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PAPER www.rsc.org/materials | Journal of Materials Chemistry

Highly efficient visible light sensitized red emission from europium

tris[1-(4-biphenoyl)-3-(2-fluoroyl)propanedione](1,10-phenanthroline)
complex grafted on silica nanoparticles
V. Divya, S. Biju, R. Luxmi Varma and M. L. P. Reddy*
Received 3rd March 2010, Accepted 15th April 2010
First published as an Advance Article on the web 20th May 2010
DOI: 10.1039/c0jm00588f

A novel class of efficient visible light sensitized antenna complexes of Eu3+ based on the use of a highly
conjugated b-diketonate, namely, 1-(4-biphenoyl)-3-(2-fluoroyl)propanedione (HBFPD) and 1,10-
Published on 20 May 2010 on http://pubs.rsc.org | doi:10.1039/C0JM00588F

phenanthroline as an ancillary ligand has been designed, synthesized, characterized and their
photophysical properties (PL) investigated. PL measurement results indicated that suitably expanded
p-conjugation in the complex molecules makes the excitation band red shift to the visible region and
hence the Eu3+ complexes exhibit intense red emission under blue light excitation (440 nm) with a solid-
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state quantum yield of 32  3%, which is the highest so far reported in the literature. Further, in the
present work, the visible sensitized Eu3+complex has been covalently anchored to the ordered
mesoporous MCM-41 via the modified HBFPD ligand for the first time to the best of our knowledge. b-
Diketonate grafted to the coupling agent 3-(triethoxysilyl)propylisocyanate was used as the precursor
for the preparation of mesoporous nanomaterials. MCM-41 consisting of ternary complex
Eu(SiBFPD)3(phen) covalently bonded to the silica-based network, which was designated as
Eu(SiBFPD)3(Phen)/MCM-41 (3), was obtained by interacting europium nitrate, SiBFPD-Na and
1,10-phenanthroline into the hybrid material via a ligand-exchange reaction. The designed material was
further characterized by powder X-ray diffraction, dynamic light scattering (DLS) technique,
thermogravimetric analysis, N2 adsorption-desorption, SEM, TEM, FT-IR, FT-Raman, 13C and 29Si
CPMAS NMR and photoluminescence spectroscopic techniques. The hybrid material covalently
bonded to MCM-41 exhibits an efficient intramolecular energy transfer process from the silylated b-
diketonate to the central Eu3+, namely, the antenna effect, which favored a stronger red/orange
intensity ratio, longer lifetime, and high thermal stability than the precursor complex.

Introduction
The fascinating photophysical properties of luminescent
lanthanide complexes have triggered numerous research efforts.1
In particular, their long lived luminescent excited states together
with narrow emission bands are of interest for various techno-
logical applications ranging from biomedical analysis2 to mate-
rials science.3 For most visible-emitting europium complexes, the
sensitization mechanism generally involves a triplet pathway,
achieved by energy transfer from a triplet excited state of organic
ligands to the central Eu3+ ion.4 The excitation window appears
to be limited to the near-UV region (generally below 380 nm) due
to the energetic constraints posed by the photophysics of sensi-
tized lanthanide luminescence.5 Recently, a challenge in the
chemistry of the lanthanide ions is to develop luminescent Eu3+
Chemical Sciences and Technology Division, National Institute for
Interdisciplinary Science & Technology (NIIST), CSIR,
Thiruvananthapuram, 695019, India. E-mail: mlpreddy55@gmail.com
Electronic supplementary information (ESI) available: Physical
characterization of SiBFPD-Na and Eu(SiBFPD)3(phen)/MCM-41 (3),
1
H NMR and 13C NMR spectra of the ligands, TG analysis, FT-IR
and FT-Raman analysis, 29Si CPMAS NMR spectrum, DLS particle
size distribution curve, SEM and TEM micrographs for 3, XRD
patterns and diffuse reflectance spectra of complexes 13 and the
standard phosphor perylene. See DOI: 10.1039/c0jm00588f
complexes that can be sensitized by visible light and this field has
become much more important because of the demand for less-
harmful labeling reagents in the life sciences and low-voltage-
driven pure-red emitters in optoelectronic technology.6 There are
two strategies that can be adopted to achieve visible light exci-
tation. One of the approaches is to introduce a 4d- or 5d-tran-
sition metal ion such as Ir(III) or Pt(II) into the Eu3+ complex
molecule, which exhibits an efficient energy transfer to the Ln3+
ion.7,8a Unfortunately, the photoluminescence efficiency of this
kind of Eu3+ complex based on the 3MMLCT (metal-metal-to-
ligand charge transfer) or 3MLCT (metal-to-ligand charge
transfer) was always very low.8 Another approach is to modify
the ligand molecule with a suitable expanded p-conjugated
system to shift the excitation band of its Eu3+ complex to the
visible region, and this expanded p-conjugated system cannot be
either too small to absorb visible light or too big to raise the
triplet state of the ligand to a degree higher than 5D0, the lowest
excited state energy level of the central Eu3+ ion.9 Some of the
typical examples of such modified ligands are Michlers ketone,10
phenalenone11 and tridentate ligands.6a,12 A highly efficient
photoluminescence quantum yield of 28% in the solid state has
also been reported for a visible-light excitable Eu(2-
TFDBC)3phen (where 2-TFDBC represents 2-(40 ,40 ,40 -trifluro-
10 ,30 -dioxobutyl)-carbazole) complex.9 However, the europium

5220 | J. Mater. Chem., 2010, 20, 52205227 This journal is The Royal Society of Chemistry 2010
 View Online

adducts of a push-pull chromophore such as Michlers ketone

and N,N-dialkyl aniline incorporated dipyrazolyltriazine to
a tris(b-diketonate) reported are only stable in solvents like
benzene and toluene. This limits their applicability significantly.
Further some of the above adducts could not be obtained in solid
state but had to be made in situ and also exhibited low quantum
yields.
The poor stabilities and low mechanical strength of the lantha-
nide complexes always hinder their use in practical applications
such as tunable solid-state lasers or phosphor devices.3b,c,13
In order to overcome these shortcomings, many research efforts
are focused on preparing lanthanide organicinorganic hybrids Scheme 1 Synthetic procedure for the ligand HBFPD.
through functionalization of the exterior and/or interior surfaces,
prompting the utilization of mesoporous materials such as
Published on 20 May 2010 on http://pubs.rsc.org | doi:10.1039/C0JM00588F

MCM-4114 and SBA-15.15 Several reports are available on the

covalent grafting of common europium b-diketone chelates to
silica hosts.3b,1417 On the other hand, a few investigations have
described the modification of b-diketones and lanthanide chelates
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directly covalently bonded to the silica host, in which bidentate

nitrogen donors bind to the central Eu3+ ions to saturate the
coordination sphere.15a,16,17e,f However, the synthesis and lumi-
nescence properties of MCM-41 mesoporous materials covalently
bonded with europium complexes by the modified b-diketonates
that absorb significantly at wavelengths especially longer than
400 nm and then transfer excitation energy efficiently and Scheme 2 Synthetic procedure for the Ln3+ complexes 1 and 4.
irreversibly to the central metal ion have not been explored
to date.
Given the important potential applications of visible light
excitation and the fascinating properties of b-diketonates,4,18 we
were prompted to prepare a series of Eu3+ complexes featuring 1-
(4-biphenoyl)-3-(2-fluoroyl)propanedione by replacing phenyl
groups with a highly conjugated fluorine and biphenyl units in
a well known dibenzoylmethane ligand system. The highly
conjugated b-diketonate functionality has a significant influence
on the distribution of p-electron density within the ligand
system, therefore a bathochromic shift in the excitation band to
longer wavelengths than 400 nm is expected. Here, we also report
on the synthesis and characterization of 1-(4-biphenoyl)-3-(2-
fluoroyl)propanedione (HBFPD) functionalized mesoporous Scheme 3 Synthetic procedure for the complex 2.
hybrid material Eu(SiBFPD)3(Phen)/MCM-41, in which
HBFPD was covalently bonded to the framework of MCM-41. HBFPD ligand in a metal-to-ligand molar ratio of 1 : 3 and one
The synthesized luminescent hybrid material was fully charac- molecule of bidentate nitrogen ligand is involved in complex 2.
terized by various spectroscopic techniques, and its photo- The FT-IR spectra of the complexes 1 and 4 show a broad
physical properties were investigated in relation to guesthost absorption in the region 30003500 cm1, indicating the presence
interactions between the organic complex and the silica matrix. of solvent molecules in these complexes. On the other hand, the
absence of the broad band in the region 30003500 cm1 for
complex 2 suggests that water has been displaced successfully by
Results and discussion the ancillary ligand, phen. The carbonyl stretching frequency of
HBFPD (1604 cm1) has been shifted to lower wavenumbers in
Synthesis and characterization of 1-(4-biphenoyl)-3-(2-
complexes 12 and 4 (1590 cm1 in 1, 1594 cm1 in 2 and
fluoroyl)propanedione (HBFPD) and Ln3+ complexes (12 and 4)
1587 cm1 in 4), indicating the involvement of carbonyl oxygen in
The ligand 1-(4-biphenoyl)-3-(2-fluoroyl)propanedione the complex formation with Ln3+ ion.4cf Further, a red shift
(HBFPD) was synthesized in 60% yield according to the method observed in the C]N stretching frequency of nitrogen donor
described in Scheme 1. The HBFPD was characterized by FT-IR, (1561 cm1) in the complex 2 (1524 cm1) shows the involvement
1
H NMR and 13C NMR spectroscopy (Fig. S1 and S2 of ESI) as of nitrogen atoms in the complex formation with Eu3+ ion.
well as by mass spectrometry (FAB-MAS) and elemental anal- The thermal behavior of the complexes 12 and 4 was exam-
ysis. The synthetic procedures for the Ln3+ complexes (12 and 4) ined by means of thermogravimetric analysis (TGA) under
are shown in Schemes 2 and 3. The microanalyses of Ln3+ nitrogen atmosphere and the results are depicted in Fig. S3
complexes revealed that each Ln3+ ion had reacted with the (in ESI). It is clear from the thermogravimetric analysis data

This journal is The Royal Society of Chemistry 2010 J. Mater. Chem., 2010, 20, 52205227 | 5221
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that complexes 1 and 4 undergo a mass loss of about 3% in the

first step (30 to 150  C), which corresponds to the elimination of
the coordinated water molecules. On the other hand, complex 2 is
more stable than the precursor sample 1 and it does not show any
weight loss up to 170  C. Subsequent thermal decomposition of
1, 2 and 4 takes place in the region of 200600  C and consists of
two steps. For each complex the residue comprises approxi-
mately 1213% of the initial mass and corresponds to the
formation of the respective lanthanide oxide.

Synthesis and characterization of modified b-diketonate

(SiBFPD-Na) and Eu3+ hexagonal mesoporous silica particles
Eu(SiBFPD)3(phen)/MCM-41 (3)
Published on 20 May 2010 on http://pubs.rsc.org | doi:10.1039/C0JM00588F

The modified b-diketonate ligand SiBFPD-Na and

Eu(SiBFPD)3(phen)/MCM-41 (3) were synthesized according to Fig. 1 UV-vis absorption spectra of the ligands HBFPD, phen and
the procedures illustrated in Scheme 4. SiBFPD-Na was complexes 12 in THF (c 2 106 M).
characterized by FT-IR, FT-Raman, 1H NMR and 13C NMR
spectroscopy (Fig. S4S7 of the ESI). Eu(SiBFPD)3(Phen)/
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region in complex 2 are due to the singlet-singlet pp* absorp-

MCM-41 (3) was obtained by interacting europium nitrate,
SiBFPD-Na and 1,10-phenanthroline into the hybrid material
via a ligand-exchange reaction. The designed material was
further characterized by powder X-ray diffraction, dynamic light
scattering (DLS) technique, thermogravimetric analysis, N2
adsorption-desorption, SEM, TEM, FT-IR, FT-Raman and
29
SiCPMAS NMR spectroscopic techniques (in ESI).
Photophysical properties
The UV-vis absorption spectra of the free ligands HBFPD, phen
and those of the corresponding Eu3+ complexes 12 measured in
THF (c 2  106 M) are shown in Fig. 1. The maximum
absorption band at 375 nm for the b-diketonate ligand and the
corresponding complexes is attributable to singlet-singlet pp*
enolic absorption of the b-diketonate.4f,g,19 A hump observed
around 308 nm in HBFPD and complexes is due to singlet-singlet
pp* absorption of the aromatic rings in the b-diketonate
ligand. On the other hand, the absorption maximum observed
around 265 nm in phen and the hump observed in the above
tion of the ancillary ligand.4d The spectral shapes of the
complexes are similar to that of HBFPD, indicating that
the coordination of Eu3+ ion does not significantly influence the
energy of the singlet state of the b-diketone ligand. The deter-
mined molar absorption coefficient values of the complexes 12
at 375 nm, 10.3  104 and 11  104 L mol1 cm1, respectively,
are about three times higher than that of the HBFPD (3.6  104
at 375 nm), indicating the presence of three b-diketonate ligands
in the corresponding complexes. Note also that the large molar
absorption coefficient value for the ligand indicates that it has
a strong ability to absorb light. It can also be seen from Fig. 1
that the absorption spectra of the ligand and complexes extend
up to the longer wavelengths.
The solid-state excitation and emission spectra of Eu3+
complexes 13 recorded at room temperature are displayed in
Fig. 2. The excitation spectra monitored at the characteristic
emission of Eu3+ ion overlap with absorption spectra in the 275
475 nm region, which indicates that energy transfer from the
ligand to the metal ion is operative. The excitation spectra of the
complexes exhibit a broad band between 275 and 500 nm (lmax
440 nm), which can be assigned to pp* electronic transition of

Scheme 4 Synthetic procedure for the ligand SiBFPD-Na and the Fig. 2 298 K excitation and emission spectra of complexes 13 in the
complex 3. solid state (lex 440 nm and emission monitored around 612 nm).

5222 | J. Mater. Chem., 2010, 20, 52205227 This journal is The Royal Society of Chemistry 2010
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the aromatic ligands. The absence of any absorption bands due Table 1 The energies of the 5D0 / 7FJ transitions (n0J), the intensity
to the ff transitions of the Eu3+ cation proves that luminescence ratio (red/orange ratio; I02/I01), radiative (ARAD) and nonradiative (ANR)
decay rates, 5D0 lifetime (sobs), intrinsic quantum yield (fLn), energy
sensitization via excitation of the ligand is effective. Compared transfer efficiency (fsen), and overall quantum yield (foverall) for
with the similar Eu3+ complex Eu(DBM)3(phen) [DBM repre- complexes 13 at 298 K in solid-state
sents dibenzoylmethane] (lmax 350360 nm) reported else-
where,20 the excitation bands of 13 showed remarkable red shift Parameters 1 2 3
by about 80 nm and were extended to the visible range (500 nm) n00/cm1 17300 17289 17289
because of the larger p-conjugation in the newly designed n01/cm1 16806 16805 16805
molecules. Thus less photodecomposition is expected for the n02/cm1 16339 16338 16338
excitation of the luminescent compounds by electromagnetic n03/cm1 15384 15383 15383
n04/cm1 14245 14249 14240
radiation of lower energy.7a,9 I02/I01 10.23 11.48 14.64
Being excited by the blue light (440nm), the room temperature sobs/ms 371  1 639  1 786  1
emission spectra of the complexes 13 showed characteristic ARAD/s1 860 643 669
ANR/s1 1835 917 601
narrow emission bands of Eu3+ corresponding to the 5D0 / 7FJ
Published on 20 May 2010 on http://pubs.rsc.org | doi:10.1039/C0JM00588F

foverall/% 71 32  3 30  3
(J 04) transitions (Fig. 2). The five expected peaks for the 5D0 fLn/% 32 41 53
/ 7F0-4 transitions are well resolved and the emission bands at fsen/% 21 78 57
580 and 650 nm are very weak since their corresponding transi-
tions 5D0 / 7F0,3 are forbidden both in magnetic and electric
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dipole schemes.4f,21 The intensity of the emission band at 593 nm complexes 13 are shown in Fig. 3. The relatively shorter lifetime
is relatively strong and independent of the coordination envi- obtained for complex 1 may be due to dominant nonradiative
ronment because the corresponding transition 5D0 / 7F1 is decay channels associated with vibronic coupling due to the
a magnetic transition; in contrast, the 5D0 / 7F2 transition is an presence of solvent molecules, as is well documented for many
induced electric dipole transition and its corresponding intense hydrated Eu3+-b-diketonate complexes.4cg,18a Longer lifetime
emission at l 613 nm is very sensitive to the coordination values have been observed for complexes 23 compared to
environment.21 This very intense 5D0 / 7F2 peak, pointing to complex 1, due to the absence of nonradiative pathways.
a highly polarizable chemical environment around the Eu3+ ion Moreover the complex 3 shows longer lifetime than 2, which may
and is responsible for the brilliant red emission of these be due to the fact that the rigid SiO polymeric network restricts
complexes. A relevant feature which may be noted for the the vibration of the HFBPD ligand considerably and so improves
complexes 13 is the very high intensity of 5D0 / 7F2 transition, the corresponding luminescence stability.17c Further, it also may
relative to the 5D0 / 7F1 lines, indicating that the Eu3+ ion be due to the H-bonding between the Eu3+ complex and the
coordinated in a local site without an inversion centre. Further, modified ligand, which is connected to the wall of MCM-41.
the emission spectra of the complexes show only one peak for Therefore, much energy is effectively absorbed by the ligand and
5
D0 / 7F0 transition and three stark components for 5D0 / 7F1 transferred to the emitting Eu3+ ion, and the relaxation time of
transition indicating the presence of a single chemical environ- hybrid material covalently bonded MCM-41 in the excited state
ment around the Eu3+ ion. The intensity ratio of the electric becomes longer in contrast to the pure complex.14c
dipole transition to the magnetic dipole transition in the The molar absorptivities of complexes 13 were found to be
lanthanide complex measures the symmetry of the coordination almost identical hence it has been assumed in the present study
sphere22 and this ratio increases with the number and mass of the that the quantum yield values qualitatively represent the emis-
ligand coordinated to the Eu3+ ion.23 The relative luminescent sion intensities of these complexes. The overall quantum yield
intensities of the 5D0 / 7F2/5D0 / 7F1 (red/orange ratio) for all
complexes are listed in Table 1. For the complex 1, in the absence
of ancillary ligand and mesoporous material, the intensity ratio
of the transitions of 5D0 / 7F2/5D0 / 7F1 is 10.23. This intensity
ratio increases to 11.48 in 2 and 14.64 in 3. In short, the presence
of ancillary ligand and mesoporous material increases the red/
orange ratio of the complexes. Interestingly, no emission bands
from the organic ligand were observed, which leads to the
conclusion that energy transfer from the ligands to Eu3+ centre is
very efficient. The CIE chromaticity coordinates for complexes
13 are computed on the basis of their emission spectra, found to
be x 0.667 and y 0.333 (1), x 0.676 and y 0.324 (2) and
x 0.670 and y 0.329 (3), respectively. These values are very
close to the National Television System Committee (NTSC)
standard CIE values for red (x 0.670, y 0.330).9,24
The 5D0 lifetime values (sobs) were determined from the lumi-
nescent decay profiles for the complexes 13 at room temperature
by fitting with a monoexponential curve, indicating the presence Fig. 3 5D0 decay profiles for complexes 13 (solid state) excited at
of a single chemical environment around the emitting Eu3+ ion 440 nm and emission monitored around 612 nm. The straight lines are the
and the values are depicted in Table 1. Typical decay profiles of best fits (r2 0.99) considering single-exponential behaviour.

This journal is The Royal Society of Chemistry 2010 J. Mater. Chem., 2010, 20, 52205227 | 5223

(foverall) for a lanthanide complex treats the system as a black
box in which the internal process is not considered explicitly.
Given that the complex absorbs a photon (i.e. the antenna is
excited), the overall quantum yield can be defined as:4e,23
foverall fsenfLn
Here, fsen represents the efficiency of energy transfer from the
ligand to the Ln3+ ion and fLn represents the intrinsic quantum
yield of the Ln3+ ion, which can be calculated as:
 
ARAD sobs
fLn (2)
ARAD ANR sRAD
For the Eu3+ complexes, the radiative lifetime (sRAD) can be
Published on 20 May 2010 on http://pubs.rsc.org | doi:10.1039/C0JM00588F
calculated using eqn (3),4cf,24,25 assuming that the energy of the
5
D0 / 7F1 transition (MD) and its oscillator strength are
constant
 
1 ITOT
ARAD AMD;0 n3 (3)
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sRAD IMD
where, AMD,0 (14.65 s1) is the spontaneous emission probability
of the 5D0 / 7F1 transition in vacuo, ITOT/IMD is the ratio of the
total area of the corrected Eu3+ emission spectrum to the area of
the 5D0 / 7F1 band and n is the refractive index of the medium.
An average index of refraction equal to 1.5 was considered.4cf
The quantum yields measured for complexes 13 employed the
technique for powdered samples described by Bril et al.,26 and are
listed in Table 1. According to energy gap theory, radiationless
transitions are prompted by ligands and solvents with high
frequency vibrational modes. Creation of Eu3+ complexes with
higher quantum yields is directly linked to suppression of radi-
ationless transitions caused by vibrational excitations in the
surrounding media.27 It is clear from Table 1 that complex 1,
having water molecules in the coordination sphere, exhibits
lower quantum yield. This is due to the presence of OH oscil-
lators in the system, which effectively quenches the luminescence
of the Eu3+ ion. On the other hand, complexes 23 exhibit high
quantum yield and lifetime values due to the displacement of
solvent molecules from the coordination sphere by the bidentate
nitrogen donor. The substantial contribution of the ancillary
Table 2 Overall quantum yield (foverall) and excitation maxima (lmax)
for some visible light sensitized luminescent Eu3+ complexes reported in
literaturea
Complex foverall(%) lmax(nm) Medium
2 32  3 440 Solid state
Eu(2-TFDBC)3(phen)9 28 429 Solid state
Eu(fod)3(MK)10 20 414 Benzene
Eu(PHN)3(H2O)(DMF)11 0.5 458 Solid state
(dfppy)2Ir(m- 17.7 480 Water
phen5f)Eu(TFAcA)38a
Eu(tta)3(Fc2phen)7a 1.75  0.15 403 Chloroform
a
Where fod 6,6,7,7,8,8,8-heptafluoro-2,2-dimethyloctane-3,5-dione,
MK 4,40 -bis(N,N-dimethylamino)benzophenone, PHN 9-
hydroxyphenal-1-one, DMF N,N-dimethyl formamide, dfppy
2-(40 ,60 -difluorophenyl)-pyridinato-N,C20 , phen5f 4,4,5,5,5-
pentafluoro-1-(10 ,100 -phenanthrolin-20 -yl)-pentane-1,3-dione, TFAcA
trifluoroacetylacetone, tta 2-thenoyltrifluoroacetone, Fc2phen
bis(ferrocenyl-ethynyl)-1,10-phenanthroline.
5224 | J. Mater. Chem., 2010, 20, 52205227
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ligand to the overall sensitization of the Eu3+-centered lumines-
cence in 23 is confirmed by (i) an increase of the intrinsic
quantum yield from 32% in 1 to 4153% in 2 and 3, which results
from removal of the quenching effect of the OH vibrations, and
(ii) the significant enhancement of fsen from 21 to 5778%. The
(1) intrinsic quantum yield (fLn) for complex 2 (41%) in the present
study is much higher than those of the well-known b-diketonate
complexes Eu(dbm)3(phen) (10%) and Eu(dbm-carb)3(phen)
(18%) [dbm dibenzoylmethane, dbm-carb 1-{[6-(9H-carba-
zol-9-yl)hexoxy]phenyl}-3-{[6-(9H-carbazol-9-yl)-hexox-
y]phenyl}propane-1,3-dione)].20 However, neither of these
reported complexes allows visible light sensitization as compared
to the present system. Moreover the overall quantum yield
(foverall) value of Eu3+ complex 2 calculated at 436 nm is higher
than most of the visible light sensitized Eu3+ complexes reported
so far in literature (Table 2).7a,8a,911
Energy transfer between ligands and Eu3+
To investigate the photoluminescence mechanism of the
complexes, the phosphorescence spectra of Gd(BFPD)3(H2O)2
and Gd(SiBFPD)3(H2O)2 solid samples were measured at 77 K
(Fig. 4). Because the coordination environments for the Gd3+
(radius 94 pm) and Eu3+ (radius 95 pm) ions are similar and
the energy absorbed by the ligands could not be transferred to
lowest excited state of Gd3+ ion (about 32000 cm1), the triplet
state of HBFPD was determined by the shortest-wavelength of
the phosphorescence peak of the corresponding Gd3+ complex
and found to be about 19342 cm1 (517 nm), which is higher than
the lowest excited state of Eu3+, 5D0 (17250 cm1).9,28 The triplet
energy level of SiBFPD-Na was found to be same as that of
HBFPD (as can be noted from Fig. 4), indicating that silylation
of the b-diketonate ligand does not change its electronic state
significantly. The singlet and triplet energy levels of phen
(1pp* 31000 and 3pp* 22100 cm1) were taken from the
literature.4d,29 The singlet energy level (S1) of HBFPD (1pp*
23364 cm1) was obtained from the higher absorption edges of
the corresponding absorption spectrum of the complex 4 (Fig. 4).
Fig. 4 UV-vis absorption spectrum of the complex Gd(BFPD)3(H2O)2
(4) at 298 K (a), and 77 K phosphorescence spectra of complexes
Gd(BFPD)3(H2O)2(4) (b), and Gd(SiBFPD)3(H2O)2 (c) in THF (c 2 
106 M).
This journal is The Royal Society of Chemistry 2010

Therefore, the photoluminescence mechanism of the Eu3+
complexes is proposed as a ligand-sensitized luminescence
process (antenna effect).28
It is well recognized that the energy-level match between the
triplet states of the ligands to the 5D0 state of the Eu3+ cation is
one of the key factors that governs the luminescence efficiency of
Eu3+ complexes.4cg The triplet energy levels of HBFPD and
SiBFPD-Na (19342 cm1) are obviously higher than the 5D0 level
of Eu3+ (17250 cm1), and their energy gaps DE (3pp*5D0)
between ligand and metal-centered levels are about DE >
2000 cm1, too high to allow an effective back energy transfer.30
On the other hand, DE (3pp*5D0) 4850 cm1 for phen and
thus it can be predicted that the triplet states of HBFPD and
SiBFPD-Na are more suitable for the sensitization of Eu3+ ion
Published on 20 May 2010 on http://pubs.rsc.org | doi:10.1039/C0JM00588F
than phen. It is also noticed that the energy gaps between the
1
pp* and 3pp* levels are 4020 and 8900 cm1 for HBFPD and
phen, respectively. According to Reinhoudts empirical rule,5b
the intersystem crossing process becomes effective when DE
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(1pp*3pp*) is around 5000 cm1, thus the intersystem crossing
process in the designed complexes is effective.
Experimental
Materials
The following chemicals were procured commercially and used
without subsequent purification. Europium(III) nitrate hexahy-
drate, 99.9% (Treibacher); gadolinium(III) nitrate hexahydrate
(Aldrich) 99.9%; 2-acetylfluorene 98% (Aldrich); 4-biphenyl
carboxylic acid 95% (Aldrich); sodium hydride 60% dispersion in
mineral oil (Aldrich); 1,10-phenanthroline 99% (Aldrich);
mesostructured hexagonal silica (MCM-41) (Aldrich); (3-iso-
cyanatopropyl)triethoxysilane (TESPIC) 95% (Alfa Aesar).
Solvents were dried using standard methods. All the other
chemicals used were of analytical reagent grade.
Characterization
Elemental analyses were performed with a Perkin-Elmer Series 2
Elemental Analyzer 2400. A Bruker 500 MHz NMR spectrom-
eter was used to record the 1H NMR spectrum of the ligands.
Mass spectra were recorded using a JEOL JMS 600 fast atom
bombardment (FAB) mass spectrometer. Infrared spectra of all
samples were performed on KBr pellets in the 4000400 cm1
region with a resolution of 4 cm1, by accumulating 64 scans
using a Perkin-Elmer Spectrum One FT-IR Spectrometer. FT-
Raman spectra of the solid samples were recorded on a Horiba
JY Lab Raman HR800 Micro Raman Spectrometer (with exci-
tation wavelength using an internal HeNe 20 mW 632 nm laser
polarized 500 : 1, spectrograph 800 mm focal length hole size
400 mm, slit 100 mm, grating 1800, objectives 10 NA 0.25, 50
NA 0.7, 100 NA 0.9). Thermogravimetric analyses were per-
formed on a TG/DTA-6200 (SII Nano Technology Inc., Japan).
29
Si and 13C Nuclear magnetic resonance spectra of the solid
samples were obtained on a Bruker DRX500 spectrometer (the
measurements were obtained in natural abundance at frequen-
cies of 75.47 and 59.61 MHz for carbon and silicon, respectively).
BET surface area of the hybrid material was measured using
a Micromeritics Gemini 2375 V5.01 surface area Analyzer. Pore
size distribution was obtained by the Barret-Joyner-Halenda
This journal is The Royal Society of Chemistry 2010
View Online
method from the desorption curve of the isotherm. X-Ray
powder diffraction was performed using Ni-filtered Cu Ka
radiation with a Philips Xpert Pro diffractometer. Data were
collected by step scanning from 2 to 10 2q. Optical reflectance
and UV absorption studies were carried out with a UV-Vis
spectrometer (Shimadzu UV-2450). Dynamic Light Scattering
experiment was conducted using a Malvern Instruments zetasizer
nano Zis Model No: ZEN 3600 to determine the particle size of
the hybrid material. TEM and SEM were used to determine the
morphology and particle size. TEM analyses were done on
a JEOL 2010 (200 kV). A pinch of material was suspended in
methanol. Then, a carbon-coated grid was dipped in the solution
and allowed to dry at room temperature. SEM analyses were
done on a JEOL JSM-5600LV. The excitation and emission
spectra of the samples were recorded on a Spex-Fluorolog FL3
22 spectrofluorimeter equipped with a double grating 0.22 m
Spex 1680 monochromator and a 450 W Xe lamp as the excita-
tion source operating in the front face mode. The lifetime
measurements were carried out at room temperature using
a Spex 1040 D phosphorimeter.
The overall quantum yields (foverall) of the europium
complexes were measured at room temperature using the tech-
nique for powdered samples described by Bril et al.,26 through the
following expression:
1  rst Ax
foverall   fst (4)
1  rX Ast
where rst and rx are the diffuse reflectance (with respect to a fixed
wavelength; Fig. S13 of the ESI) of the complexes and of the
standard phosphor, respectively, and fst is the quantum yield of
the standard phosphor. The terms Ax and Ast represent the area
under the complex and the standard emission spectra, respectively.
In order to have absolute intensity values BaSO4 was used as
a reflecting standard. The standard phosphor used was perylene
(Aldrich), whose emission spectrum is formed as a large broad
band peaking around 580 nm, with a constant f value (fst 98%,
lex 436 nm).31 Three measurements were carried out for each
sample, so that the presented foverall value corresponds to the
arithmetic mean value. The errors in the quantum yield values
associated with this technique were estimated within 10%.32
Synthetic procedures
Synthesis of methyl 4-biphenyl carboxylate. 2 g of 4-biphenyl
carboxylic acid is dissolved in 20 ml methanol and a catalytic
amount of conc. H2SO4 added, then stirred at 70  C for 24 h
(Scheme 1). The reaction mixture is poured into ice cold water,
ester precipitated out, filtered, dried and used for further
synthesis steps. Yield (90%). 1H NMR (CDC13, 500 MHz):
d (ppm) 8.11 (d, 2H, J 15 Hz), 7.65 (q, 4H, J 18 Hz), 7.44 (m,
3H), 3.94 (s, 3H). 13C NMR (125 MHz, CDCl3) d (ppm): 167.02,
145.65, 140.01, 130.10, 128.92, 128.14, 127.28, 127.05, 52.13.
m/z 213 (M + H)+.
Synthesis of the ligand 1-(4-biphenoyl)-3-(2-fluo-
royl)propanedione (HBFPD). The ligand HBFPD was synthe-
sized according to Scheme 1. Acetylfluorene (1 mmol) and
methyl 4-biphenyl carboxylate (1mmol) were added to 20 mL of
dry tetrahydrofuran (THF) and stirred for 10 min at 0  C in an
J. Mater. Chem., 2010, 20, 52205227 | 5225

ice bath. To this solution, sodium hydride (2 mmol) was added in
an inert atmosphere and stirred for 30 min followed by further
stirring at 70  C for 12 h. To the resulting solution, 2 M HCl
(50 mL) was added, and extracted twice with dichloromethane
(2  35 mL). The organic layer was separated and dried over
Na2SO4, and the solvent was evaporated. The crude product thus
obtained was then purified by column chromatography on silica
gel with a mixture of chloroform and hexane (1 : 10) as the eluent
to get the product as a yellow solid (yield 60%). Elemental
analysis (%): calcd for C28H20O2 (388.15): C 86.57, H 5.19;
Found: C 86.19, H 5.41. 1H NMR (CDC13, 500 MHz): d (ppm)
17.10 (broad, enolOH), 8.22 (s, 1H), 8.08 (t, 3H, J 15 Hz),
7.89 (t, 2H, J 10 Hz), 7.35 (d, 2H, J 15 Hz), 7.67 (d, 2H, J Raman nmax (cm1): 748, 1196, 1284, 1404, 1486, 1606 (Fig. S5 of
15 Hz), 7.60 (d,1H), 7.46 (t, 2H, J 15 Hz), 7.40 (t, 2H, J
Published on 20 May 2010 on http://pubs.rsc.org | doi:10.1039/C0JM00588F
15 Hz), 6.98 (s, 1H), 4.00 (s, 2H) (Fig. S1 of the ESI). 13C NMR
(125 MHz, CDCl3) d (ppm): 186.10, 184.71, 146.10, 145.1,
144.36, 143.52, 140.65, 139.99 134.38, 133.94, 127.97, 128.16,
127.97127.08, 126.44, 125.28, 123.90, 120.79, 119.89, 93.12,
Downloaded by University of Sussex on 29 June 2012
77.2876.78 (CDCl3), 36.94 (Fig. S2 of the ESI). IR (KBr) nmax
(cm1): 2923, 1604, 1447, 1307, 1242, 1125, 1002, 762. m/z
389.39 (M + H)+.
Synthesis of complexes Ln(BFPD)3(H2O)2 [Ln Eu (1), Gd
(4)]. To a solution of HBFPD (6 mmol) in THF was added 6
mmol of NaOH in water and the resulting mixture was stirred for
5 min. To this mixture, 2 mmol of Ln(NO3)3$6(H2O) in 2 mL
water was added dropwise and stirred for 24 h at room
temperature (Scheme 2). The reaction mixture was extracted with
CHCl3 and crude products were obtained after solvent evapo-
ration. The products were purified by recrystallization from
chloroform solution and used for further analysis and photo-
physical studies. Efforts to grow single crystals of complexes
1 and 4 were not fruitful.
Eu(BFPD)3(H2O)2 (1). Elemental analysis (%): calcd for
C84H61O8Eu (1349.74): C 74.80, H 5.07. Found: C 74.91, H 5.38.
IR (KBr) nmax (cm1): 3434, 2922, 1590, 1449, 1308, 1218, 1117,
1005, 758. m/z 928.14 [Eu(BFPD)2 + 1]+.
Gd(BFPD)3(H2O)2 (4). Elemental analysis (%): calcd for
C84H61O8Gd (1355.06): C 74.59, H 4.57. Found: C 75.03, H 4.63.
IR (KBr) nmax (cm1): 3434, 2923, 1587, 1449, 1306, 1214, 1119,
1005, 758. m/z 932.14 [Gd(BFPD)2 + 1]+.
Synthesis of complex Eu(BFPD)3(phen) (2). Complex 2 was
prepared by stirring equimolar solutions of 1 and phen in CHCl3
solution for 24 h at 70  C (Scheme 3). The products were isolated
by solvent evaporation and purified by recrystallization from
a chloroform/hexane mixture. Efforts to grow single crystals of
complex 2 were not fruitful. Elemental analysis (%): calcd for
C96H65O6N2Eu (1493.95): C 77.23, H 4.48, N 1.86. Found: C
77.51, H 4.43, N 1.93. IR (KBr) nmax (cm1): 2924, 1594, 1524,
1448, 1306, 1217, 1117, 1005, 758. m/z 1105.86
[Eu(BFPD)2(phen)]+.
Synthesis of the ligand SiBFPD-Na. 1 mmol of HBFPD was
first dissolved in dry THF and 2.5 mmol of NaH was added
under argon atmosphere while stirring at room temperature.
Two hours later, 1 mmol of 3-(triethoxysilyl)propyl isocyanate
5226 | J. Mater. Chem., 2010, 20, 52205227
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(TESPIC) was added dropwise into the refluxing solution at
70  C and stirring continued for another 12 h (Scheme 4). After
isolation and purification, the sodium salt of SiBFPD-Na was
obtained as a yellow solid, which was used without further
purification. 1H NMR: (CDC13, 500 MHz): d (ppm) 0.77 (t, 2H,
J 75Hz), 1.47 (t, 9H, J 35Hz), 1.87 (m, 2H, J 25Hz), 3.56
(2H, m, J 60Hz), 4.22 (m, 8H, J 50Hz), 5.12 (broad, 1H),
7.308.12 (aromatic), (Fig. S6 of the ESI). 13C NMR (75.47 Hz,
solid state) d (ppm): 185.13, 182.99, 159.96, 142.33, 134.90,
126.81, 58.05, 43.05, 36.71, 25.91, 18.63, 8.77 (Fig. S7 of the
ESI). FT-IR (KBr) nmax(cm1): 3335, 2923, 2961, 2851, 1629,
1590, 1443, 1282, 1076, 961, 690 (Fig. S4 of the ESI). FT-
the ESI). The detailed vibrational spectral data are given in
Table S1.
Synthesis of Eu3+ luminescent hexagonal mesoporous silica
particles Eu(SiBFPD)3(phen)/MCM-41 (3). 3 mmol of SiBFPD-
Na was dissolved in 20 mL THF with stirring. Then an
appropriate amount of MCM-41 (molar ratio of MCM-
41 : SiBFPD-Na 1 : 1) was added to the solution. Six hours
later, the required amounts of Eu(NO3)3$6H2O (1 mmol) and
1,10-phenanthroline (1 mmol) were added and stirred vigorously
in argon atmosphere at room temperature for 48 h (Scheme 4).
Finally, the solid product was recovered by centrifugation,
washed with THF and dried at 80  C. The 29Si CPMAS NMR
spectrum of 3 is shown in Fig. S8 of the ESI. FT-IR (KBr)
nmax(cm1): 3410, 2925, 2961, 2851, 1629, 1568, 1519, 1443, 1282,
1188, 1100, 961, 760, 682 (Fig. S4 of the ESI). FT-Raman
nmax(cm1): 748, 1196, 1284, 1404, 1486, 1606 (Fig.S5 of the
ESI). The detailed vibrational spectral data are given in Table
S1. The surface area of complex 3 11 m2 g1; the pore volume
0.02 cm3 g1; average particle size 364 nm (Fig. S9 of the ESI).
The SEM and TEM pictures of the complex 3 are shown in
Fig. S10 and S11 (ESI), respectively. The thermogravimetric
curve for complex 3 is shown in Fig. S3 (ESI). XRD patterns of
MCM-41 and complex 3 are shown in Fig. S12 (ESI).
Conclusions
A novel efficient antenna complex of Eu3+ supported by the 1-(4-
biphenoyl)-3-(2-fluoroyl)propanedione ligand in the presence of
an ancillary ligand has been synthesized and fully characterized
and its photophysical properties evaluated. Suitably expanded p-
conjugation in the complex molecule makes the excitation
window red shift to the visible region. The results demonstrated
that the ternary Eu3+ complex exhibits intense red emission with
an overall quantum yield of 32% under blue light excitation
(lmax 440 nm). Further in the present work, the visible sensi-
tized Eu3+ luminescent complex has been covalently immobilized
into the ordered MCM-41 mesoporous host through the modi-
fication of a novel highly conjugated b-diketonate with 3-(trie-
thoxysilyl)propylisocyanate by a co-condensation route. The
newly designed mesoporous hybrid material shows a stronger
red/orange intensity ratio, higher 5D0 quantum efficiency, longer
lifetimes, and better thermal stability than the precursor
complex. All of the results indicate that the currently designed
Eu3+ complexes are promising candidates as visible-light excit-
able red phosphors for luminescent applications.
This journal is The Royal Society of Chemistry 2010

Acknowledgements
The authors acknowledge financial support from the Council of
Scientific and Industrial Research (NWP 0023). One of the
authors (V. D.) thanks the Council of Scientific & Industrial
Research (CSIR), New Delhi for awarding her a Junior Research
Fellowship.
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