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Serpe, L. Marchi, M. Saba, A. Mura, M. L. Mercuri, G. Bongiovanni, P. Deplano and F. Quochi, J. Mater.
Chem. C, 2015, DOI: 10.1039/C5TC02985F.

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ARTICLE
Controlling Nd-to-Yb Energy Transfer through a Molecular
Approach
Received 00th January 20xx,
Accepted 00th January 20xx

,a,b

Flavia Artizzu,* Angela Serpe, Luciano Marchi, Michele Saba, Andrea Mura, Maria Laura
b
a
,a,b
,a
Mercuri, Giovanni Bongiovanni, Paola Deplano,* and Francesco Quochi.*

DOI: 10.1039/x0xx00000x
www.rsc.org/

Nd-to-Yb energy transfer (ET) at molecular level has been investigated in the novel heterobimetallic NdYb2Q9 (Q = 8quinolinolate) complex where the Q ligand works as high cross-section optical antenna. The remarkable ion size-driven
templating effect of Nd3+ allows for a good control of molecular speciation through a simple one-pot synthetic procedure.
Short intermetallic distances and enhanced donor (Nd)/acceptor (Yb) spectral overlap in the molecular assembly strongly
favor Nd-to-Yb energy transfer, which reaches nearly unitary efficiency, while detrimental processes such as concentration
quenching and energy back transfer are ruled out. The devised approach allows to obtain a controlled assembly of
heterolanthanide compounds whose features hold potential for the development of highly performing Yb3+-based optical
materials.
3+

Introduction
3+

Near-infrared (NIR) emitting lanthanide (Ln) ions such as Nd ,

3+
3+
Er and Yb , are of unique importance in several fields
1-3
including optical technologies and biomedical applications.
In particular, these ions play a special role in fiber-optic
communications for signal amplification, and for the
fabrication of laser systems working in the NIR.3 Yb3+-based
emitters are of relevant interest in view of the simple twolevel manifolds energy diagram of this ion, giving rise to
emission at 1 m from the 2F5/2 2F7/2 transition with no
energy loss due to non-radiative cascade decay from the
photoexcited levels to the emitting one (quantum defect).
Additional benefits of Yb-based optical materials are the
absence
of
excited-state
absorption,
up-conversion
phenomena, concentration quenching, and luminescence
lifetime one order of magnitude longer than those of the other
typical NIR-emitting lanthanides, such as Nd3+, allowing for
larger energy storage efficiency.4 These features make Ybbased materials very convenient sources for NIR optical
amplifiers and lasers.5 Nevertheless, direct photoexcitation of
Yb3+ ions suffers from low absorption cross section and an
adequate optical sensitizer is highly beneficial. In particular the
performances of these materials can be considerably improved

a. a

Dipartimento di Fisica, Universit di Cagliari, Complesso Universitario di

Monserrato, I-09042 Monserrato-Cagliari, Italy.
Dipartimento di Scienze Chimiche e Geologiche, Universit di Cagliari, Complesso
Universitario di Monserrato, I-09042 Monserrato-Cagliari, Italy.
c.
Dipartimento di Chimica, Universit di Parma, Parco Area delle Scienze 17A, I43100 Parma, Italy..
Electronic Supplementary Information (ESI) available: FT-IR, powder XRD
patterns, supplementary ESI-mass and spectroscopic data, time-resolved PL fit
equations
and
parameters,
Frsters
model
analyses.
See
DOI: 10.1039/x0xx00000x
b.

3+

by resorting to Nd as the optical sensitizer of Yb through

metal-to-metal energy transfer (ET). This allows for convenient
3+
3+
indirect optical excitation of Yb at 800 nm, where the Nd
4
4
F3/2 I9/2 absorption band lies and high-power laser diodes
6
4-5,7-8
are available, while still ensuring a low quantum defect.
The limited number of studies available in literature so far on
Nd-to-Yb ET are restricted to codoped laser crystals, ceramics
4,7-9
and glasses.
and estimated efficiencies of these materials
3+
4,8
are crucially dependent on the Ln doping concentration. In
3+
these systems both ET and competitive processes such as Nd
upconversion are in general mediated by energy migration
3+
between Nd ions, which can hinder observation of direct ET
processes and make the determination of their rate constants
4,7-9
difficult in transient optical emission experiments.
Indeed,
neat observation of direct Nd-to-Yb ET requires independent
control of the spatial separation of the two ions and of their
effective concentration in the host, which is intrinsically
difficult to achieve for co-doped or co-implanted inorganic
materials obtained through commonly used techniques such
as melting.
A suitable approach to address this point resorts to
polynuclear molecular frameworks embedding selected
lanthanide ions at short and controlled intermetallic distances
10(<<10 ) that can definitely favor efficient metal-to-metal ET.
11
These heterometallic molecules also enable the
incorporation of organic ligands as high cross-section optical
antennas, hence providing lanthanide emitters with additional
3+
excitation channels. Moreover, Ln encapsulation with organic
ligands improves their solubility into host matrices, affording
processing versatility and easy tunability of effective metal
concentration. Such molecular strategy seems therefore
particularly useful for achieving direct and efficient

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intermetallic communication in solution-processable molecular

materials.
Trinuclear lanthanide complexes of 8-hydroxy-quinoline (Q), of
general formula Ln3Q9, are ideal candidates to prepare
heterobimetallic assemblies where efficient intermetallic
communication can be realized thanks to short metal site
12
separation within the molecular framework (~ 3.6 ). The
attractiveness of these class of complexes is further enhanced
3+
by the relevant ion size-driven templating effect of the Nd
ion in the synthesis of Ln3Q9 heterometallic complexes with
3+
3+
smaller ions, such as Yb and Er , that enables the control of
the number and the relative position of the different
lanthanide ions in the molecule.12 In this work, the
heterobimetallic NdYb2Q9 (1) complex has been synthesized
and characterized to investigate the Nd-to-Yb ET at molecular
level, through the comparison with the analogous
homometallic complexes, Nd3Q9 (2) and Yb3Q9 (3) as suitable
references.13-14

Results and discussion

Synthesis and characterization
1 was obtained through a simple one-pot synthetic procedure
by mixing the ligand and the chloride salts of the metals in
appropriate ratios and fully characterized by powder X-ray
diffraction, spectroscopic and analytical data, confirming the
11
isostructurality with the known NdErYbQ9 and 3 (see SI). As
recently observed, the central coordination site in the bridged
trinuclear structural arrangement is preferential for the larger
3+
3+
Nd whereas smaller ions, such as Yb , tend to occupy the
12
inequivalent terminal sites (Figure 1). As a consequence of
3+
the templating effect of Nd , the degrees of freedom of the
occupancy, otherwise statistical, of the different lanthanide
ions over the three available coordination sites are drastically
reduced, and, as a result, molecular speciation (i. e. the
number of molecular species of different metal composition
coexisting in the sample) is significantly lowered. Accordingly,
only three molecular species can be predicted to be
constituting the sample: Yb2NdQ9, Yb3Q9 and Nd3Q9. This
observation is corroborated by the analysis of the electrospray
ionization (ESI)-mass spectrum of 1 in positive ion mode,
reported in Figure 1.

Fig. 1. Molecular structure (Nd, green, Yb, purple) and ESI-mass spectrum of 1 in the
1560-1690 m/z range (red line) and calculated models (black dots) for labeled
molecular fragments.

In the ESI-mass spectrum of 1, two main peaks related to

different molecular species are recognized (red line): the peak
+
centered at m/z 1672 corresponds to the [Yb3Q8] species,
whereas the one at m/z 1565-1585 reflects the isotopic
distribution of molecular fragments containing one Nd and
+
two Yb ions, and is attributed to the [NdYb2Q7DMF] (DMF =
dimethylformamide) species. The accordance of the model
mass spectra (black dots, Figure 1) calculated for the isotopic
distribution of these two molecular fragments with
experimental data confirms these attributions. In agreement
11
with previous findings, no peaks relatable to molecular
species containing more than one Nd ion are observed, (see
also Figure S3 in SI), confirming the templating effect of
neodymium for the assembly of heterolanthanide
3+
quinolinolato complexes with smaller ions such as Yb .
However, a quantitative assessment of the molar fractions of
the molecular species present in the sample cannot be done
solely on the basis of ESI-mass data as it appears that the Ndcontaining molecular species do not undergo the same
fragmentation as homometallic Yb3Q9 molecules under the
experimental conditions used for electrospray ionization. On
this basis, although no evidence of a parent ion relatable to
Nd3Q9 is observed, its presence cannot be definitely ruled out.
Metal composition in 1 was then accurately determined by
inductively coupled plasma (ICP)-mass spectrometry and
Nd0.93Yb2.07Q9 formulation was retrieved, pointing out a small
3+
excess of Yb amount in the sample, as expected given the
slightly stronger affinity of the Q ligand towards smaller Ln
15
ions.
Analytical data were complemented by time-resolved PL
spectroscopy to assess the molar fractions of molecular
species, as described in the related section.
Spectroscopic and photophysical studies
The Nd-to-Yb ET dynamics was investigated by transient
photoluminescence (PL) spectroscopy. Comparative studies of
the photophysical properties of 1 and the reference

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compounds 2-3 were done by exciting the complexes with

subnanosecond pulses centered at a fixed wavelength (355
nm) in the Q ligand absorption band, and normalizing all NIR
(metal-centered) signal intensities for absorbed pump power.
Upon single-wavelength pulsed excitation, compounds 1-3
show metal-centered emission in the NIR (Figure 2). The
ultrafast decay of Q ligand fluorescence in the visible (Figure
S4, SI) suggests that intersystem crossing and, consequently,
metal sensitization, are extremely efficient processes in all the
15-16
investigated compounds.
3+ 2
2
1 simultaneously displays Yb
F5/2 F7/2 emission at 1 m
3+ 4
4
and a less intense band related to Nd F3/2 I13/2 at 1.35 m
3+
(Figure 2). While the intensity of Yb emission is comparable
to that observed for the corresponding homometallic 3
complex, the spectroscopic features related to Nd3+ are
considerably weakened with respect to 2, and no evidence of
Nd3+ intense peaks 4F3/24I9/2 and 4F3/24I11/2 at 0.9 and 1.1
m respectively, are detectable. These observations suggest
that Nd emission is efficiently quenched by ET to Yb. However,
this process could be more clearly evaluated through the
analysis of the donor (Nd)-acceptor (Yb) temporal dynamics in
the NIR. Results of time-resolved spectroscopy in the NIR for 13 in diluted (510-4 M) DMSO solution, are summarized in
Figure 3, fit equations and related parameters (time constants,
amplitudes) are reported in the SI.

3+

3+

Fig. 3. NIR temporal dynamics of Nd (red) and Yb (blue) for 1-3 at 977 and 1340 nm,
respectively. Dots correspond to experimental data and solid lines represent
(multi)exponential fit curves. Blue dashed lines represent predictions for Yb3Q9
contribution to the observed signal in 1 according to models a and b (Table 1). In the
inset the Nd3+ signal is reported on a shorter timescale and the possible contribution of
homometallic Nd3Q9 is evidenced (dashed line). Signals are normalized for absorbed
power at excitation wavelength (355 nm).

The same monoexponential Yb3+ decay dynamics is observed

at 977 nm for 1 and 3, with very similar time constants (Yb~10
s, Table S1), indicating that ytterbium decay is unaffected by
changes of metal composition in the molecular framework. In
1, this signal is the result of the weighted contribution of
heterometallic NdYb2Q9 and homometallic Yb3Q9 molecular
species coexisting in the sample, as evidenced by dashed blue
lines in Figure 3, which represent the signal attributable to
homometallic molecules according to models a and b of the
molecular speciation (Table 1) estimated through simple
calculations (see SI) by taking into account the exact metal
composition obtained from ICP-mass data. Model a was
calculated under the following constraints: i) a negligible
presence of homometallic Nd3Q9, ii) one Nd3+ ion per molecule
to form NdYb2Q9 species, iii) the excess Yb3+ ions giving rise to
homometallic Yb3Q9 molecules in the sample. Model b was
instead estimated by taking into account a sizeable quantity of
Nd3Q9 (~13%) as evidenced by transient photoluminescence
(PL) spectroscopy experiments, as discussed below.
Fig. 2. PL spectra in the 800-1500 nm region for 1 (purple), 2 (red) and 3 (blue), under
excitation in the lowest ligand absorption band at 355 nm (inset). Spectra are
normalized for absorbed power at excitation wavelength (upward pointing arrow).

Table 1. Molar fractions (%) of molecular species with different Nd/Yb atomic ratios for
1-3.

NdxYb(3-x)Q9
compound
1

x=3

x=1

x=0

model a

92.7(2)

7.3(2)

model b

13(1)

55(1)

32(1)

100

100

For 1 molecular speciation is predicted according to models a and b (see text)

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time constants of the donor in the absence (Nd) and in the
presence (Nd*) of the acceptor according to:

1 
  1

(1)

and
  1    

(2)

The calculated parameters (Table 2) suggest that Nd-to-Yb ET

is ultrafast and nearly quantitative for heterometallic Nd/Yb
3+
molecular species where Nd is directly excited through ET
from the ligand. Although we can reasonably infer that Nd-toYb intermetallic cross-conversion is fully effective in these
heterometallic assemblies, a more quantitative analysis could
be done on the basis of the normalized Yb3+ signal amplitudes.
To this aim, the amplitude ( ) of the signal solely related to
sensitization by Nd3+ was compared to that (, ) one would
expect to measure in an equal amount of homometallic Yb3Q9
(dashed lines in Figure 4). Such reference signal, which
represents the maximum signal level achievable upon
completion of the Yb3+ activation transient for a 100% efficient
Nd-to-Yb ET process, was calculated by simply rescaling the
Yb3+ signal measured in 3 for the NdYb2Q9 abundance in 1. The
ratio between the ligand-to-Yb sensitization efficiency in the
Nd-mediated process ( ) and that of Yb3+-ion
sensitization in a non-mediated process ( ) could be
evaluated as follows:
 

Fig. 4. NIR temporal dynamics of Nd3+ and Yb3+ in NdYb2Q9 complexes on a short time
scale. Decay traces at 1340 nm (Nd3+) and at 977 nm (Yb3+) were obtained by
subtracting the long-lived components attributed to homometallic species, according
to models a (blue) and b (black, Yb3+, and red, Nd3+). Intensities are normalized for
absorbed pump power at 355 nm. Solid lines are best fits of model function to the NIR
PL transients (see SI for details). Dotted lines represent the signal amplitude related to
3+
Yb ions directly sensitized by the photoexcited Q ligand. Dashed lines display the
3+
predicted Yb signal for an equimolar amount of Yb3Q9.
3+

Yb signal rising at 977 nm appears as a combined process for

which part of the excited level population is promptly reached
within instrumental temporal resolution limits (dotted lines)
whereas the remaining fraction shows a slower activation
3+
dynamics which is complementary to the Nd signal decay
(Table S1) at 1340 nm, providing evidence for Nd-to-Yb ET. The
time constant (Nd-Yb) and the efficiency (Nd-Yb) of this process
can be therefore estimated by taking into consideration the








,!"  

(3)

where  is the ligand-to-Nd sensitization efficiency, and

 is the signal amplitude of the Yb3+ ions directly sensitized
by Q ligands (dotted lines in Figure 4). The relative efficiency 
ranges from ~45 to ~85% depending on the model assumed for
molecular speciation in 1 (Table 2). It results evident that the
evaluation of the whole photocycle leading to Yb3+ emission
after metal-to-metal ET is crucially dependent on the
assessment of molecular speciation. Time-resolved PL
spectroscopy is particularly sensitive to the nature of
molecular species giving rise to emission, and reliable
predictions made on the basis of model b are consistent with
findings based on eqs. (1) and (2), confirming our
understanding of Nd-to-Yb cross-conversion as a highly
efficient process in the heterobimetallic NdYb2Q9 complex.
Table 2. Nd-to-Yb sensitization parameters.

model

Nd-Yb (ns)

Nd-Yb (%)

(%)

46(1)

95(4)*

44(4)*

46(1)

95(4)

85(15)

*Error is evaluated on the basis of ICP-mass compositional data; Error is

estimated on the basis of ICP-mass data and NIR emission intensities.

Nd-to-Yb Energy Transfer

The effectiveness of metal-to-metal ET in heterometallic
assemblies, where intermetallic distance is fixed, depends on
the overlap integral (J) between the emission band of the
donor and the absorption band of the acceptor, and on the
donor lifetime (D).17 The rate constant of the donor-acceptor

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3+

As the Nd emissive transitions of interest share the same

4
starting level ( F3/2), decay transients were conveniently
studied for the most spectrally resolved band at 1340 nm to
3+
avoid Yb signal superposition. A monoexponential decay is
3+
detected for Nd in 2, whereas for 1 two signal components
are clearly distinguishable, with time constants differing by
almost two orders of magnitude (see Table S1 in SI). The
longer decay component shows a similar dynamics to 2 and

may result from a fraction of Nd3Q9 species, detected only by

time-resolved spectroscopy, whose molar fraction can be
estimated by the analysis of signal amplitudes (inset of Figure
3, Table S1 in SI). On the basis of this observation, molecular
speciation may be then described by model b in Table 1. The
ultrafast signal component of Nd3+ dynamics is instead reliably
ascribed to Nd-to-Yb ET, as substantiated by the inspection of
Figure 4, where the NIR dynamics of 1 is reported on a short
timescale for donor (Nd3+) and acceptor (Yb3+) signals at 1340
and 977 nm respectively. Appropriate signal subtractions were
made according to models a (blue) and b (black) for Yb3+ and
model b for Nd3+ (red) and resulting components are solely
related to heterometallic NdYb 2Q9 molecules.

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energy transfer (ET) scales as #$% ' (, where ( 

) *+ ,-. ,,/ 0,, FD() is the emission spectral density of the
donor and A() is the acceptor absorption cross-section (see
Figure 5). As Nd-to-Yb ET is an intrinsically non-resonant
process (see Figure S7 in the SI), the entity of this parameter is
4,8
crucial to allow for intermetallic communication. For this
reason, the design of efficient codoped Nd/Yb 1 m emissive
systems usually requires an accurate selection of the host
3+ 4
material, with suitable phonon energy matching the Nd F3/2
3+ 4
8
Yb F5/2 gap, to allow for phonon-assisted Nd-to-Yb ET. In
molecular complexes with organic ligands, crystal-field effects
partially remove the degeneracy of the energy level manifolds
of the lanthanide ions resulting in band broadening and
consequently in a large spectral overlap between the emission
band(s) of Nd3+ and the absorption band of Yb3+, as observed
for 1 (Figure 5a), for which J ~ 104 nm6. Conversely, the
negligible (J ~ 50 nm6) overlap of the Yb3+ emission band with
Nd3+ absorption spectrum (Figure 5b), and the ~10 times
longer bare donor lifetime of Yb3+ with respect to Nd3+,
hamper undesired energy back transfer phenomena.8

Figure 5. Spectral overlaps between donor-acceptor emission-absorption bands in the

850-1150 nm region. Spectral data for Nd3+ (red) and Yb3+ (blue) were measured in
reference homometallic compounds 2 and 3 and appropriately normalized to a single
metal ion. Thick lines represent absorption, thin lines emission.

In the light of the above considerations it is then reasonable to

neglect Yb-to-Nd energy back transfer as a competitive
mechanism when estimating the efficiency of the intermetallic
communication in 1. It is also worth mentioning that the
3+
templating effect leading to a single occupancy of Nd in the
trinuclear molecular arrangement results in a Nd-diluted
material where potential Nd-Nd up-conversion or cross18
relaxation processes are ruled out. These observations
3+
suggest that Yb emission sensitization is by far the most
probable relaxation channel in the photocycle in this kind of
heterolanthanide molecular material. A detailed analysis of
metal-to-metal energy transfers in the framework of the
Frsters theory of dipolar energy transfer is reported in SI.

However, it has to be pointed out that Forsters dipolar model

underestimates the time constant for Nd-to-Yb ET (Nd-Yb ~6
ns) with respect to that experimentally observed (46 ns, Table
2), suggesting that multipolar mechanisms such as dipolequadrupole interaction cannot be ruled out.

Conclusions
In conclusion, a novel heterolanthanide Nd/Yb trinuclear
quinolinolato complex (1) of general formula Ln3Q9 (Ln = Nd,
Yb) was synthesized and characterized, and its photophysical
properties fully investigated and compared to the analogous
Nd3Q9 (2) and Yb3Q9 (3) complexes as appropriate references.
In 1, relevant ion-size driven templating effects of the larger
3+
3+
Nd ion with respect to the smaller Yb govern the assembly
of the heterolanthanide trinuclear molecular edifice,
drastically reducing molecular speciation. Analytical data were
complemented by time-resolved PL spectroscopy as a
powerful and sensitive tool to assess the molar fractions of
molecular species, either heterometallic, (NdYb2Q9) or
homometallic (Yb3Q9, Nd3Q9), coexisting in the sample.
Short intermetallic distances and enhanced spectral overlap
3+
3+
between the Nd (donor) emission and the Yb (acceptor)
absorption bands, broadened by crystal field effects in the
molecular assembly, strongly favor the intrinsically nonresonant Nd-to-Yb ET process, which reaches nearly unitary
efficiency in 1. Competitive mechanisms such as Yb-to-Nd
energy back transfer and Nd-Nd up-conversion are unlikely as
3+
a consequence of spectral (null overlap integral for Yb
3+
emission and Nd absorption) and structural (only one Nd ion
per molecule) features of such molecular material, which can
15
also be easily processed through mild solution methods. In
the light of these results, molecular heterolanthanide Nd/Yb
assemblies with suitable organic ligands represent a promising
3+
strategy for the development of innovative Yb -based
materials for optical amplification at 1 m, which are currently
under investigation in our laboratories.

Experimental
General
All the reagents and solvents were purchased from Aldrich and
used without further purification.
Elemental analysis: data were collected using a Flash 2000
Fisher Scientific Thermo Electron Analyzer. ESI-mass: Mass
spectra were obtained with a Micromass ZMD spectrometer
operating in positive ionization mode. Few drops of DMF were
added to the solution of the complex in CH3CN to improve
solubility. Electronic UV-Vis-NIR spectroscopy: Solution
absorption and diffuse reflectance (DR) spectra on solid
samples deposited on Teflon films and were collected using a
Agilent Cary 5000 spectrophotometer. Absorption cross3+
sections were calculated by taking into account Ln
concentrations retrieved from ICP-mass analysis. Vibrational
spectroscopy: FTIR spectra on KBr pellets were collected using
a
Bruker
Equinox
55
spectrophotometer.
ICP-MS

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-4

determinations: 220mg of a DMSO solution (510 M, approx)

of the selected sample, were introduced in a TFM vessel
containing a mixture of HNO3 (65%, 4 mL), H2O2 (30%, 0.5 mL)
and H2O (bidistilled, 4 mL) thus treated in a Milestone Ethos 1
Microwave digestor, equipped with a HPR1000/10S high
pressure segmented rotor, ATC-400CE automatic temperature
control and Terminal 640 with easyCONTROL software. The
treatment was performed by applying a microwave program
consisting of two steps each lasting 10 minutes, at the
temperature of 200C and microwave power up to 1000W. The
samples were prepared for the analysis by diluting the
digested solutions with 5% HNO3 (suprapur grade) blank and
then the metals were determined using a quadrupole ICP-MS
Varian mod. RT equipped with a 90 reflecting ion mirror
(Varian, Mulgrave, Australia), a Micromist glass low flow
concentric nebulizer, a Peltier-cooled (3C) double pass glass
spray chamber and a glass torch, with respect to 4-points
-1
external aqueous calibration plots in the 0.1-25 ng L range for
each metal (Correlation Coefficients > 0.999990, Limit of
-1
Detection (LoD) for the different analytes: 0.5-5 ng L ). X-ray
powder
diffraction:
Wide-angle
XRD-patterns
on
microcrystalline powder samples were recorded with a
Panalytical Empyrean diffractometer equipped with a graphite
monochromator and a XCelerator linear detector. The scans
were collected within the range 5-40 (2) using Cu K
radiation.
Syntheses and analytical data
Synthesis of 1: Few drops of NH3 28% up to pH ~ 10 were
added to a suspension of 8-hydroxy-quinoline (0.622 g, 4.28
mmol) in H2O (150 mL) under mixing. After 30 min a water
solution containing 0.57 mmol (0.205 g) of NdCl36H2O and
0.86 mmol of YbCl36H2O (0.332 g) in 30 mL of water was
added to the above mixture which was allowed to react at
reflux for 2 days until the white solid due to the unreacted
ligand disappears. A yellow precipitate was formed, collected
by filtration, washed with water, NaOH 0.1 M, water, and dried
in oven at 60C (yield 86% ). Yellow microcrystals were
obtained after recrystallization from CH3CN. Analytical and
spectroscopic
data.
CHN
Found
(Calculated
for
C81H54Yb2NdN9O9): C% 55.01(54.42), H% 3.30(3.04), N%
7.45(7.05). ICP-mass (average on 15 repeated measurements,
-1
atomic ratios): Nd:Yb 1:2.24. FT-IR, cm : 3046 m, 1601 m,
1570 s, 1541 w, 1498 vs, 1465 vs, 1423 mw, 1383 s, 1319 s,
1276 m, 1231 m, 1174 w, 1107 vs, 1035 w, 905 w, 823 m, 804
m, 787 m, 731 s, 648 m, 605 m, 569 w, 503 m, 490 m. UV-Vis2
NIR absorption, nm, [cross section, cm ]), DMSO:
-17
-17
3+
340[4.900.0210 ],
380[5.600.0210 ],
527
(Nd
2
2
4
3+ 2
2
4
3+
G7/2+ G9/2 I9/2), 582 (Nd
G7/2+ G5/2 I9/2), 747 (Nd
4
4
4
-20
3+ 4
2
4
F7/2+ S3/2 I9/2) [2.190.1110 ], 801 (Nd F5/2+ H9/2 I9/2)
-20
3+ 4
4
-20
[3.230.1410 ], 875 (Nd
F3/2 I9/2) [0.950.0910 ], 977
3+ 2
2
-20
(Yb
F5/2 F7/2) [7.100.1510 ]. Diffuse reflectance, nm:
262, 344, 385, 583, 737, 804, 871, 979, 1147 (3CH), 1683
(2CH).
Synthesis of 2 and 3: Syntheses were carried out following the
same procedure described for 1. Briefly, 2 was prepared by
adding to a suspension of 0.685 g (4.71 mmol) of the ligand in

150 mL of H2O/NH3 (pH ~ 10), a water solution (30 mL)

containing a slight excess (1.63 mmol, 0.586 g) of NdCl36H2O.
The crude product was then redissolved in hot CH3CN, and an
amorphous yellow precipitate was formed. Analytical results
are in agreement with Nd3Q9 formulation. Yellow microcrystals
of 3 were obtained after recrystallizing in CH3CN the product
precipitated from a water mixture containing 3 mmol of HQ
and 1.05 mmol of YbCl36H2O. Analytical and spectroscopic
data. 2. CHN Found (Calculated for C81H54Nd3N9O93H2O): C%
-1
54.64(54.53), H% 3.80(3.39), N% 7.28(7.07). FT-IR, cm : 3045
m, 1599 m, 1566 s, 1497 vs, 1464 vs, 1423 mw, 1381 s, 1317 s,
1277 m, 1229 m, 1175 w, 1105 vs, 1031 w, 901 w, 823 m, 802
m, 789 m, 746 m, 729 s, 648 m, 602 m, 592 w; 561 w, 502 m,
2
486 m. UV-Vis-NIR absorption, nm, [cross section, cm ]),
-17
-17
3+
DMSO: 339[5.810.0210 ], 386[6.680.0210 ], 527 (Nd
2
2
4
-20
3+
G7/2+ G9/2 I9/2)
[3.840.0510 ],
582
(Nd
2
2
4
-19
3+ 4
4
G7/2+ G5/2 I9/2) [2.060.0610 ], 680 (Nd
F9/2 I9/2)
-21
3+ 4
4
4
-20
[7.20.0510 ], 744 (Nd
F7/2+ S3/2 I9/2) [9.480.0510 ],
3+ 4
2
4
-19
3+
801 (Nd
F5/2+ H9/2 I9/2) [1.180.0210 ], 875 (Nd
4
4
-20
F3/2 I9/2) [3.54 0.0710 ]. Diffuse reflectance, nm: 262,
344, 385, 583, 679, 737, 804, 871, 979, 1147 (3CH), 1683
(2CH).
3. CHN Found (Calculated for C81H54Yb3N9O9): C% 54.07
-1
(53.56); H% 3.20 (3.00); N% 7.56 (6.94). FT-IR, cm : 3047 m,
1601 m, 1571 s, 1498 vs, 1466 vs, 1424 mw, 1383 s, 1318 s,
1276 m, 1231 m, 1174 w, 1109 vs, 1035 w, 907 w, 823 m, 804
m, 788 m, 732 s, 648 m, 607 m, 592 w; 571 w, 504 m, 490 m,
458 w, 419 mw, 397 m, 384 m, 376 m, 353 m, 335 vw, 326 w,
315 vw, 303 w, 290 w, 280 m, 266 w, 253 m, 247 m, 226 m,
203 m, 177 m, 151 ms, 140 m, 132 m, 121 m, 101m 90 m 80
mw, 74 mw, 57 mw. UV-Vis-NIR absorption, nm, [cross section,
2
-17
-17
cm ]), DMSO: 339[5.140.0210 ], 378[7.680.0210 ], 977
3+ 2
2
-20
(Yb
F5/2 F7/2) [7.750.1010 ]. Diffuse reflectance, nm:
262, 344, 385, 979, 1147 (3CH), 1683 (2CH). ESI-Mass
+
(CH3CN/CH3OH 3/1), m/z: 1671.87 [Yb3Q8 ].

Acknowledgements
The Regione Autonoma della Sardegna (CRP-17571) and Banco
di Sardegna Foundation are gratefully acknowledged for
financial support. The authors thank Dr. D. Loche for powder
XRD measurements.

Notes and references

3+

The small difference in Nd decay dynamics in 1 (longer

component) with respect to 2 may be ascribed to a slightly
different structural arrangement, affecting excited-state nonradiative decay to some extent (see Table S1 in SI). The low
crystallinity of 2 in the solid state hampers further
investigations.
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189-227.
3 J.-C. G. Bnzli and S. V. Eliseeva, J. Rare Earths, 2010, 28,
824-842.

6 | J. Name., 2012, 00, 1-3

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Graphical abstract

Fully efficient Nd-to-Er energy transfer has been studied at molecular level in the heterobimetallic NdYb2Q9 light molecular
converter.

Journal of Materials Chemistry C Accepted Manuscript

DOI: 10.1039/C5TC02985F