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Composition Control in Molecular Cluster-Aggregates: A Toolbox for

Optical Output Tunability via Energy Transfer Pathways
Claudia M. S. Calado, Diogo A. Gálico, and Muralee Murugesu*
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ABSTRACT: Composition control is a powerful tool for obtaining

high-performance lanthanide (Ln) luminescent materials with
Downloaded via UNIV ESTADUAL PAULISTA on May 20, 2024 at 22:27:42 (UTC).

adjustable optical outputs. This strategy is well-established for

hierarchically structured nanoparticles, but it is rarely applied to
molecular compounds due to the limited number of metal centers
within a single unit. In this work, we present a series of molecular
cluster-aggregates (MCAs) with an icosanuclear core {Ln2Eu2Tb16}
(Ln = Ce, Pr, Nd, Sm, Gd, Dy, Ho, Er, Tm, and Yb) in which we
explore composition control, akin to nanoparticles, to modulate the
optical output. More specifically, we target to understand how the
presence of a third LnIII doping ion would impact the well-known
TbIII → EuIII energy transfer and the ratiometric optical
thermometry performance based on the TbIII/EuIII pair. Photo-
physical properties at room and at varying temperatures were investigated. Based on experimental data and well-established intrinsic
features, such as spin−orbit coupling strength and LnIII 4f energy levels’ structure, we discuss the possible luminescent processes
present in each MCA and provide insight into qualitative trends that can be rationally correlated throughout the series.
KEYWORDS: molecular cluster-aggregates, optical thermometry, lanthanides, composition control, energy transfer

■ INTRODUCTION
In recent decades, the increasing demand for tailored systems
communications, energy harvesting, anti-counterfeiting, and
luminescent probes, including temperature sensing.10−13
Composition control is a well-known strategy to achieve
in nanophotonics has raised the challenge of producing
high-performance luminescence in Ln-doped inorganic nano-
luminescent materials with well-controlled and tunable proper-
particles (NPs). By designing hierarchically structured core@
ties. In this context, optical systems based on lanthanides (Ln) shell architectures, spatial confinement of optical centers
are known to rely on the crystalline structure and chemical usually reduces quenching effects and enables control over
composition, and precise control of these features is crucial for interfacial energy migration. For example, different combina-
attaining high performances.1−5 tions of dopants and concentrations in distinct layers are a
The intrinsic properties of LnIII ions arise from intra- common approach to adjusting upconversion luminescence in
configurational 4f−4f electronic transitions, which lead to NPs.14 Moreover, through the balance of the composition,
characteristic optical profiles with narrow emission bands and layer position, and thickness, it is also possible to obtain
long emission lifetimes (μs to ms range).6,7 The discrete and multicolor emission with high color purity in single NPs.15
ladder-like energy levels of LnIII are ideal for building These strategies have been used to tackle specific applications,
luminescent systems with control over energy transfer (ET) including optical encoding, photodynamic therapy, and
and back energy transfer (BET) processes.8,9 By precisely security printing.3,15−17 However, it also means that optical
controlling the composition, one can select different LnIII to properties in NPs are crystalline phase-, layer thickness-, and
act as emitting states or as bridging pathways for ET or BET. size-dependent. Although many improvements have been
This strategy provides control over the electronic population, made in the last decade, achieving a narrow size distribution
determining whether it will decay radiatively (emission of
light) or nonradiatively (undergoing through energy transfer, Received: July 20, 2023
multiphonon deactivation, cross-relaxation, heat loss, etc.). Accepted: August 30, 2023
Therefore, a rational design can be used to prepare Ln-based Published: September 11, 2023
luminescent materials that emit electromagnetic radiation with
a fine-tuned behavior. These materials are the foundation of
many modern photonics applications, such as fiber-optic

© 2023 American Chemical Society https://doi.org/10.1021/acsami.3c10648

44137 ACS Appl. Mater. Interfaces 2023, 15, 44137−44146
ACS Applied Materials & Interfaces www.acsami.org Research Article

Figure 1. (A) Molecular core structure of {Ln2Eu2Tb16} MCA. Metal atoms are randomly assigned. Color code: green for TbIII, salmon for EuIII,
purple for doping LnIII, red for oxygen, and gray for carbon. (B) Schematic partial energy level diagram of {Ln2Eu2Tb16} showing possible
processes, namely, intersystem crossing (ISC), energy transfer (ET), back energy transfer (BET), and radiative (color gradient) and nonradiative
decays (wavy arrow).

Figure 2. (A) Partial energy level diagram of {Gd2Eu2Tb16} MCA illustrating possible ET pathways. (B) Excitation and (C) emission spectra (λexc
= 300 nm) of {Gd2Eu2Tb16} MCA at 20 °C. (D) Emission spectra of {Gd2Eu2Tb16} at varying temperatures (λexc = 300 nm). Integrated areas
used for temperature studies are highlighted. (E) Partial energy level diagram of LnIII ions. The energy difference between EuIII 5D0 and TbIII 5D4 is
highlighted and the increase of spin−orbit coupling (SOC) strength in the series in indicated by the arrow.

is still a synthetic challenge, and a minimal deviation means a icosanuclear MCAs, {Ln20} (Figures 1A and S1). We
difference of hundreds of atoms in nanostructures.18−20 successfully demonstrated the {Ln20} potential for lumines-
From this perspective, LnIII-based molecular cluster- cence thermometry, anti-counterfeiting security, and molecular
aggregates (MCAs) have emerged as a suitable platform for upconversion.34−37
luminescence at the nanoscale.21−24 In addition to a large Based on our previous works, we questioned ourselves if
number of emitting centers within a precise crystalline there would be any rational trends throughout the 4f row that
structure, MCAs offer excellent control over uniformity and could serve as guidelines when designing the {Ln20}
composition.25−33 On top of that, the careful choice of a ligand composition to achieve specific optical outputs. Moreover,
moiety ensures, at the same time, core rigidity (which reduces we wondered if one could take advantage of the ladder-like
phonon-assisted deactivation routes) and a suitable way to energy level structure of LnIII ions to modulate ET and BET
efficiently sensitize LnIII optical centers. The so-called “antenna processes in MCAs (Figure 1B), a strategy so well explored on
effect” is essential to account for the low absorption coefficient NP systems. In essence, we aimed to shine some light on
of LnIII and accomplish high performance. In the past couple of knowledge acquired over the last decades in the field of NPs
years, our group has studied several strategically designed and assess it from the perspective of MCAs.
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To reach this goal, we investigated a series of trimetallic reported at 24,961 cm−1, and it efficiently sensitizes TbIII 5D4
MCAs, {Ln2Eu2Tb16}, where Ln = Ce, Pr, Nd, Sm, Gd, Dy, (≈ 20,500 cm−1) through a T1 → TbIII ET. In contrast,
Ho, Er, Tm, and Yb. We kept a common Eu 2 Tb 16 EuIII 5D0 (≈17,500 cm−1) can only be populated via TbIII →
composition, while replacing the third LnIII within the MCA EuIII ET, as it is too low in energy to be directly populated by
structure. The constant pair of emitting ions gives us a ground the ligand. An Eu-based ligand-to-metal charge-transfer
base to understand the optical features. This allows us to (LMCT) state, around 20,500 cm−1, is also known to act as
investigate the influence of the third LnIII intrinsic character- a deactivation pathway of EuIII emission.35
istics, such as energy level structure and spin−orbit coupling In addition to keeping the structure as intact as possible, the
(SOC) strength, on TbIII → EuIII ET and the final emission general composition {Ln2Eu2Tb16} was also designed to attain
output. By exploring the temperature-dependent luminescence an optimal TbIII → EuIII energy transfer efficiency (ηET).
and rationalizing possible ET processes, we demonstrate for Incorporating only two other LnIII ions minimizes the
the first time how the intrinsic properties of different LnIII ions possibility of T1 → LnIII ET and establishes TbIII as the
can show tremendous impacts in the luminescence of LnIII- primary acceptor of the antenna effect, at least in the first
based MCAs, in special when targeting their potential for instance. Furthermore, by keeping the amount of EuIII ions
thermometry applications. constant, we ensure that the impact of the LMCT state will be
the same for all MCAs. The doping of a third LnIII ion leads to
■ RESULTS AND DISCUSSION
To assess the impact of a third LnIII ion on TbIII → EuIII
the insertion of energy levels besides those from the TbIII/EuIII
pair. These energy levels may or may not have appropriate
intracluster ET and luminescence thermometry performance, energy to play a role in the ET processes, acting as bridging
we synthesized a series of levels for energy migration, nonradiative loss, or a BET
[Ln2Eu 2 Tb 16(chp) 30(CO3 ) 12(NO3 ) 6(H 2 O)6 ]·H2 O MCAs, pathway (Figure 2E). Besides that, changes in the strength of
where Ln = Ce, Pr, Nd, Sm, Gd, Dy, Ho, Er, Tm, and Yb SOC are also known for affecting the radiative and non-
and chp = deprotonated 6-chloro-2-pyridinol, {Ln2Eu2Tb16}, radiative decay rates involved in ligand intersystem crossing
according to the method previously reported by our (ISC) and the sensitization of LnIII excited levels. Hasegawa
group.34−37 Due to the similar ionic radii, substituting one and co-workers have shown that a strong SOC favors Sn → T1
LnIII ion for another in a matrix is a well-established practice ISC and disfavors T1 → LnIII ET, while weak SOC has the
for many materials. The chosen composition ensures that the opposite effect.52 Therefore, by mixing different LnIII in the
crystalline lattice will not be significantly distorted, as TbIII and composition of a cluster, one can achieve an optimal SOC
EuIII have very similar sizes (1.09 and 1.12 Å, respectively, for strength to obtain high efficiency.
an ennea-coordination environment).38 Thus, the doping of For the Ln-doped MCAs, similar excitation spectra (Figure
only two other LnIII atoms with a more substantial difference S6) and slightly different emission outputs (Figure 3A,B) were
should not considerably modify the atomic distances and the obtained. By carefully selecting the composition, TbIII and EuIII
local coordination. Additionally, the TbIII/EuIII pair is the most relative emission intensities can be entirely modulated.
studied LnIII pair for luminescence thermometry, thus Compared to the base composition, MCAs doped with CeIII
providing us a foundation for understanding the effect of and YbIII favor TbIII emission bands, while the remaining lead
different LnIII ions on the thermometric performance.39−50 to an opposite profile which favors EuIII. This is the first
Powder X-ray diffraction (PXRD) confirms that all MCAs are indication that the third LnIII is affecting TbIII → EuIII ET.
isostructural to the reported {Ln20}, which crystallizes in a Nonetheless, the shape and number of components on each
trigonal R3̅ space group (Figure S2).30,34 Fourier transform emission band remain the same. As LnIII ions are known for
infrared (FTIR) spectra exhibit the expected bands (Figure being sensitive to the coordination environment, this supports
S3). Nominal composition was qualitatively confirmed through that the crystalline lattice is not considerably distorted. Due to
energy-dispersive X-ray spectroscopy (EDS) (Figure S4), and the composition modulation, a different color output is
inductively coupled plasma optical emission (ICP-OES) data observed, as shown in the CIE 1931 diagram (Figure 4).
show a good agreement with the expected ion percentage ratio Photographs of MCAs under natural light and 300 nm
in each MCA (see the Methods Section). To provide a ground excitation are provided on the supplementary material (Figure
basis for our LnIII doping luminescence studies, we focused our S7). A shift toward the pink region is observed for the Er-
attention on the {Gd 2 Eu 2 Tb 16 } MCA. In this base doped MCA due to ligand fluorescence (Figure S8), as this ion
composition, we only have EuIII and TbIII as optically active has an excited state, 2G9/2 (≈24,750 cm−1), close in resonance
ions (Figure 2A) since the GdIII first excited 4f level (6P7/2, with chp T1, which allows ErIII → T1 BET.
≈32,200 cm−1) lies above EuIII, TbIII, and the chp ligand Sm-doped MCA also exhibits bands assigned to SmIII
excited states (Figure S5).51 transitions, namely, 4G5/2 → 6H5/2, 4G5/2 → 6H7/2, and 4G5/2
Photoluminescence measurements were performed in → 6H9/2 (Figure S9). Emission bands from EuIII, TbIII, and
acetonitrile solution (0.1 mg mL−1), as the stability of SmIII are observed because the large gap separating their
{Ln20} MCAs in this solvent has been proved before by emitting level from the next energy level reduces the
nuclear magnetic resonance (NMR) and dynamic light probability of energy loss by multiphonon relaxation.7,53
scattering (DLS) studies.35 Excitation spectra of the base Despite {Ln20} core rigidity, the presence of only one or two
composition, {Gd2Eu2Tb16}, show an intense broadband O−H oscillators (νOH ≈ 3300−3500 cm−1) is more than
assigned to the chp excited singlet state (Figure 2B). This enough to quench the emission of other LnIII.54−56 Moreover,
confirms that the ligand moiety effectively harvests the energy SmIII has excited states with appropriate energy for TbIII →
further transferred to the LnIII center. Upon 300 nm excitation, SmIII ET, which populates the 4G5/2 emitting level. As for the
the emission spectrum exhibits the characteristic sharp bands other LnIII, even if their energy levels have an appropriate
assigned to TbIII (5D4 → 7FJ, J = 6−0) and EuIII (5D0 → 7FJ, J position to intervene in ET and BET processes (mainly
= 0−6) (Figure 2C,D) transitions. The chp triplet state (T1) is through temperature-activated pathways, as it will be further
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t1
t ·I(t )· dt
t0
< >= t1
I(t )·dt
t0 (1)
In a higher or lesser degree, a decrease in τTbIII and τEuIII is
observed for all Ln-doped MCAs in comparison with the base
composition (Figure 5A). To further comprehend these results

Figure 3. (A, B) Emission spectra of Ln-doped MCAs at 20 °C. Most

intense transitions of TbIII (5D4 → 7F5) and EuIII (5D0 → 7F2) are
highlighted. *SmIII emission bands.

Figure 5. (A) EuIII 5D0 and TbIII 5D4 emitting state average lifetime
according to MCA doping composition. (B) TbIII → LnIII ET
efficiency of Ln-doped MCAs.

and understand the dynamic properties of TbIII in the presence

and absence of an acceptor species, a sample with composition
{Gd4Tb16} was prepared. An average lifetime value of 2310 μs
was found for TbIII in these conditions (Figure S20).
Accordingly, TbIII → LnIII ηET was calculated, considering
the lifetime of the donor ion (TbIII) in the presence (τa) or the
Figure 4. CIE 1931 chromaticity diagram of emission output of Ln- absence (τ0) of an acceptor (any LnIII) species, as given by eq
doped MCAs at 20 °C. 260
ÄÅ É
ÅÅ
ÅÅ ij a yzÑÑÑÑ
TbIII Ln III(%) = Å Å1 jjjj zzzzÑÑÑ· 100
ÅÅ Ñ
ÅÇ k 0 {ÑÑÖ (2)
discussed), quenching through nonradiative energy loss is
inevitable. Followed by the decrease in τTbIII and τEuIII lifetimes, an increase
To better assess the energy transfer processes involved in in ηET is observed for all Ln-doped MCAs (Figure 5B and
TbIII/EuIII emission modulation, decay curves of emitting Table S1). This suggests that, aside from GdIII, when a third
states were collected by monitoring both optical centers LnIII is present, TbIII → EuIII ET is not the only ET process
taking place. In fact, processes such as ET and BET with the
(Figures S10−S18). Within the {Ln20} crystalline structure,
third LnIII excited levels, energy migration, and other effects
LnIII ions occupy four slightly different crystallographic sites, must be considered. Although these processes are very tricky
which lead to multiexponential emission decay curves.34 to elucidate in a complex system like ours, containing 20 metal
Therefore, the average lifetime was calculated using the atoms, some conclusions might be suggested, keeping in mind
integrated area method, as given by eq 1, where t0 is the that the experimental lifetime value of an emitting state
time in which the decay curve reaches its maximum intensity considers both radiative and nonradiative processes that lead
and t1 is the time in which it returns to the background.57−59 to the deactivation of this state.
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Figure 6. Variable-temperature emission spectra of (A) {Dy2Eu2Tb16}, (B) {Sm2Eu2Tb16}, and (C) {Ce2Eu2Tb16} MCAs and (D−F) partial
energy level diagram showing the suggested luminescent processes of each system.

CeIII and YbIII affect τTbIII the least, which is expected due to To rationalize these behaviors, as well as the pathways
a lack of energy levels with appropriate positions. In contrast, through which they happen, one must consider two character-
all other LnIII ions reduce τTbIII by almost half, while ηET shows istics that can be affected by the presence of a third LnIII:
a significant raise. This trend agrees with a probable TbIII → firstly, the change in SOC strength and how it impacts T1 →
LnIII ET. Besides that, EuIII → LnIII ET might also happen and TbIII sensitization and, secondly, the energy level positions and
reduce the electronic population being radiatively emitted by how they can act as a deactivation pathway or as an energy
EuIII, leading to a decrease of τEuIII as well. Therefore, the migration bridge for the electronic population.
position of excited levels arising from the third LnIII plays a The base composition, {Gd2Eu2Tb16}, as well as the MCAs
crucial role in modulating the luminescent profile, either doped with heavy LnIII show a quenching of TbIII emission
through TbIII → LnIII or EuIII → LnIII ET. Depending on the bands accordingly to the temperature increase, which is caused
LnIII energy level’s structure, part of its electronic population by a decrease in the population of the TbIII emitting state
might be transferred back to TbIII (LnIII → TbIII BET), decay (Figures 6A and S23−S25). Due to the heavy atom effect,
radiatively, or be lost nonradiatively. Temperature-dependent which leads to a stronger SOC, a reduction in T1 → TbIII ET
luminescence spectra were collected to assess these ET efficiency is expected. Hence, with the increase in temperature,
processes’ influence on the thermometric performance and it becomes easier for TbIII 5D4 to be deactivated nonradiatively.
gain insights into the possible pathways through which they Besides that, aside from GdIII, the emitting state of TbIII is
occur (Figure 6). close in energy to the excited states of DyIII (4F9/2, ≈21,100
A quenching of the emission is expected with the increase in cm−1), HoIII (5F3, ≈20,750 cm−1), ErIII (4F7/2, ≈20,650 cm−1),
temperature, since higher temperatures favor the probability of and TmIII (1G4, ≈21,250 cm−1), which favors TbIII → LnIII ET
electronic depopulation through nonradiative routes. This and LnIII → TbIII BET, with less probability of the latter
quenching significantly impacts EuIII emission due to the because of the short lifetime of these LnIII states (Figures 6D
LMCT state, which is a thermally favored nonradiative and S26−S28).
pathway.61−64 Therefore, the overall color output, according In contrast, the MCAs doped with light LnIII lead to an
to the increase in temperature, goes from an orange-reddish
almost constant emission of TbIII components, even with the
emission toward a yellow-greenish profile (Figures S21 and
increase in temperature (Figures 6B, S29, and S30). This
S22). When one considers the third LnIII in each composition,
indicates that the electronic population of TbIII is not being
three distinct temperature-dependent behaviors are seen
deactivated nonradiatively with as much significance as seen
regarding TbIII components:
with the heavy LnIII MCAs. In this case, the weaker SOC favors
(1) For middle and heavy LnIII ions (GdIII, DyIII, HoIII, ErIII, T1 → TbIII sensitization, which facilitates this state to have an
and TmIII), an emission quenching is observed (Figure almost constant population regardless of the increase in
6A shows {Dy2Gd2Tb16}). temperature and nonradiative depopulation. Furthermore,
(2) For light LnIII ions (PrIII, NdIII, and SmIII), an almost despite these LnIII present excited levels close to TbIII 5D4,
constant profile is observed (Figure 6B shows namely, PrIII 3P0 (≈20,900 cm−1), NdIII 4G9/2 (≈19,800 cm−1),
{Sm2Eu2Tb16}). and SmIII 4I9/2 (≈20,500 cm−1), they also have levels close to
(3) For CeIII and YbIII, there is an emission enhancement EuIII 5D0, which are PrIII 1D2 (≈17,000 cm−1), NdIII 4G5/2, and
(Figure 6C shows {Ce2Eu2Tb16}). 4
G7/2 (both ≈17400 cm−1), and SmIII 4G5/2 (≈17,900 cm−1).
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NdIII and SmIII have excited energy levels between EuIII 5D0 1
and TbIII 5D4, which can act as a thermally assisted pathway for Sr (%) = ·100
T (4)
EuIII → LnIII → TbIII migration ET and favor TbIII emission
bands (Figures 6E and S31). Regarding PrIII, there are no As a consequence of the processes discussed, which lead to a
ladder-like excited levels that could allow this process. change in the luminescence intensity ratio of TbIII and EuIII
Conversely, it does have a series of levels in addition to 3P0, and affect their respective radiative and nonradiative decays
namely, 3P1 (≈21,500 cm−1), 1I6 (≈21,550 cm−1), and 3P2 according to the increase of temperature, a modulation of the
(≈22,650 cm−1), with appropriate energy to be sensitized by thermometric parameter is observed (Figure 7A). Accordingly,
the ligand and transfer the electronic population further to both maximum Sr value (Srmax) and the temperature at which it
TbIII 5D4. Therefore, a T1 → PrIII ET may be happening with is reached change throughout the series (Figure 7B and Table
enough efficiency to be a second pathway to populate TbIII, 1).
through T1 → PrIII → TbIII energy migration (Figure S32). Compared to GdIII base composition, a higher Srmax is
TbIII emission boost observed at higher temperatures for observed for all MCAs doped with a third active LnIII ion,
CeIII- and YbIII-doped MCAs indicates temperature-activated except for DyIII and TmIII. As mentioned, GdIII does not
processes since an initial decrease in emission is followed by its interfere in the ET process, while other LnIII ions actively play
enhancement (Figures 6C and S33). As previously mentioned,
neither YbIII nor CeIII have energy levels close to EuIII or TbIII
emitting states. The increase is particular to each MCA and
happens for different reasons. For Yb-doped MCA, a Yb-based
LMCT state (19,305 cm−1), confirmed through diffuse
reflectance spectroscopy (Figure S34), has a critical function
as an energy transfer pathway.65−70 Due to Boltzmann
distribution, an increase in temperature means an increase in
the electronic population at higher-energy vibrational levels.
Therefore, the position of this Yb-based LMCT state, right
between EuIII 5D0 and TbIII 5D4, leads to a higher probability of
EuIII → LMCT → TbIII energy migration, a process in which
the LMCT state acts as a bridge (Figure S35). Regarding the
Ce-doped MCA boost of TbIII emission, although CeIII is well-
known for presenting 4f1 → 4f 05d1 transitions under UV
excitation,71−73 from which a hypothetical CeIII → TbIII ET
could take place, the excitation spectra collected does not show
any suggestion that this could be happening in our system
(Figure S6A). In this case, we propose that the enhancement
of TbIII emission bands happens due to the match between
CeIII 2F7/2 and 2F5/2 energy level gap (≈3300 cm−1) and the
energy difference between the emitting levels of TbIII and EuIII
(≈3000 cm−1) (Figure 6F). The match between these
resonant gaps favors an EuIII → TbIII BET process instead of
leading to cross-relaxation, as commonly reported in the
literature. 74−77 As far as we know, this behavior is
unprecedented and a CeIII-mediated energy transfer pathway
in these terms has not been reported before.
The temperature reading on a luminescent probe is carried
off by monitoring a thermally dependent optical signal, also
known as the thermometric parameter (Δ). Based on the
variable-temperature emission spectra collected and employing
the so-called ratiometric approach, we used the integrated
luminescence intensity ratio between the most intense
emission bands of TbIII (5D4 → 7F5, I1 = 530−565 nm) and
EuIII (5D0 → 7F2, I2 = 605−640 nm) to obtain Δ for each
MCA, by applying eq 3.
I2
=
I1 (3)

To assess the thermometric performance of our systems, we

calculated the relative thermal sensitivity (Sr) using eq 4. Since
the temperature dependence of Δ shows a good fit with a Figure 7. (A) Temperature dependence of the thermometric
Boltzmann-like mathematical function, as given by eq S1, we parameter (Δ) based on the luminescence intensity ratio (LIR) of
applied the given equation to the fitted function.13,78−80 Best- EuIII(5D0 → 7F2)/TbIII(5D4 → 7F5), (B) relative thermal sensitivities
fitting parameters are given in Table S2. (Sr) and (C) temperature uncertainty (δT).

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Table 1. Maximum Relative Sensitivity (Srmax) of balance between these effects is crucial to attain high
{Ln2Eu2Tb16} MCAs and Their Respective Temperatures performance in such systems.
LnIII
Gd III

CeIII
Srmax (% °C−1)
2.82
3.00
T (°C)
35.3
22.8
■ CONCLUSIONS
In this study, we have successfully modulated the optical
PrIII 3.25 32.1 properties of LnIII-based MCAs by controlling their compo-
NdIII 3.79 29.7 sition and employing doping strategies. Our strategy involved
SmIII 2.94 29.8 harnessing the intrinsic characteristics of a LnIII ion, such as the
DyIII 2.27 37.0 strength of spin−orbit coupling (SOC) and the energy
HoIII 3.08 34.3 structure of their 4f levels. To achieve fine-tuning, we
ErIII 3.70 38.2 synthesized a series of trimetallic icosanuclear MCAs with a
TmIII 2.68 39.7 consistent core ratio {Ln2Eu2Tb16}. The number of EuIII and
YbIII 2.95 40.9 TbIII ions remained constant, while varying only the nature of
the third LnIII ion. We have found that carefully selecting this
third ion can lead to specific optical outputs, including the
emission color, emission band intensity ratio, and temperature-
a role depending on their energy level structure. Contrasting dependent luminescent behavior. By analyzing average values
with the rest of the series, DyIII and TmIII are the only ions that of the decay lifetimes (τ) for TbIII and EuIII ions, as well as the
present energy levels close to TbIII 5D4 but none close to energy transfer efficiency (ηET) percentage and the variation of
EuIII 5D0 or in between the gap of 5D4/5D0 emitting states. The emission with temperature, we proposed luminescent pathways
MCA prepared with NdIII presents the highest Srmax (3.78% that could explain those observed outputs. We demonstrate
°C−1 at 29.7 °C), while the DyIII one shows the lowest Srmax that the change in SOC strength due to the doping with
(2.27% °C−1 at 37 °C). The temperature of optimal working is different LnIII ions could either favor T1 → TbIII ET (weaker
also modulated according to the composition. While NdIII is SOC due to lighter LnIII) or hinder it (stronger SOC due to
the best probe to work between 20 and 30 °C, ErIII stands out heavier LnIII), thereby affecting the population of the TbIII
in a narrow range close to 40 °C (Sr max 3.70% °C−1 at 38.2 emitting state. Furthermore, we demonstrated how the
°C). positioning of excited levels within the MCAs can affect the
Another parameter used to quantify the performance of a luminescent processes, leading to enhanced temperature-
thermometer is the temperature uncertainty (δT), which dependent properties or undesirable effects. These discoveries
represents the lowest temperature change that can be detected provide insights into the intricate interplay between
by the probe.13,80 We calculated δT by applying the average composition, doping, SOC strength, excited level positions,
method, shown in eq 5, to the normalized variable-temperature and the resulting optical properties of LnIII-based MCAs.
emission spectra, where δI is the noise fluctuation in a range
with no emission (Table S3) and I = 1 due to the
normalization. To calculate the noise fluctuation, we selected
the spectral range from 510 to 520 nm for all MCA systems,
■ METHODS
Synthesis. All manipulations were performed under aerobic
conditions and all solvents and chemicals were of reagent grade.
except the Er-doped one. Due to the ligand fluorescence MCAs were prepared according to the previously reported
observed for this sample, in its case we considered the noise procedure.34−37 In a typical synthesis, 1.00 mmol of Ln(NO3)3·
within the 560 to 570 nm range. 6H2O (Ln = Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, and Yb, in
their respective doping mol % according to composition) and 1.00
1 I mmol of 6-chloro-2-pyridinol (130 mg) were added to 20 mL of
T (T ) = · 2· · 100
Sr I (5) MeOH/MeCN (1:1). After precursor solubilization, 1.00 mmol of
triethylamine (0.139 mL) was added to the solution, and the vial was
As shown in Figure 7C, fairly low values of δT are obtained kept closed under stirring for 12 h. At the end of this time, the system
for all MCAs, with minimums ranging from 0.09 °C (GdIII, was left open and undisturbed for solvent evaporation. Pale-yellow
DyIII, and TmIII) to 0.02 °C (CeIII). The smaller the δT, the crystals were obtained in the following 5−10 days with yields between
more precise and, consequently, more efficient a thermal 30 and 45%.
probe. The value registered for the Ce-doped system is due to Compositions. {Gd4Tb16}: Gd(NO3)3·6H2O: 90 mg; Tb(NO3)3·
the high intensity of TbIII emission bands close to the range 6H2O: 362 mg. ICP analysis: calcd (20% Gd, 80% Tb); obtained
(17.5% Gd, 82.5% Tb).
selected for noise calculation, as this is a parameter known for {Gd2Eu2Tb16}: Gd(NO3)3·6H2O: 45 mg; Eu(NO3)3·6H2O: 45
being highly sensitive to data treatment and the instrument mg; Tb(NO3)3·6H2O: 362 mg. ICP analysis: calcd (10% Gd, 10% Eu,
setup.13,81 80% Tb); obtained (11.8% Gd, 8.6% Eu, 79.6% Tb).
Based on these results, we suggest that the presence of {Ce2Eu2Tb16}: Ce(NO3)3·6H2O: 43 mg; Eu(NO3)3·6H2O: 45 mg;
energy levels close to either TbIII 5D4 or EuIII 5D0 or between Tb(NO3)3·6H2O: 362 mg. ICP analysis: calcd (10% Ce, 10% Eu, 80%
the 5D4/5D0 energy gap is the key to modulating the thermal Tb); obtained (7.9% Ce, 11.7% Eu, 80.4% Tb).
behavior in an MCA temperature probe based on the TbIII/ {Pr2Eu2Tb16}: Pr(NO3)3·6H2O: 43 mg; Eu(NO3)3·6H2O: 45 mg;
EuIII emitting pair. The ability of the third LnIII to either Tb(NO3)3·6H2O: 362 mg. ICP analysis: calcd (10% Pr, 10% Eu, 80%
quench EuIII emission more easily through nonradiative routes Tb); obtained (11.2% Pr, 10.1% Eu, 78.7% Tb).
{Nd2Eu2Tb16}: Nd(NO3)3·6H2O: 44 mg; Eu(NO3)3·6H2O: 45
(as seen with ErIII) or to boost TbIII population through the mg; Tb(NO3)3·6H2O: 362 mg. ICP analysis: calcd (10% Nd, 10% Eu,
impact of SOC in T1 → TbIII ET and a thermally assisted EuIII 80% Tb); obtained (9.6% Nd, 11.2% Eu, 79.2% Tb).
→ LnIII → TbIII BET (as seen with NdIII) is what ultimately {Sm2Eu2Tb16}: Sm(NO3)3·6H2O: 44 mg; Eu(NO3)3·6H2O: 45
drives to a higher sensitivity accordingly with the variable- mg; Tb(NO3)3·6H2O: 362 mg. ICP analysis: calcd (10% Sm, 10% Eu,
temperature emission ratio change. Therefore, an optimal 80% Tb); obtained (12.8% Sm, 8.3% Eu, 78.9% Tb).

44143 https://doi.org/10.1021/acsami.3c10648
ACS Appl. Mater. Interfaces 2023, 15, 44137−44146
ACS Applied Materials & Interfaces www.acsami.org Research Article

{Dy2Eu2Tb16}: Dy(NO3)3·6H2O: 46 mg; Eu(NO3)3·6H2O: 45 https://pubs.acs.org/10.1021/acsami.3c10648

mg; Tb(NO3)3·6H2O: 362 mg. ICP analysis: calcd (10% Dy, 10% Eu,
80% Tb); obtained (8.5% Dy, 11.9% Eu, 79.6% Tb). Author Contributions
{Ho2Eu2Tb16}: Ho(NO3)3·6H2O: 46 mg; Eu(NO3)3·6H2O: 45 The manuscript was written through the contributions of all
mg; Tb(NO3)3·6H2O: 362 mg. ICP analysis: calcd (10% Ho, 10% Eu,
80% Tb); obtained (8.8% Ho, 8.9% Eu, 82.3% Tb). authors. All authors have approved the final version of the
{Er2Eu2Tb16}: Er(NO3)3·6H2O: 46 mg; Eu(NO3)3·6H2O: 45 mg; manuscript.
Tb(NO3)3·6H2O: 362 mg. ICP analysis: calcd (10% Er, 10% Eu, 80% Notes
Tb); obtained (10.8% Er, 9.7% Eu, 79.5% Tb). The authors declare no competing financial interest.
{Tm2Eu2Tb16}: Tm(NO3)3·6H2O: 46 mg; Eu(NO3)3·6H2O: 45
mg; Tb(NO3)3·6H2O: 362 mg. ICP analysis: calcd (10% Tm, 10%
Eu, 80% Tb); obtained (7.6% Tm, 10.7% Eu, 81.7% Tb).
{Yb2Eu2Tb16}: Yb(NO3)3·6H2O: 47 mg; Eu(NO3)3·6H2O: 45 mg;
■ ACKNOWLEDGMENTS
The authors thank the Canada Foundation for Innovation
Tb(NO3)3·6H2O: 362 mg. ICP analysis: calcd (10% Yb, 10% Eu, 80% (CFI) and the Natural Sciences and Engineering Research
Tb); obtained (7.6% Yb, 12.7% Eu, 79.7% Tb). Council of Canada (NSERC) for financial support of this
{Yb2Gd18}: Yb(NO3)3·6H2O: 47 mg; Gd(NO3)3·6H2O: 406 mg. work.
ICP analysis: calcd (10% Yb, 90% Gd); obtained (11.9% Yb, 88.1%
Gd).
Characterizations. Powder X-ray diffraction (PXRD) data were
collected in a Rigaku Ultima IV diffractometer with a Cu Kα (1.5418
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