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Bianchin, S. Roppa, V. Bertolasi and F. Enrichi, Dalton Trans., 2014, DOI: 10.1039/C4DT00643G.
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Yttrium and lanthanide complexes of -dialdehydes: synthesis, characterization and
Published on 09 May 2014. Downloaded by Universidad de Sonora on 12/05/2014 22:50:20.
Marco Bortoluzzi a*, Elena Bianchin a, Stefania Roppa a, Valerio Bertolasi b, Francesco Enrichi c, d
a
Dipartimento di Scienze Molecolari e Nanosistemi, Universit Ca Foscari Venezia, Dorsoduro
2137, 30123 Venezia, Italy.
Dipartimento di Scienze Chimiche e Farmaceutiche e Centro di
Strutturistica Diffrattometrica, Universit di Ferrara, via Borsari 46, 44100 Ferrara, Italy. c Veneto
Nanotech, Laboratorio Nanofab, Via delle Industrie 5, 30175 Marghera, Venezia, Italy. d CNR-IFN,
Istituto di Fotonica e Nanotecnologie, Laboratorio CSMFO, via alla Cascata 56/C, 38123 Povo,
Trento, Italy.
* Corresponding author. E-mail: markos@unive.it
Keywords: yttrium, lanthanides, -dialdehydes, nitromalonaldehyde, luminescence
Abstract
Coordination compounds having formulae [AsPh4][Ln(NMA)4] (1Ln), Ln(NMA)3(tppo)2 (2Ln),

Ln(NMA)3(bipyO2) (3Ln), Ln(NMA)3(phen) (4Ln) and Ln(NMA)3(terpy) (5Ln) (Ln = Y and some
lanthanides; NMA = conjugate base of nitromalonaldehyde; tppo = triphenylphosphine oxide;
bipyO2 = 2,2-bipyridine-N,N-dioxide; phen = 1,10-phenantroline; terpy = 2,2:6,2-terpyridine)
were synthesized and characterized and X-Ray diffraction data were collected for
[AsPh4][Y(NMA)4] (1Y). The neutral europium derivatives showed appreciable luminescence in the
solid state upon excitation with UV light and photoluminescence measurements were carried out.
These compounds were used as dopants for the preparation of luminescent poly(methyl
methacrylate). Luminescent polyvinylpirrolidone samples were obtained by reacting the pure
polymer with water solutions containing NMA and trivalent europium ion.
Dalton Transactions Accepted Manuscript
luminescence of coordination compounds with the conjugate base of nitromalonaldehyde
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Introduction
chemistry and a huge number of neutral and charged complexes is known. The coordination
sphere can be composed by only -diketonates, but often other ligands are present, mainly monoand polydentate oxygen- and nitrogen-donors. The most common coordination numbers are eight
and nine. These compounds have been studied in detail as luminescent materials, NMR shift
reagents, MOCVD precursors, and catalysts for organic reactions. Several -diketonate complexes
of trivalent lanthanide ions are of current interest for the preparation of advanced materials for
frontier technology applications, for example novel devices for light conversion and amplification
and new biomedical sensors [1].
The coordination chemistry of -dialdehydes, such as malonaldehyde and its derivatives, has been
less studied with respect to -diketonates, despite the lower steric bulk. To the best of our
knowledge no lanthanide compound with these ligands is actually reported in the literature and
the few known complexes have d-block elements as metal centres. The first synthesized complex
was the chromium derivative Cr(MA)3 (MA = conjugate base of malonaldehyde), which was
obtained by reacting freshly prepared malonaldehyde with CrCl3 in the presence of Zn dust
[2]
Successively, Albertin and co-workers reported the synthesis and reactivity of a number of iron,
cobalt, nickel, palladium, platinum, copper and zinc complexes of the ligands NMA [3] and BrMA [4],
where NMA and BrMA are the conjugate bases of nitromalonaldehyde and bromomalonaldehyde,
respectively.
The lack of experimental data regarding the coordination chemistry of -dialdehydes towards
group 3 and lanthanide elements prompted us to start a research in this field of inorganic
chemistry. In the framework of our interest towards novel luminescent lanthanide complexes and
polymeric materials containing lanthanide derivatives [5], we have recently described the synthesis,
photoluminescence and electrochemistry of novel yttrium, europium and terbium complexes with
BrMA as ligand
[6]
. in this paper we report some results concerning the synthesis and
characterization of novel yttrium and lanthanide complexes of NMA, together with

photoluminescence measurements and the preparation of luminescent doped plastic materials.
-diketonates are among the most studied ligands in the field of lanthanide coordination
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Results and discussion
Complexes of general formula [AsPh4][Ln(NMA)4] (1Ln; Ln = Y, Eu, Tb, Yb), having four NMA ligands
coordinated to trivalent group 3 and lanthanide ions, were obtained by reacting YCl3 or LnCl3 with
four equivalents of Na[NMA]H2O in water. Products were isolated by subsequent addition of
[AsPh4]Cl, as depicted in Scheme 1.
Scheme 1. Synthesis of [AsPh4][Ln(NMA)4] (1Ln).

Besides the signals of the cation, the 1H NMR spectra of the complexes 1Ln in CDCl3 show only one
resonance for the aldehyde hydrogen atoms, which are therefore equivalent on the NMR
timescale. The chemical shift is strongly dependent upon the nature of the metal centre. For the
diamagnetic 1Y derivative is 9.58 ppm at 298 K, while the values recorded for the other
complexes indicate a strong paramagnetic shift and are -15.86 ppm (1Eu), 0.33 ppm (1Tb) and 4.95
ppm (1Yb). As an example, Figure 1 compares the 1H NMR spectra of 1Y and 1Eu. The 13C {1H} NMR
spectrum of 1Y displays a resonance at 182.9 ppm for the carbonyl carbons and a singlet at 120.2
ppm corresponding to C-NO2.
The IR spectra of all these compounds are very similar and show three strong bands, one around
1640-1650 cm-1 attributable to C=O stretching and other two at about 1530 cm-1 and 1340 cm-1
related to the asymmetric and symmetric stretchings of the NO2 group (see for example the
spectrum of 1Y in Figure 2). Conductivity measurements agree with the formation of 1:1
electrolytes. Solutions of 1Ln in CH2Cl2 exhibit strong absorptions for wavelengths below 375 nm,
with a maximum at around 298 nm.
Synthesis and characterization of the complexes
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Figure 1. 1H NMR spectra of 1Y and 1Eu (CDCl3, 298 K).
Figure 2. IR spectrum (KBr pellet) of 1Y.

In the case of 1Y crystals suitable for X-Ray diffraction were obtained from water/acetone
solutions. ORTEP
[7]
view of the of the anion [Y(NMA)4]- is shown in Figure 3 and a selection of
bond distances and angles is given in Table 1. Figure 3 also highlights the square-antiprismatic
coordination
around
the
metal
centre,
similar
tetrakis(hexafluoroacetylacetonato) yttrium(III) anions [8].
to
that
observed
in
analogous
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Table 1. Selected bond lengths () and angles () for the anion of 1Y.
Y1-O1
Y1-O9
C1-O1
C7-O9
2.310(2)
2.326(2)
1.251(3)
1.254(3)
Y1-O2
Y1-O10
C3-O2
C9-O10
2.386(2)
2.319(2)
1.237(3)
1.250(3)
Y1-O5
Y1-O13
C4-O5
C10-O13
2.352(2)
2.339(2)
1.234(3)
1.241(3)
Y1-O6
Y1-O14
C6-O6
C12-O14
2.319(2)
2.341(2)
1.245(3)
1.246(3)
72.28(6)
144.09(6)
76.21(7)
74.15(7)
127.24(8)
78.01(6)
72.15(6)
O1-Y5-O5
O1-Y1-O13
O2-Y1-O9
O5-Y1-O6
O5-Y1-O14
O6-Y1-O14
O10-Y1-O13
77.75(8)
144.12(6)
128.59(7)
71.57(6)
114.18(6)
144.08(6)
71.72(7)
O1-Y1-O6
O1-Y1-O14
O2-Y1-O10
O5-Y1-O9
O6-Y1-O9
O9-Y1-O10
O10-Y1-O14
89.03(7)
100.71(7)
143.53(7)
72.67(6)
143.64(6)
74.46(6)
91.14(7)
O1-Y1-O9
O2-Y1-O5
O2-Y1-O13
O5-Y1-O10
O6-Y1-O10
O9-Y1-O13
O13-Y1-O14
77.18(6)
135.85(7)
72.17(6)
73.13(8)
101.01(7)
130.86(6)
73.96(6)
Angles
O1-Y1-O2
O1-Y1-O10
O2-Y1-O6
O2-Y1-O14
O5-Y1-O13
O6-Y1-O13
O9-Y1-O14
Figure 3. (a) ORTEP view of the anion of 1Y showing the thermal ellipsoids at 30% probability level.
(b) Distorted square-antiprismatic coordination around the Y(III) cation.
Several complexes having three NMA and neutral oxygen- or nitrogen-donor moieties in the
coordination sphere were synthesized by subsequent addition of the ligands to water solutions of
the proper metal chloride. In particular, Ln(NMA)3(tppo)2 (2Ln), Ln(NMA)3(bipyO2) (3Ln),
Ln(NMA)3(phen) (4Ln) and Ln(NMA)3(terpy) (5Ln) were isolated and characterized (tppo =
triphenylphosphine oxide; bipyO2 = 2,2-bipyridine-N,N-dioxide; phen = 1,10-phenantroline; terpy
= 2,2:6,2-terpyridine). The reactions leading to the products 2Ln - 5Ln are sketched in Scheme 2.
The elemental analyses agree with the proposed formulations and conductivity measurements
indicate that these complexes are neutral. All the IR spectra show the characteristic CO and
Lengths
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asymmetric and symmetric NO2 bands of NMA. Moreover, the P-O stretchings are observable
around 1130 cm-1 for the tppo-derivatives 2Ln. All the UV-VIS spectra show strong absorptions in
the range 250 375 nm and those of 2Ln and 3Ln in CH2Cl2 resemble the previously described
maxima, one at 263 nm and the other at 327 nm. The absorption range is about the same also for
4Ln and 5Ln and the phenantroline derivatives in CH2Cl2 display two maxima at 271 and 295 nm. In
the case of 4Yb the weak absorption of the trivalent metal ion was also observed around 970 nm,
corresponding to the 2F5/22F7/2 transition. The presence of the terpy ligand instead of phen in the
coordination sphere meaningfully increases the absorption of the complexes in the near-UV range.
Scheme 2. Synthesis of Ln(NMA)3(tppo)2 (2Ln), Ln(NMA)3(bipyO2) (3Ln), Ln(NMA)3(phen) (4Ln) and

Ln(NMA)3(terpy) (5Ln).
spectra of 1Ln. The 3Ln complexes in water are instead characterized by two distinct absorption
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The 1H NMR spectra of 2Ln complexes in CDCl3 solution at 298 K show, besides the resonances of
the tppo aromatic rings, a singlet attributable to NMA protons with chemical shift strongly
dependent upon the nature of the metal centre. The
31
P {1H} NMR spectra of the 2Ln complexes
2Y the scalar coupling between 31P and 89Y is observable (2JP-Y = 8.9 Hz, see Figure 4). In the case of
the 3Ln complexes the 1H NMR spectra recorded in (CD3)2SO show, besides a singlet for the NMA
ligands which is strongly affected by paramagnetic shift, a set of four signals for the bipyO2 ligand,
slightly broadened and shifted in the cases of paramagnetic metal centres. The two pyridine-Noxide rings are therefore equivalent on the NMR timescale. Also in the 1H NMR spectra of 4Ln in
CDCl3 five resonances are present, four corresponding to phenantroline hydrogen atoms and one
to the NMA ligands, and all these signals are strongly influenced by the electronic configuration of
the metal centres. As an example, Figure 5 compares the 1H NMR spectra of the yttrium and
europium complexes. Finally, the 1H NMR spectra of 5Y and 5Eu in (CD3)2SO show six resonances for
the terpy ligand and one singlet for the aldehyde moieties. The chemical shift of this last signal is
9.64 ppm at 317 K for 5Y, while it is shifted at 2.26 ppm in the spectrum of 5Eu at the same
temperature. The terpyridine signals are instead closely comparable between the two complexes
and very similar to those of the free ligand, this suggesting that a dissociation equilibrium occurs in
DMSO solution. Unfortunately, we were unable collect resolved 1H NMR spectra of 5Ln compounds
in non-coordinating solvents.
Figure 4. 31P {1H} NMR of 2Y (CDCl3, 222 K).
recorded at low temperature display a single resonance and in the case of the yttrium derivative
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Figure 5. 1H NMR spectra of 4Y and 4Eu (CDCl3, 317 K).

Information about the coordination sphere around the metal centres was obtained by carrying out
DFT calculations on the diamagnetic yttrium derivatives 2Y - 5Y. A previous comparison between
experimental and theoretical data for the anion of 1Y confirmed the validity of the computational
method, with an average error on the bond lengths below 1%. The optimized geometries are
reported in Figure 6, while the computed bond lengths between yttrium and the donor atoms are
collected in Table 2. In 2Y, 3Y and 4Y the stationary points correspond to eight-coordinated
distorted square antiprisms, while the coordination number in 5Y is nine and the equilibrium
geometry is strongly influenced by the planarity of the coordinated terpy ligand. The Y-O(NMA)
bond lengths fall in the range 2.306 2.411 and the average Y-O(NMA) distance is slightly longer
for the 9-coordinated compound 5Y with respect to the other complexes. The Y-O(tppo) bonds in
2Y have comparable equilibrium values with respect to Y-O(NMA). Only one of the two Y-O(bipyO2)
bonds in 3Y is instead comparable with those formed by NMA with the metal centre, while the
other is meaningfully longer, more than 0.1 . The Y-N distances in 4Y and 5Y are comprised
between 2.561 and 2.614 and the longest bond is that between Y(III) and the central ring of
terpyridine.
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Figure 6. DFT-optimized geometries of 2Y - 5Y. Hydrogen atoms on aromatic rings were omitted for
clarity.
Table 2. Computed bond lengths () between yttrium and the donor atoms in 2Y, 3Y, 4Y and 5Y.
2Y
Y-O(NMA)
Y-O(tppo)
2.370
2.323
2.374
2.343
2.360
2.354
2.340
2.340
2.336
2.351
2.366
2.473
2.306
2.355
2.319
2.350
2.340
2.565
2.346
2.561
2.335
2.338
2.314
2.333
2.378
2.587
2.411
2.614
2.382
2.563
2.375
2.352
2.376
3Y
Y-O(NMA)
Y-O(bipyO2)
4Y
Y-O(NMA)
Y-N(phen)
5Y
Y-O(NMA)
Y-N(terpy)
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Photoluminescence measurements on the pure complexes

Photoluminescence studies were initially carried out on 1Ln complexes. No appreciable
luminescence was observed in solution or at the solid state for the derivatives of the visible
effect. A photoluminescence (PL) spectrum of solid 1Eu showing the characteristic 5D07FJ
transitions (J = 0 - 4) was however collected by direct excitation of the metal centre at 394 nm. The
most intense signal (62.6%) falls at 612 nm and corresponds to the 5D07F2 transition.
Photoluminescence excitation (PLE) measurements confirm that luminescent emissions in 1Eu can
be achieved only by direct excitation of the Eu(III) ion. The measured lifetime () is 0.419 ms,
comparable to the values of several homoleptic -diketonate europium complexes
[9]
, and
corresponds to an intrinsic quantum yield (Qi) of 24%. In the case of the ytterbium derivative 1Yb a
weak emission around 1000 nm is observable upon excitation with radiation in the near-UV range.
This signal is related to the 2F5/22F7/2 transition and is composed by several peaks because of the
Stark effect. The lifetime of such an emission is quite low, 4.48 s, if compared to the values
reported for several common ytterbium -diketonates
[10]
. This last result can be tentatively
ascribed to the presence of the high-energy oscillators H-C(=O) near the metal centre, which
favours the non-radiative decay of the NIR-emitter Yb(III).
Differently from 1Eu, solid samples of the europium complexes 2Eu - 5Eu are visibly
photoluminescent upon irradiation with UV light. In all the cases the PL spectra show the 5D07FJ
transitions of the metal centre, without meaningful emissions from the excited states of the
coordinated ligands, and the most intense band is the 5D07F2 in the range 610 - 626 nm. As an
example Figure 7 reports the PL spectrum of the terpy-derivative 5Eu. PLE measurements indicate
that the antenna-effect from the coordinated ligands is the dominant process of population of the
resonance level of Eu(III) and occurs for excitation in the UV-range below 350 nm.
The change of ligands around the Eu(III) ion mainly influences the luminescence lifetimes. The
decay curves are in all the cases mono-exponential and the values are collected in Table 3,
together with the corresponding intrinsic quantum yields. A comparison with data reported in the
literature for similar compounds having -diketonates instead of NMA suggests that the nonradiative decay is more favoured for the -dialdehyde derivatives here described. The
phenantroline-complex 4Eu exhibits a particularly short value (0.190 ms) with respect to
comparable -diketonates: for example, the phen-europium derivatives of dibenzoylmethane,
emitting Eu(III) and Tb(III) ions upon excitation with UV light, this suggesting a very poor antenna-
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dimethoxydibenzoylmethane, benzoylacetone and 4-methylbenzoyl-2-furanoylmethane have

values ranging from 0.34 to 0.47 ms
[11]
. The closeness to the metal ion of C-H oscillators may
explain the quite fast decays, but also the relatively low steric bulk of NMA may have a role, for
by the fact that the highest values reported in Table 3 are those of 3Eu, where the spacedemanding ligand tppo is coordinated, and of 5Eu, which is a nine-coordinate complex. This last
compound is the most interesting photoluminescent species here described, because it has a
rather good intrinsic quantum yield (67%). Moreover, the PLE maximum falls between 300 and
350 nm, a spectral region characterized by high absorptions.
Figure 7. PL spectrum of 5Eu (solid sample, 298 K, excitation = 310 nm).

Table 3. Emission decay times (), intrinsic quantum yields (Qi) and 5D07F2/5D07F1 ratios of 2Eu 5Eu.
Eu
2
Eu
3
Eu
4
Eu
5
(ms)
0.364
0.322
0.190
0.487
Qi (%)
35
18
15
67
D07F2/5D07F1
12.0
13.2
10.3
16.2
The replacement of Eu(III) with Tb(III) led in most of the cases to complexes having negligible
emissions in the visible range, indicating that NMA is a ligand unable to efficiently sensitize the
example allowing the interaction of Eu(III) with water traces. This hypothesis is partially supported
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trivalent terbium ion. The complex having the most easily appreciable green emission is 3Tb, whose
PL spectrum shows the 5D47FJ (J = 6 - 3) transitions characteristic of the metal centre upon
excitation at 286 nm. No fluorescence from the excited ligands is present and the most intense
intrinsic quantum yield below 1%
[12]
. In order to understand the behaviour of NMA towards
Tb(III), the triplet-state relative energy of the model compound Tb(NMA)3(H2O)2 was estimated
using PM7/sparkle calculations
[13]
, and resulted around 21800 cm-1. The fact that NMA is unable
to efficiently sensitize Tb(III) can be therefore ascribed to a too low triplet state of the coordinated
ligand. As described by Latva ad co-workers
[14]
, back-energy transfer from the metal ion to the
ligand is expected when the the triplet state energy is below 22300 cm-1.
The coordination spheres here considered revealed to be scarcely efficient also for the
sensitization of Yb(III). Both 2Yb and 4Yb showed the characteristic 2F5/22F7/2 transition around
1000 nm upon excitation with radiation in the near-UV range, but the measured lifetimes are quite
short (7.17 s for 2Yb, 3.58 s for 4Yb) and similar to that of 1Yb. In the case of 4Yb the intrinsic
quantum yield was estimated on the basis of the absorption spectrum to be around 0.4%.
Preparation and characterization of luminescent doped polymers

The complexes having significant luminescence in the visible range were studied as dopants for
the preparation of photoluminescent poly(methyl methacrylate) PMMA. The samples were
obtained by adding a known amount of the proper complex to a solution of PMMA in
dichloromethane and subsequent slow removal of the solvent. The concentration of complexes in
the doped polymers ranges from 10 to 50 mol/g and all these materials exhibit appreciable
luminescence if irradiated with UV light.
The PL spectra of all the europium-based materials display only the typical 5D07FJ transitions of
the Eu(III) ion. The and Qi values for 2Eu@PMMA, 3Eu@PMMA, 4Eu@PMMA and 5Eu@PMMA are
collected in Table 4. The comparison with the data reported in Table 3 shows that for the oxygendonor derivatives 2Eu and 3Eu the embedding of the complexes causes a reduction of the lifetimes,
while the opposite effect occurs for the phen and terpy derivatives 4Eu and 5Eu. The only polymer
showing a noticeable increment of Qi with respect to the corresponding pure compound is
4Eu@PMMA. The variations of intrinsic quantum yields are not directly proportional to the
band corresponds to the 5D47F5 transition. The lifetime is very short, 14 s, and indicates an
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changes of , because the PL spectra of the doped polymers have different 5D07F2/5D07F1 ratios
with respect to the corresponding complexes at the solid state, as observable from the
comparison of data reported in Tables 3 and 4. This suggests a variation of site symmetry caused
5Eu. The effects of the encapsulation in PMMA are therefore not limited to expected phenomena
such as the reduction of the concentration quenching, the protection of the metal centres from
water traces, and the non-radiative decay caused by the polymer chains surrounding the
complexes.
Table 4. Emission decay times (), intrinsic quantum yields (Qi) and 5D07F2/5D07F1 ratios of
2Eu@PMMA - 5Eu@PMMA.
Eu
2 @PMMA
3Eu@PMMA
4Eu@PMMA
5Eu@PMMA
(ms)
0.215
0.267
0.457
0.671
Qi (%)
17
13
26
51
D0 F2/ D0 F1
10.8
12.3
11.5
11.8
The green luminescence of the terbium-complex 3Tb prompted us to prepare the corresponding
doped polymer 3Tb@PMMA. Both the PL spectrum and the lifetime (10 s) of this plastic material
closely resemble the data collected for the pure compound. No enhancement of the luminescence
is therefore caused by the embedding of 3Tb in PMMA.
Another way to obtain plastic materials showing luminescence in the visible range was the
addition of polyvinylpirrolidone (PVP, average MW = 10000 g mol-1) to a water solution containing
EuCl3 and Na[NMA]H2O in 1:3 molar ratio. This solution probably contains a complex of the type
Eu(NMA)3(H2O)x, whose 1H NMR spectrum in (CD3)2SO shows only a broad NMA resonance
strongly influenced by paramagnetic shift ( = 5.70 ppm at 298 K, 4.88 ppm at 317 K). After
removal of water under reduced pressure the doped polyvinylpirrolidone Eu-NMA@PVP was
isolated. The purification was carried out from ethanol and the same solvent was used to prepare
thin films by the doctor blade tape technique. The material has a Eu:monomer ratio of about 1:45
and is visibly luminescent upon irradiation with UV light. On the contrary, the replacement of
Eu(III) with Tb(III) led to plastics having no appreciable luminescence.
The PL spectrum of Eu-NMA@PVP displays only the typical emissions of the metal ion. The
strongest band is centred at 614 nm and corresponds to the 5D07F2 transition. The PLE spectrum
showed that the antenna-effect is the dominating pathway for the population of the 5D0 emitting
by the interaction of PMMA with Eu(III), which is particularly pronounced for the terpy-derivative
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level and occurs for excitation below 340 nm. The emission decay time is 0.678 ms, higher than the
value recently reported for PVP doped with Eu(tta)3 (tta = thenoyltrifluoroacetoacetonate). The
corresponding intrinsic quantum yield (31%) is however about the half of the value calculated for
Conclusion
In this paper we reported the first examples of coordination compounds of trivalent yttrium and
lanthanide ions with the conjugate base of nitromalonaldehyde. The homoleptic anionic
complexes of visible-emitting metal centres have negligible photoluminescence, while the
antenna-effect causes the typical Eu(III) red emission in the neutral derivatives having three NMA
in the coordination sphere. Luminescent plastic materials containing Eu(III) and NMA were
prepared, using PMMA and PVP polymers. NMA revealed to be almost unable to sensitize the
green-emitter Tb(III). The lifetimes of the Yb(III) derivatives suggest that the presence of highenergy oscillators near the metal centre makes the non-radiative decay prevailing with respect to
the NIR emission.
Experimental section
Materials and methods

The reagents used for the preparation of the lanthanide complexes and the doped polymers were
Aldrich products used without further purifications, with the exception of the anhydrous YCl3 and
LnCl3 salts (Strem). Na[NMA]H2O was prepared following a reported procedure, starting from
mucobromic acid and sodium nitrite
[16]
. The ligand bipyO2 was synthesized by reaction of 2,2-
bipyridine with H2O2 in acetic acid [17].

Conductivity measurements were carried out at 298 K on 10-3 mol dm-3 solutions using a
radiometer Copenhagen CDM 83 instrument. Elemental analyses were performed at the C.N.R. of
Padua. NMR spectra were recorded at variable temperature on a Bruker Avance 300 or a Bruker
the tta derivative [15].
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AC 200 spectrometer using CDCl3 or (CD3)2SO as solvents. 1H and
13
C NMR chemical shifts are
reported relative to tetramethylsilane. The solvent signals, quoted with respect to TMS ( = 0
ppm), were used as internal references. 31P NMR resonances are referred to external H3PO4 (85%
One spectrophotometer. Samples were dispersed in KBr. UV-VIS-NIR absorption spectra were
recorded in solution using a Perkin Elmer Lambda 40 spectrophotometer. Photoluminescence
emission (PL) and excitation (PLE) measurements were carried out on solid samples at room
temperature by a Horiba Jobin Yvon Fluorolog-3 spectrofluorometer. A xenon arc lamp was used
as continuous-spectrum source selecting the excitation wavelength by a double grating CzernyTurner monochromator. A single grating monochromator coupled to a R928 Hamamatsu
photomultiplier tube (PMT) was used as detection system for optical emission measurements.
Excitation and emission spectra were corrected for the instrumental functions. Time-resolved
analyses were performed in Multi Channel Scaling modality (MCS) by using a tuneable pulsed
Nd:YAG laser system as excitation source. The luminescence lifetimes were derived from the
luminescence decay curves, fitting the data with the least squares method by using exponential
equations for all the materials. The intrinsic quantum yield of the Ln ion (Qi) was estimated on the
basis of equation (1), where is the measured luminescence lifetime. rad was obtained for the
europium-based compounds from equation (2), where n indicates the refractive index of the
sample and the value of 1.5 is assumed in this work for comparative purposes. I(5D07FJ)/
I(5D07F1) is the ratio between the total integrated emission from the Eu(5D0) level to the 7FJ
manifold and the integrated intensity of the transition 5D07F1
[18]
. In the case of ytterbium as
metal centre rad was estimated using equation (3) [19], where the constant c is the speed of light,
is the frequency of the transition, Na is the Avogadros constant, () is the absorption spectrum of
the transition, gg and ge denote the degeneracies (2J+1) of the ground and excited states
respectively.

(1)

14.65

2303
!" #" %&

$
(2)
%'
( ) * +*
(3)
water solution). IR spectra were recorded from 4000 to 400 cm-1 using a Perkin Elmer Spectrum
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Synthesis of [AsPh4][Ln(NMA)4] (1Ln) (Ln = Y, Eu, Tb, Yb)
solution containing 1.0 mmol of yttrium or lanthanide trichloride in 15 mL of water. The reaction
mixture was left under stirring at room temperature for 4 hours, then a solution containing 1
mmol (0.419 g) of tetraphenylarsonium chloride hydrate in 15 mL of water was dropwise added.
The product which separated out was filtered, washed with water and dried under reduced
pressure. The products were purified by slow evaporation of saturated water/acetone solutions.
Yield > 90% in all the cases.
Characterization of 1Y
C36H28AsN4O16Y: calcd. C 46.2, H 3.01, N 5.98; found C 45.9, H 3.05, N 5.95. M(acetone): 46 -1
mol-1 cm2. IR (KBr): CO = 1644 cm-1; aNO2 = 1509 cm-1; sNO2 = 1314 cm-1. UV-VIS (CH2Cl2, 298 K, nm,
max): 293. 1H NMR (CDCl3, 298 K, ): 9.58 (s, 8H, NMA-H); 8.00-7.55 (m, 20H, AsPh4). 13C {1H} NMR
(CDCl3, 298 K, ): 182.9 (HC=O); 135.4 (AsPh4-Cipso); 135.2, 132.8, 131.5 (AsPh4-CH); 120.2 (C-NO2).
Characterization of 1Eu
C36H28AsN4O16Eu: calcd. C 43.3, H 2.82, N 5.61; found C 43.0, H 2.85, N 5.55. M(acetone): 48 -1
max): 297. 1H NMR (CDCl3, 298 K, ): 7.91 (t, 4H, 3JHH = 7.7 Hz, AsPh4-para); 7.77 (t, 8H, 3JHH = 7.7
Hz, AsPh4-meta); 7.56 (d, 8H, 3JHH = 7.7 Hz, AsPh4-ortho); -15.86 (s, 8H, NMA-H). PL (solid sample,
exc = 394 nm, 298 K, nm): 589, 594 (5D07F1); 611, 615 (5D07F2); 650, 656 (5D07F3); 691, 699705 (5D07F4). PLE (solid sample, em = 615 nm, 298 K, nm): 382, 385, 393, 397, 415, 417, 434, 438
(Eu3+ excitation). Emission decay time (solid sample, 298 K): = 0.419 ms (exc = 394 nm, em = 614
nm). Qi = 24 %
Characterization of 1Tb
C36H28AsN4O16Tb: calcd. C 43.0, H 2.80, N 5.57; found C 42.7, H 2.85, N 5.50. M(acetone): 49 -1
max): 297. 1H NMR (CDCl3, 298 K, ): 8.79 (s, slightly br, 8H, AsPh4); 8.18 (s, slightly br, 8H, AsPh4);
7.92 (s, slightly br, 4H, AsPh4); 0.33 (s, br, 8H, NMA-H).
A water solution (10 mL) containing 4.0 mmol (0.628 g) of Na[NMA]H2O was slowly added to
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Characterization of 1Yb
C36H28AsN4O16Yb: calcd. C 42.4, H 2.77, N 5.49; found C 42.2, H 2.80, N 5.45. M(acetone): 48 -1
JHH = 7.2 Hz, AsPh4-para); 7.76 (t, 8H, 3JHH = 7.2 Hz, AsPh4-meta); 7.47 (d, 8H, 3JHH = 7.2 Hz, AsPh4-
ortho); 4.95 (s, slightly br, 8H, NMA-H). PL (solid sample, exc = 410 nm, 298 K, nm): 973-1034, max
1022 (2F5/22F7/2). Emission decay time (solid sample, 298 K): = 4.48 s (exc = 410 nm, em = 1000
nm).
Synthesis of Ln(NMA)3(tppo)2 (2Ln) (Ln = Y, Eu, Tb, Yb), Ln(NMA)3(bipyO2) (3Ln) (Ln = Y, Eu, Tb),
Ln(NMA)3(phen) (4Ln) (Ln = Y, Eu, Tb, Yb), Ln(NMA)3(terpy) (5Ln) (Ln = Y, Eu)
Na[NMA]H2O (1.5 mmol, 0.236 g) dissolved in 10 mL of water is slowly added to a solution
containing 0.5 mmol of yttrium or lanthanide chloride in 15 mL of water. The resulting solution is
left under stirring at room temperature for six hours, then a solution of the proper neutral ligand is
added (1.0 mmol, 0.278 g of triphenylphosphine oxide in 40 mL of acetone for 2Ln; 0.5 mmol, 0.094
g of 2,2-bipyridine-N,N-dioxide in 10 mL of water for 3Ln; 0.5 mmol, 0.101 g of 1,10-phenantroline
in 5 mL of HCl 0.1 N in water for 4Ln; 0.5 mmol, 0.117 g of 2,2:6,2-terpyridine in 5 mL of HCl 0.1
N in water for 5Ln). The reaction mixture is left overnight under stirring at room temperature. The
2Ln complexes were precipitated by removal of most of acetone under reduced pressure. 3Ln
separated from the solution after concentration at ca. 10 mL and cooling at 4C. In the cases of 4Ln
and 5Ln water was removed under reduced pressure and the crude products were dissolved in
nitromethane (20 mL). The solutions were filtered, then CH3NO2 was evaporated and the residual
solid was triturated with diethyl ether 10 mL. In all the cases the solid products were collected by
filtration and dried under vacuum. Yields > 90% for 2Ln, > 80% for 3Ln, >85% for 4Ln and 5Ln.
C45H36N3O14P2Y: calcd. C 54.4, H 3.65, N 4.23; found C 54.1, H 3.60, N 4.20. IR (KBr): CO = 1652 cm1
; aNO2 = 1507 cm-1; sNO2 = 1311 cm-1; PO = 1130 cm-1. UV-VIS (CH2Cl2, 298 K, nm, max): 295. 1H
NMR (CDCl3, 222 K, ): 9.24 (s, 6H, NMA-H); 7.80-7.30 (m, 30H, tppo). 31P {1H} NMR (CDCl3, 222 K,
): 37.5 (d, 2JP-Y = 8.9 Hz).
max): 296. NIR (CH2Cl2, 298 K, nm): 966-1022 (2F5/22F7/2). 1H NMR (CDCl3, 298 K, ): 7.93 (t, 4H,
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C45H36N3O14P2Eu: calcd. C 51.2, H 3.43, N 3.98; found C 50.9, H 3.45, N 3.95. IR (KBr): CO = 1647
cm-1; aNO2 = 1509 cm-1; sNO2 = 1314 cm-1; PO = 1135 cm-1. 1H NMR (CDCl3, 298 K, ): 8.30-7.40 (m,
nm, 298 K, nm): 579 (5D07F0); 587, 594 (5D07F1); 610, 616 (5D07F2); 650, 656 (5D07F3); 691,
700-705 (5D07F4). PLE (solid sample, em = 612 nm, 298 K, nm): 320 (ligand excitation); 370-423,
max 394 (Eu3+ excitation). Emission decay time (solid sample, 298 K): = 0.364 ms (exc = 310 nm,
em = 614 nm). Qi = 35%.
C45H36N3O14P2Tb: calcd. C 50.8, H 3.41, N 3.95; found C 50.5, H 3.45, N 3.90. IR (KBr): CO = 1650
cm-1; aNO2 = 1509 cm-1; sNO2 = 1316 cm-1; PO = 1131 cm-1. 1H NMR (CDCl3, 223 K, ): 7.85 (s, br,
30H, tppo); -3.94 (s, br, 6H, NMA-H). 31P {1H} NMR (CDCl3, 223 K, ): 32.3.
C45H36N3O14P2Yb: calcd. C 50.2, H 3.37, N 3.90; found C 49.9, H 3.40, N 3.85. IR (KBr): CO = 1651
cm-1; aNO2 = 1507 cm-1; sNO2 = 1314 cm-1; PO = 1129 cm-1. UV-VIS (CH2Cl2, 298 K, nm, max): 294.
NIR (CH2Cl2, 298 K, nm): 935-1022 (2F5/22F7/2). 1H NMR (CDCl3, 298 K, ): 10.90 (s, slightly br, 12H,
tppo); 8.38 (s, slightly br, 12H, tppo); 8.02 (m, slighlty br, 6H, tppo); 3.06 (s, slightly br, 6H, NMA-H).
31
P {1H} NMR (CDCl3, 251 K, ): 12.3. PL (solid sample, exc = 410 nm, 298 K, nm): 973-1023, max
978 (2F5/22F7/2). Emission decay time (solid sample, 298 K): = 7.17 s (exc = 410 nm, em = 1000
nm).
C19H17N5O14Y: calcd. C 36.5, H 2.72, N 11.2; found C 36.5, H 2.70, N 11.2. IR (KBr): CO = 1649 cm-1;
aNO2 = 1510 cm-1; sNO2 = 1325 cm-1. UV-VIS (CH2Cl2, 298 K, nm, max): 290. UV-VIS (H2O, 298 K,
nm, max): 263, 326. 1H NMR ((CD3)2SO, 298 K, ): 9.68 (s, 6H, NMA-H); 8.46 (d, 2H, 3JHH = 5.2 Hz,
bipyO2-H6-H6); 7.91-7.58 (m, 6H, bipyO2-H3-H3-H4-H4-H5-H5).

C19H17N5O14Eu: calcd. C 41.9, H 2.47, N 10.2; found C 41.8, H 2.45, N 10.2. IR (KBr): CO = 1650 cm-1;
aNO2 = 1502 cm-1; sNO2 = 1313 cm-1. UV-VIS (CH2Cl2, 298 K, nm, max): 290. UV-VIS (H2O, 298 K, nm,
30H, tppo); -14.14 (s, 6H, NMA-H). 31P {1H} NMR (CDCl3, 222 K, ): 32.1. PL (solid sample, exc = 310
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max): 263, 328. 1H NMR ((CD3)2SO, 298 K, ): 8.32 (d, slightly br, 2H, 3JHH = 5.7 Hz, bipyO2-H6-H6);
8.00 (s, br, 6H, NMA-H); 7.70 (t, 2H, 3JHH = 7.7 Hz, bipyO2-H4-H4); 7.49 (dd, 2H,3JHH = 5.7 Hz, 3JHH =
7.7 Hz, bipyO2-H5-H5); 7.39 (d, 2H, 3JHH = 7.7 Hz, bipyO2-H3-H3). PL (solid sample, exc = 320 nm,
sample, em = 613 nm, 298 K, nm): 340, max 298 (ligand excitation); 394, 417, 464 (Eu3+
excitation). Emission decay time (solid sample, 298 K): = 0.322 ms (exc = 320 nm, em = 613 nm).
Qi = 18%.
C19H17N5O14Tb: calcd. C 32.8, H 2.45, N 10.1; found C 32.7, H.2.50, N 10.0. IR (KBr): CO = 1643 cm-1;
aNO2 = 1506 cm-1; sNO2 = 1313 cm-1. UV-VIS (CH2Cl2, 298 K, nm, max): 300. UV-VIS (H2O, 298 K, nm,
max): 263, 327. 1H NMR ((CD3)2SO, 315 K, ): 14.73 (s, very br, 2H, bipyO2-H6-H6); 9.34 (s, slightly
br, 2H, bipyO2); 9.12 (s, slightly br, 6H, NMA-H); 8.66 (s, slightly br, 2H, bipyO2); 7.53 (s, slightly br,
2H, bipyO2). PL (solid sample, exc = 286 nm, 298 K, nm): 488, 494 (5D47F6); 545 (5D47F5); 582,
589 (5D47F4); 618, 621 (5D47F3). PLE (solid sample, em = 544 nm, 298 K, nm): 335 (ligand
excitation). Emission decay time (solid sample, 298 K): = 14 s (exc = 320 nm, em = 544 nm).
aNO2 = 1514 cm-1; sNO2 = 1328 cm-1. UV-VIS (CH2Cl2, 298 K, nm, max): 268, 294. 1H NMR (CDCl3,
321 K, ): 9.55 (s, 6H, NMA-H); 9.42 (d, slightly br, 2H, 3JHH = 4.6 Hz, phen-H2-H9); 8.52 (d, slightly
br, 2H, 3JHH = 8.3 Hz, phen-H4-H7); 7.98 (s, 2H, phen-H5-H6); 7.89 (m, br, 2H, phen-H3-H8).
317 K, ): 10.35 (s, br, 2H, phen); 8.75 (s, br, 2H, phen); 7.88 (s, br, 2H, phen); 7.64 (s, br, 2H, phen);
-17.51 (s, slightly br, 6H, NMA-H). PL (solid sample, exc =320 nm, 298 K, nm): 578, 580 (5D07F0);
588, 597 (5D07F1); 609, 622 (5D07F2); 648, 657 (5D07F3); 683, 707 (5D07F4). PLE (solid sample,
em = 612 nm, 298 K, nm): 340 (ligand excitation); 332, 346, 389 (Eu3+ excitation). Emission decay
time (solid sample, 298 K): = 0.190 ms (exc = 320 nm, em = 614 nm). Qi = 15 %
298 K, nm): 584, 591 (5D07F1); 614 (5D07F2); 652 (5D07F3); 688, 695-700 (5D07F4). PLE (solid
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C21H14N5O12Tb: calcd. C 36.7, H 2.05, N 10.2; found C 36.5, H 2.10, N 10.1. IR (KBr): CO = 1644 cm-1;
298 K, ): 13.53 (s, br, 6H, NMA-H); 8.05 (s, br, 2H, phen); -2.05 (s, br, 2H, phen); -6.44 (s, br, 2H,
C21H14N5O12Yb: calcd. C 36.0, H 2.01, N 10.0; found C 35.8, H 2.05, N 9.95. IR (KBr): CO = 1638 cm-1;
aNO2 = 1512 cm-1; sNO2 = 1314 cm-1. UV-VIS (CH2Cl2, 298 K, nm, max): 271, 296. NIR (CH2Cl2, 298 K,
nm): 934-977 (2F5/22F7/2). 1H NMR (CDCl3, 298 K, ): 14.82 (s, slighlty br, 2H, phen); 14.54 (s,
slighlty br, 2H, phen); 12.35 (s, slighlty br, 2H, phen); 11.67 (s, slighlty br, 2H, phen); -0.78 (s,
slightly br, 6H, NMA-H). PL (solid sample, exc = 393 nm, 298 K, nm): 973-1035, max 1005
(2F5/22F7/2). Emission decay time (solid sample, 298 K): = 7.17 s (exc = 410 nm, em = 1000 nm).
Qi = 0.4 %.
aNO2 = 1507 cm-1; sNO2 = 1320 cm-1. UV-VIS (CH2Cl2, 298 K, nm, max): 287, 305. 1H NMR ((CD3)2SO,
317 K, ): 9.64 (s, 6H, NMA-H); 8.76 (d, 2H, 3JHH = 5.1 Hz, terpy-H6-H6); 8.70 (d, 2H, 3JHH = 8.1 Hz,
terpy-H3-H3); 8.49 (d, 2H, 3JHH = 7.9 Hz, terpy-H3-H5); 8.20-8.04 (m, 3H, terpy-H4-H4-H4); 7.57
(dd, 2H, 3JHH = 5.1 Hz, 3JHH = 7.7 Hz, terpy-H5-H5).
13
C {1H} NMR (DEPT-135, (CD3)2SO, 317 K, ):
181.0 (NMA-CH), 149.4, 138.8, 138.0, 137.9, 124.8, 121.3 (terpy-CH).
aNO2 = 1506 cm-1; sNO2 = 1314 cm-1. UV-VIS (CH2Cl2, 298 K, nm, max): 287, 305. 1H NMR (CD3)2SO,
298 K, ): 8.76 (d, 2H, 3JHH = 5.1 Hz, terpy-H6-H6); 8.70 (d, 2H, 3JHH = 8.1 Hz, terpy-H3-H3); 8.49 (d,
2H, 3JHH = 7.9 Hz, terpy-H3-H5); 8.13 (t, 1H, 3JHH = 7.9 Hz, terpy-H4); 8.10 (t, 2H, 3JHH = 7.7 Hz, terpy-
H4-H4); 7.57 (dd, 2H, 3JHH = 5.1 Hz, 3JHH = 7.7 Hz, terpy-H5-H5); 3.12 (s, br, 6H, NMA-H). NMA-H
signal falls at 2.26 ppm at 317 K. PL (solid sample, exc = 310 nm, 298 K, nm): 579, 581 (5D07F0);
589, 597 (5D07F1); 612, 626 (5D07F2); 646, 662 (5D07F3); 679, 704 (5D07F4). PLE (solid sample,
em = 612 nm, 298 K, nm): 375 (ligand excitation). Emission decay time (solid sample, 298 K): =
0.487 ms (exc = 320 nm, em = 614 nm). Qi = 67%.
phen); -27.36 (s, br, 2H, phen).
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Crystal structure determination of 1Y
diffractometer with graphite monochromated Mo-K radiation. The data sets were integrated
with the Denzo-SMN package
(SORTAV)
[20]
and corrected for Lorentz, polarization and absorption effects
[21]
. The structures were solved by direct methods using SIR97
[22]
system of programs
and refined using full-matrix least-squares with all non-hydrogen atoms anisotropically and
hydrogens included on calculated positions, riding on their carrier atoms. All calculations were
performed using SHELXL-97 [23] and PARST [24] implemented in WINGX [25] system of programs. The
crystal data are given in Table 5.
Table 5. Crystallographic data for 1Y.

Formula
M
[C12H8N4O16Y]-[AsC24H20]+
936.45
Space group
Crystal system
P-1
Triclinic
F(000)
944
-1
(Mo-K)/cm
24.88
Measured Reflections
22838
Unique Reflections
10914
0.0346
a/
10.7426(2)
Rint
b/
13.4270(2)
Obs. Refl.ns [I
2(I)]
c/
14.1483(3)
min- max/
71.1379(6)
hkl ranges
78.6566(6)
R(F ) (Obs.Refl.ns)
85.7839(6)
wR(F ) (All Refl.ns)
1893.34(6)
No. Variables
U/
Z
T/K
Dc/g cm-3
2
295
1.643
Goodness of fit
max; min /e -3
CCDC Deposition N.
8199
4.31 30.00
-14,15;-18,18;-16,19
0.0410
0.1037
523
1.031
0.71; -0.62
982341
Crystallographic data (excluding structure factors) have been deposited at the Cambridge
Crystallographic Data Centre and allocated (deposition number CCDC 982341). These data can be
The crystal data of compounds 1Y were collected at room temperature using a Nonius Kappa CCD
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obtained free of charge via www.ccdc.cam.ac.uk/conts/retrieving.html or on application to CCDC,
Preparation of doped PMMA

2Eu@PMMA, 3Eu@PMMA, 3Tb@PMMA, 4Eu@PMMA and 5Eu@PMMA were prepared by adding a
known amount of a freshly prepared 10-4 M solution of the proper complex in CH2Cl2 to a solution
of 1.00 g of PMMA in 50 mL of dichloromethane, to obtain complex : PMMA ratios ranging from
10 to 50 mol gPMMA-1. The solutions were then concentrated to ca. 5 mL by gentle heating and
transferred in a plastic polyethylene holder having 20 mm diameter. The residual solvent was
allowed to evaporate overnight at room temperature and then the samples were kept under 10-3
torr pressure for 6 hours. Plastic glasses having about 2-3 mm thickness were obtained. Attempts
to further increase the concentration of complex led to materials having reduced transparency.
Characterization of 2Eu@PMMA
PL (solid sample, exc = 310 nm, 298 K, nm): 579 (5D07F0); 586, 597 (5D07F1); 610, 622 (5D07F2);
649, 660 (5D07F3); 688, 705 (5D07F4). PLE (solid sample, em = 612 nm, 298 K, nm): 320, max
280 (ligand excitation). Emission decay time (solid sample, 298 K): = 0.215 ms (exc = 310 nm, em
= 614 nm). Qi = 17%.
PL (solid sample, exc = 310 nm, 298 K, nm): 590, 594 (5D07F1); 613 (5D07F2); 653 (5D07F3); 690,
701 (5D07F4). PLE (solid sample, em = 613 nm, 298 K, nm): 340, max 281 (ligand excitation);
394, 415, 464 (Eu3+ excitation). Emission decay time (solid sample, 298 K): = 0.267 ms (exc = 320
nm, em = 613 nm). Qi = 13%.
Characterization of 3Tb@PMMA
PL (solid sample, exc = 286 nm, 298 K, nm): 488, 491 (5D47F6); 544 (5D47F5); 582, 587 (5D47F4);
618, 622 (5D47F3). PLE (solid sample, em = 544 nm, 298 K, nm): 335, max 285 (ligand
excitation). Emission decay time (solid sample, 298 K): = 10 s (exc = 320 nm, em = 544 nm).
Union Road, Cambridge, CB2 1EZ, UK [fax: (+44)1223-336033, e-mail: deposit@ccdc.cam.ac.uk].
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PL (solid sample, exc =320 nm, 298 K, nm): 580 (5D07F0); 587, 597 (5D07F1); 610, 620 (5D07F2);
648, 656 (5D07F3); 690, 706 (5D07F4). PLE (solid sample, em = 615 nm, 298 K, nm): 340 nm
= 0.457 ms (exc = 320 nm, em = 614 nm). Qi = 26 %.
PL (solid sample, exc =337 nm, 298 K, nm): 579 (5D07F0); 588, 597 (5D07F1); 610, 624 (5D07F2);
651 (5D07F3); 684-702 (5D07F4). PLE (solid sample, em = 616 nm, 298 K, nm): 375, max 337
(ligand excitation). Emission decay time (solid sample, 298 K): = 0.671 ms (exc = 325 nm, em =
616 nm). Qi = 51 %.
Preparation of Eu-NMA@PVP
A solution containing 0.15 mmol (0.024 g) of Na[NMA]H2O in 10 mL of water was slowly added to
a stirred solution of EuCl3 (0.05 mmol, 0.013 g) in water (15 mL). Polyvinylpirrolidone (PVP, 0.5 g,
average Mw = 10000 g mol-1) dissolved in 10 mL of water was added after 4 hours. After stirring
the resulting reaction mixture overnight at room temperature, the solvent was removed under
reduced pressure and the crude product was dried under vacuum in the presence of P2O5. The
solid was then dissolved in the minimum volume of ethanol and the resulting solution was filtered.
The doped polymer was collected after evaporation of the solvent at reduced pressure. Thin films
were obtained using the doctor blade tape technique from ethanol solutions, using glass plates as
substrates.
Characterization of Eu-NMA@PVP
PL (solid sample, exc = 330 nm, 298 K, nm): 584, 591 (5D07F1); 614 (5D07F2); 652 (5D07F3); 688,
695-700 (5D07F4). PLE (solid sample, em = 613 nm, 298 K, nm): 340 nm (ligand excitation); 394,
417, 464 (Eu3+ excitation). Emission decay time (solid sample, 298 K): = 0.678 s (exc = 320 nm,
em = 613 nm). Qi = 31 %.
(ligand excitation); 358-389, max 394 (Eu3+ excitation). Emission decay time (solid sample, 298 K):
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Theoretical calculations
The computational geometry optimization of the yttrium complexes was carried out using the
[26]
without symmetry constrains in combination with the polarized
double- quality basis set LACVP**, having a small-core ECP on the metal centre
[27]
. The
restricted formalism was applied in all the calculations and the stationary points were
characterized by IR simulation
[28]
. All the calculations were performed on a Intel-based x86-64
workstation and the software used was Spartan 08 [29].
Supplementary data
Photoluminescence excitation spectra (PLE) of the europium derivatives 1Eu 5Eu and of the
corresponding doped PMMA samples are available in a separated Supplementary Data file.
References
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Yttrium and lanthanide complexes of -dialdehydes: synthesis, characterization and

Published on 09 May 2014. Downloaded by Universidad de Sonora on 12/05/2014 22:50:20.

Dipartimento di Scienze Molecolari e Nanosistemi, Universit Ca Foscari Venezia, Dorsoduro

2137, 30123 Venezia, Italy.

Dipartimento di Scienze Chimiche e Farmaceutiche e Centro di

Keywords: yttrium, lanthanides, -dialdehydes, nitromalonaldehyde, luminescence

Coordination compounds having formulae [AsPh4][Ln(NMA)4] (1Ln), Ln(NMA)3(tppo)2 (2Ln),