZrP In addition to steady state fluorescence studies, time
loadings (kexc = 260 nm, 0.008% (m/v) MV2+-exchanged ZrP domain fluorescence measurements were performed. The
suspensions). results are shown in Supporting Information, Table 2.
The data were successfully fitted using a mono-exponential
imum at ca. 337 nm that is independent of the MV2+ load- decay function with v2 values between 0.8 and 1.2. The life-
ing. The fluorescence kmax in MV2+-exchanged ZrP is blue times are in the order of hundreds of picoseconds. Previous
shifted with respect to MV2+ in acetonitrile solution
(350 nm) [25], which is consistent with the more rigid envi-
ronment in ZrP than in solution (a rigidochromic effect)
[35,41]. In contrast, the observed kmax in ZrP is similar,
although slightly red shifted, compared to that previously
observed in hectorite (kmax = 328 nm) [24], montmorillon-
ite (kmax = 330 nm) [24] and zeolites (kmax = 330 nm)
[36,40]. The red shift observed in ZrP compared to those
materials can be associated with the greater polarity of
the ZrP interlamellar region in comparison with clays
and zeolites. In addition, the excitation spectra (data not
shown), of MV2+-exchanged ZrP materials totally agree
with their UV–Vis absorption spectra (Fig. 4) also showing
the red shift in kmax with respect to the spectra in clays and
zeolites. This result confirms that the fluorescence comes
from the excited state of MV2+ and not from any impurity
or decomposition products.
Fig. 6. Fluorescence spectra of MV2+-exchanged ZrP (0.008%, m/v),
In addition to the fluorescence band observed at 330 nm
1.92 M loading at different times upon irradiation at 260 nm (Xe lamp,
for MV2+ immobilized in zeolites, Alvaro et al. reported I260 nm = 1.2 mW). The inset shows the fluorescence intensity at 450 nm as
another luminescence band at 420 nm [37,42,40,36]. This a function of time.
A.A. Martı́ et al. / Inorganica Chimica Acta 360 (2007) 1535–1542 1541

Table 1 10.2 to 10.6 Å. Using the XRPD data, IR measurements


Fluorescence quantum yield for MV2+-exchanged ZrP materials and the published crystal structure of MV2+, we propose
MV2+-exchanged ZrP loading (M) Quantum yield, / a configuration for MV2+ within the ZrP layers where
2.07 (4.1 ± 0.8) · 104 the pyridinium rings are rotated relative to each other by
1.92 (3.7 ± 0.7) · 104 68. The UV–Vis spectra showed red shifts with an increase
1.14 (3.5 ± 0.7) · 104 in loading level. Excitation of MV2+-exchanged ZrP mate-
0.77 (2.7 ± 0.6) · 104
0.35 (2.9 ± 0.5) · 104
rials in their UV absorption bands leads to fluorescence
emission. Irradiation of the solid material or suspensions
at 290 nm in the presence of oxygen leads to the appear-
studies of MV2+ in hectorite gave fluorescence lifetimes of ance of a luminescence band at ca. 450 nm that has been
4.37 and 1.38 ns (biexponential fit) while in montmorillon- identified as an oxidation photoproduct. This band was
ite the lifetimes were 0.95, 0.37 and 0.089 ns (triexponential never observed in diluted suspensions when the materials
fit) [24]. Our measurements yield an average lifetime of were purged with nitrogen prior to irradiation. Fluores-
0.24 ns which is comparable to the 0.37 ns component in cence lifetime measurements were performed indicating
montmorillonite. The reduced fluorescence lifetime in ZrP no dependence of the fluorescence lifetime on MV2+ load-
can be attributed to the more polar environment in the ing and yielding an average lifetime of 0.24 ns. Fluores-
ZrP layer which favors excited state deactivation by dipolar cence quantum yields were also determined showing that
coupling or to self-quenching of the excited state. However, the emission of MV2+-exchanged ZrP is not significantly
the fluorescence lifetime measurements do not indicate a stronger than that of MV2+ in aqueous solution. The calcu-
systematic decrease in the fluorescence lifetime with an lation of radiative and non-radiative rate constants indicate
increase in the MV2+ loading, which rules out the possibil- very favorable deactivation pathways for the non-radiative
ity of collisional or dynamic self-quenching. deactivation of the MV2+ excited state probably caused by
To further characterize the excited state emission of the coupling of its excited state with dipoles present in the ZrP
MV2+-exchanged ZrP materials, the fluorescence quantum framework. The intercalation of MV2+ within ZrP presents
yields using L-tyrosine as a fluorescence standard were different spectroscopic characteristics in comparison with
determined. The results are shown in Table 1. These quan- zeolite and clay materials, which can be explained based
tum yields are very small in comparison with other lumi- on the physical characteristics of the ZrP heterogenous
nescent MV2+ systems and are similar to the quantum microenvironment. This study provides valuable informa-
yield of MV2+ in water [38].2 Calculation from these data tion on the intercalation, photophysics and photochemistry
of the radiative and non-radiative decay rate constants of MV2+ in a ZrP material, which can be used in conjunc-
shows that the non-radiative rate constant is on average tion with the data from other MV2+-containing materials
three orders of magnitude larger than the radiative rate to tune the photophysical properties of MV2+ when design-
constant (Supporting Information, Table 2). This value ing new light harvesting solid state systems containing this
indicates very favorable deactivation pathways for the molecule or when using this ion as a mediator in
non-radiative deactivation of MV2+ within ZrP. This biosensors.
observation is expected since the environment within ZrP
is polar due to the phosphate groups and the remaining Acknowledgments
amount of co-intercalated water favoring the deactivation
of the excited state by coupling with the water or the frame- We thank NIH-RISE (Grant R25GM061151) and NIH-
work dipoles. Because the rotation through the C4–C4 0 SCORE (Grant S06GM08102) for financial support.
bond must be restricted within the interlayer region, its
rotation inhibition should not be the major factor for the Appendix A. Supporting material
observance of enhanced luminescence in other rigid sys-
tems [24]. An alternative explanation is that MV2+ is more Elemental analysis data, time domain luminescence
fluorescent in systems that promote the conservation of its transients, space fill illustration of MV2+ with molecular
planarity. This alternative explanation is consistent with dimensions, fluorescence spectra of solid materials in the
the low quantum yield observed for MV2+ in ZrP in which presence of air, fluorescence lifetimes of the MV2+-
MV2+ C4–C4 0 rotation is inhibited but the methylpyridi- exchanged ZrP materials and radiative and non-radiative
nium groups are not in the same plane; however, it does decay rate constants. Supplementary data associated with
not explain the relatively high fluorescence emission in fluid this article can be found, in the online version, at
media such as acetonitrile. doi:10.1016/j.ica.2006.08.052.

4. Conclusions
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