Dyes and Pigments 201 (2022) 110233

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Dyes and Pigments

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Influence of β-diketone structure on optical properties of formed by Eu(III)

adducts photostable transparent films with effective luminescence
Andrey A. Knyazev a, *, Maksim E. Karyakin a, Aleksandr S. Krupin a, Yuriy G. Galyametdinov a, b
a
Physical and Colloid Chemistry Department, Kazan National Research Technological University, Kazan, 420015, Russia
b
Kazan Physical-Technical Institute, RAS, Kazan, 420029, Russia

A R T I C L E I N F O A B S T R A C T

Keywords: Luminescent adducts of Eu(III) tris(β-diketonate) with 1,10-phenanthroline were synthesized. The effect of the
β-diketonate β-diketone structure on thermodynamic and photophysical properties of Eu(III) complexes was characterized.
Europium(III) Sensitization of Eu(III) ion by various β-diketones was evaluated. The synthesized compounds are shown to form
Films
isotropic vitrified structures at room temperature allowing to produce optically isotropic vitrified films with light
Luminescence
Luminescent thermosensor
transmittance of over 90% and efficient luminescence. These photostable films were characterized as potential
luminescent temperature sensors.

1. Introduction ligand should significantly exceed the emitting state of the Eu(III) ion,
(2) the resulting complexes should possess high photo- and thermal
Coordination compounds of lanthanides(III) with specific aniso­ stabilities, and (3) these complexes should be capable of forming ho­
metric structure represent an interesting class of substances that can be mogeneous thin films without aggregation and crystallization and
efficient luminescent materials with various applications [1–10]. Their distribute evenly in the structure of a conductive polymer, what is
main advantage is the luminescence effect provided by the Ln(III) ion especially important for OLED technologies. Since the uniform distri­
and not by organic ligands. In such compounds, a central ion has a poor bution of Ln (III) compounds in the emitter allows to increase the
absorptive capacity, so the excitation energy is transferred to it from the effective energy transfer, the service life and efficiency of electrolumi­
surrounding organic ligands (the “antenna effect”) [11]. An ion, there­ nescent devices [23]. Hence, synthesis of new Eu(III) complexes ac­
fore, makes a predominant contribution to the luminescence spectrum of cording to the specified requirements is a relevant and important
a substance, while all the other parameters depend on ligands [12,13]. problem for production of various luminescent materials, especially
Considerable efforts in this research area focus on development of new fluorescent temperature sensors [24,25].
ligands or modification of well-known ones that increase the efficiency Currently, luminescence thermometry is a promising technique for
of the energy transfer to an emitting ion and influence the performance various fields of microelectronics, photonics, biology, and medicine, due
of the resulting luminescent materials [14]. Derivatives of β-diketones to its high sensitivity, fast response, and small size of sensitive elements
are among the most promising and well-tested chromophores with a [24,26,27]. Several types of luminescent materials have been investi­
high energy transfer efficiency [15–17]. Particular attention is drawn to gated as temperature sensors [28–31]. The main operating characteris­
Ln(III) complexes based on mixed ligands of the general formula Ln(Dk) tics required for a temperature sensor are intense luminescence, a decay
3 L, where Dk is an anionic β-diketonate ligand that represents a time longer than 1 μs, and low oxygen sensitivity for obtaining repro­
particularly interesting chelating system and L is a Lewis base such as 2, ducible results. Due to their unique properties, europium(III) β-diketo­
2′ -bipyridine, 1,10-phenanthroline, or phosphine oxide [18–22]. Such a nate complexes meet these criteria. Unfortunately, poor photostability
combination of ligands allows to complete the coordination sphere of under UV irradiation is the main disadvantage that restricts application
the Ln(III) ion by chromophores in stable and neutral complexes and of film probes based on europium(III) β-diketonate complexes as oper­
increase the resulting luminescence efficiency. At the same time, ating elements of luminescent thermometers [32–35]. The photo­
development of new ligands and modification of known β-diketones are stability of such complexes can be enhanced by their doping into
governed by several basic principles: (1) the triplet excited state of the different polymer matrices. Even in solid matrices, however,

* Corresponding author.
E-mail address: knjazev2001@mail.ru (A.A. Knyazev).

https://doi.org/10.1016/j.dyepig.2022.110233
Received 14 January 2022; Received in revised form 21 February 2022; Accepted 6 March 2022
Available online 12 March 2022
0143-7208/© 2022 Elsevier Ltd. All rights reserved.
A.A. Knyazev et al. Dyes and Pigments 201 (2022) 110233

photodegradation causes intensity losses of more than 15% per hour melting temperatures vary in the range of 104 ◦ C – 151 ◦ C. The Eu
under UV irradiation [32,33,36,37]. An alternative way to overcome (CPDk3-C3F7)3Phen complex demonstrates “cold crystallization” [41]
this drawback is to use photostable luminescent temperature probes when heated to 178 ◦ C (Fig. 1, b). Cooling all the complexes down to
based on mesogenic lanthanide(III) β-diketonate complexes. In com­ room temperature results in their vitrification and formation of trans­
parison with their analogues, such complexes possess an anisometric parent films. Their differential scanning calorimetry (DSC) curves (as
geometry in their vitrified state. The probes made from these complexes shown for the Eu(CPDk3-cyclo)3Phen complex) show no crystallization
are represented by vitrified films. These films are fabricated from peaks (Fig. 1, а). The films are optically isotropic, homogeneous, and
powders of the complexes by sandwiching them between two quartz contain no crystal inclusions. Fig. S1 represents the polarized optical
plates and applying a melt-processing technique. The technological microscopy (POM) image of the vitrified film produced from the Eu
advantages of such films are ease of production, resistance to atmo­ (CPDk3-C3F7)3Phen complex. The POM image was taken with crossed
spheric oxygen, intensive luminescence, and high transparency in the polarizers at the 100х magnification. Table 1 provides the phase tran­
visible region [38–40]. These properties make them very promising for sition temperatures and the respective enthalpy values.
fabrication of film-type luminescent temperature probes for modern According to the experimental data, phase transitions of the com­
molecular photonics. plexes to their isotropic liquid states occur at lower temperatures if rigid
In this work, we investigate the effect of the structure of β-diketones benzene groups in the β-diketone fragments are substituted by alkyl
on producibility of thin luminescent film materials from Eu (III) com­ groups. Introduction of a fluorocarbon substituent into a β-diketone
plexes with 1,10-phenanthroline by vitrifying their melts placed be­ fragment results in a substantial increase of the melting temperature and
tween two quartz plates. This approach allows to isolate films from the favors crystallization (Table 1).
environment and make them photostable. A series of various β-diketones
was synthesized. Optical and thermodynamic properties of the resulting 2.3. Energy levels of β-diketones
complexes in their vitrified films were investigated. Moreover, a high
photostability of film materials made it possible to consider them as The triplet states of ligands play a leading role in energy migration
promising probes for reusable luminescent thermometers suitable for between organic ligands and Ln(III) ions by either participating in the
long-term temperature monitoring. sensitization process when the lowest energy of the triplet state with the
0-phonon energy is located above the emitting state or quenching the
2. Results and discussion metal-centered excited state when it lies below it [17]. Therefore, to
reveal the mechanisms of photophysical processes occurring in the
2.1. Synthesis ligand environment of Eu(III) ions, we obtained phosphorescence
spectra of the Gd(CPDk3-R)3(H2O)2 adducts at 77 K. Fig. 2 shows the
Scheme 1 shows a series of the synthesized Eu(III) adducts, four of example of such spectral data collected for the Gd(CPDk3-C3F7)3(H2O)2
which are new Eu(CPDk3-R)3L complexes. An ethanol solution of EuCl3 complex. A substantial energy gap (≈32000 cm− 1) between the main
× 6H2O was added dropwise to a stirred hot alcohol solution containing state S7/2 and the first excited state 6P7/2 of the Gd(III) ion [44] forbids
the respective β-diketonate ligand (CPDk3-R), 1,10-phenantroline, and the energy transfer from the ligands to the metal atom in the Gd
KOH. The resulting light-yellow precipitate was isolated by hot filtra­ (CPDK3-R)3(H2O)2 complex. Only the luminescence of the ligands was
tion, washed with hot alcohol, and dried under vacuum (the yields are detected.
49–58%). The compositions and structures of the synthesized com­ The phosphorescence emission band with the maximum at 510 nm
pounds were confirmed by elemental analysis, mass spectrometry, and corresponds to the transition from the phosphorescence state to the
luminescence spectroscopy. oscillation set in the main state. Thus, we determined the triplet level for
the CPDK3-C3F7 complex, which equals to 19 607 cm− 1. The triplet level
2.2. Thermal behavior energies of other β-diketones are summarized in Table 2. The phos­
phorescence spectra of Gd(III) β-diketonate adducts are shown in
All the synthesized complexes (with the exception of the Eu(CPDk3- Figs. S2–S4.
C3F7)3Phen complex) are amorphous powders in their solid states. Their In all the studied cases, replacement of the hydrocarbon substituent

Scheme 1. Synthesis of tris(β-diketonate)europium adducts with 1,10-phenanthroline.

2
 A.A. Knyazev et al. Dyes and Pigments 201 (2022) 110233

Fig. 2. Luminescence spectrum of the Gd(CPDk3-C3F7)3(H2O)2 complex in a

solid state at 77 K.

in the β-diketone structure of the Eu(CPDk3-5)3Phen complex reduces the

triplet level energy (Table 2). With the exception of the Eu(CPDk3-
− 1
cyclo)3Phen complex, Δ2 ≥ 2000 cm for all the synthesized complexes,
which corresponds to the range of optimal values according to Sato and
Latva [45,46]. Thus, the triplet energy values of the synthesized
β-diketones make them suitable for sensitizing the Eu(III) ion emission.
In addition, these values are sufficiently high to prevent this system from
a reverse metal-to-ligand energy transfer. This statement is confirmed by
comparing the intensities of the 5D0-7F2 transition in the luminescence
spectra of the complex’s solutions (Fig. 4). As for the Eu(CPDk3-cyclo)3
Phen complex, its energy values are Δ1 = 184 cm− 1 and Δ2 = 1930
cm− 1. These values are outside optimal ranges. As compared with other
complexes, reduction of Eu(III) excitation by ligands can be observed in
this case. A triplet state of ligands is quite important for sensitizing
luminescence of lanthanides. However, this is not the only factor we
should consider for development of highly efficient lanthanide emitters.
High energy oscillations (C–H, O–H, N–H) can also exert influence on
the emission of lanthanide ions.

Fig. 1. DSC thermogram of the Eu(CPDk3-cyclo)3Phen (a) and Eu(CPDk3-

C3F7)3Phen (b) complexes.

Table 1
Thermodynamic parameters of the synthesized complexes.
Entry Complex Transition T ΔСP ΔH
[◦ C] [kJ⋅mol− 1⋅K− 1] [kJ⋅mol− 1]

1 Eu(CPDk3- G→Iso 104 112,7 –

cyclo)3Phen
2 Eu(CPDk3- G→Cr 178 – 42.0
C3F7)3Phen Cr→Iso 223.8 – 50.9
3 Eu(CPDk3- G→Iso 151 6,92 –
Tol)3Phen
4 Eu(CPDk3-Ph- G→Iso 127 56,41 –
F)3Phen
5 Eu(CPDk3- G→Iso 142 84,3 –
Ph)3Phen [42]
6 Eu(CPDk3- G→Iso 110 – –
5)3Phen [43]

Fig. 3. Room temperature absorption spectra of the Eu(III) complexes in hex­

ane (1 × 10− 5 mol l− 1).

3
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A.A. Knyazev et al. Dyes and Pigments 201 (2022) 110233

Eu(III) complexes measured for solutions in hexane (1 × 10− 5 mol l− 1).

The QY values do not exceed 1%, with the exception of the Eu(CPDk3-
C3F7)3Phen complex (QY = 3.7%). Such results may be due to the high
degree of energy dissipation by solvent molecules [47], which is
confirmed by the high values of non-radiative decay rates (ANR).

2.5. Fabricating thin films and characterizing their optical and

luminescent properties

Dissolved complexes were placed between two quartz plates and

heated to their isotropic states. Further cooling down (10◦ С/min) to
room temperature produced homogeneous films. The thickness of the
films was controlled by placing 6,1 μm polystyrene spacers between the
plates. As we can see from the light transmittance spectra, the films of
the complexes absorb the UV radiation almost completely. The visible
light transmittance coefficient grows with the wavelength of light and
reaches its maximum of 90% with the films of the Eu(CPDk3-C3F7)3Phen
Fig. 4. Room temperature luminescence spectra of Eu(III) complexes in hexane complex (Fig. 5).
(1 × 10− 5 mol l− 1). Fig. 6 represents the excitation spectra of the thin films produced
from the Eu(III) complexes. The luminescence excitation spectra of the
2.4. Optical and luminescent properties of solutions films containing Eu(CPDk3-tol)3Phen, Eu(CPDk3-5)3Phen, Eu(CPDk3-Ph-
F)3Phen, or Eu(CPDk3-cyclo)3Phen complexes were obtained by moni­

Optical and luminescent properties of the synthesized complexes toring emission at the wavelength of 613 nm at room temperature. These
were characterized by studying their solutions in hexane. The concen­ spectra consist of two broad bands. The band with the maximum at 340
tration of each complex was 1 × 10− 5 moL/l. The absorption spectra nm corresponds to the ligand-centered singlet-singlet (S0→S1) transi­
(Fig. 3) show maximums in the range of 320–353 nm for various tions of β-diketones. The second band in each spectrum contains maxi­
β-diketone ligands. These spectra are represented by broad bands, which mums in the range between 400 nm and 450 nm. These bands indicate
correspond to the ligand-centered singlet-singlet transitions. The ab­ formation of aggregates. The aggregation process was confirmed by the
sorption bands of the complexes are similar to individual ligands authors for similar complexes [41] and agrees with the literature data
(β-diketones) in the region of 300–400 nm (рис. S5, SI). Replacement of [48].
hydrocarbon and fluorocarbon substituents with benzene ring in the The Eu(CPDk3-C3F7)3Phen complex contains a fluorocarbon substit­
structure of the primary antenna leads to a significant increase in the uent and possesses different spectral characteristics. This complex
molar absorption coefficient (Table S1) of ligands in Eu(III) complexes demonstrates a hypsochromic shift of the excitation maximum to the
(εLigand = 19500 ÷ 26600; εcomplex = 60100 ÷ 82400). Despite this, shorter wavelength of 340 nm and the narrower band in the 400 nm
complexes have low photoluminescence intensity. The absorption band section of the spectrum. According to these data, aggregation of this
maxima of the synthesized Eu(III) complexes are shifted to longer complex is less intensive in the vitrified state.
wavelengths relative to the individual ligands. It has happened due to The films of all the complexes demonstrate intensive red photo­
the coordination of diketone ligand with metal ion which helps in the luminescence in response to the UV excitation at the wavelength cor­
extension of conjugation. responding to the excitation maximum (Fig. 7). The most intensive
The solutions of the complexes demonstrate red luminescence in photoluminescence was observed for the Eu(CPDk3-C3F7)3Phen and Eu
response to a UV excitation at the wavelengths corresponding to the (CPDk3-tol)3Phen complexes. We should note that the emission spectra of
excitation maximums (Fig. 4). The luminescence spectra of the com­ the films produced from the Eu(III) complexes show no phosphorescence
plexes contain the maximum at 613 nm and the series of distinguished from the ligands indicating efficient intermolecular transfer of energy
secondary maximums that indicate the transitions from the 5D0 level of from the ligands to the emitting Eu(III) ion.
the excited state to the 7FJ sublevels of the main multiplet (J = 0–4). The To evaluate the effect of substituents in the β-diketone molecule on
fluorescence lifetimes of lanthanide complexes in solutions are within the efficiency of the energy transfer from the ligands to the emitting Eu
112–613 μs that is typical for β-diketonates of Eu(III). The most intensive (III) ion, we measured the luminescence lifetimes and the luminescence
luminescence is demonstrated by the Eu(CPDk3-C3F7)3Phen solution: the quantum yields (intrinsic and relative) of the synthesized Eu(III) com­
ratio of intensities of the electric dipole transition and the magnetic plexes in solid films (Table 3). The measured fluorescence lifetime of the
dipole transition is 16:1. lanthanide complexes is found to be within 316–535 μs that is typical for
Table 3 summarizes the photoluminescent parameters, namely the Eu(III) complexes with β-diketone ligands. The highest quantum yield
luminescence lifetime (τobs), radiative lifetime (τrad), radiative (AR) and (27.4%) and the most efficient intermolecular energy transfer (78%)
non-radiative (ANR) decay rates, the intrinsic quantum yield (QEuEu), the were observed for the Eu(CPDk3-C3F7)3Phen complex. There may be two
relative quantum yield (QLEu) and energy transfer efficiencies (ηsens) of factors responsible for such values. The first factor is the optimal energy
difference between the triplet level energies of the ligands and the
emitting level of the Eu(III) ion. The second factor is the substitution of
Table 2 C–H bonds by C–F bonds in the Eu(CPDk3-C3F7)3Phen complex and the
Energies of the triplet (ET1) states of the ligands and values Δ1 = ET1 - E5D1 resulting reduced intensity of non-emission processes. Such processes
(cm− 1), Δ2 = ET1 - E5D0 (cm− 1). T = 77 K. are active in the Eu(CPDk3-5)3Phen complex due to a multy-phonon
Entry Complex ET1 [cm− 1] Δ1[cm− 1] Δ2[cm− 1] relaxation of C–H oscillations [49].
Comparison of the properties in solution and solid states reveals that
1 Gd(CPDk3-cyclo)3(H2O)2 19 157 184 1930
2 Gd(CPDk3-C3F7)3(H2O)2 19 607 634 2380 the mechanism of the coordination effects of the β-diketonate ligands.
3 Gd(CPDk3-Tol)3(H2O)2 19 417 444 2190 QEuEu of complexes in the solid state is much larger than in the solution.
4 Gd(CPDk3-Ph-F)3(H2O)2 19 305 332 2078 ANR of complexes in solid films is much shorter than in solution and
5 Gd(CPDk3-Ph)3(H2O)2 19 300 327 2 073 these results cause the remarkable increment of QLEu in solid state. This
6 Gd(CPDk3-5)3(H2O)2 20 200 1 227 2 973
is because there is no energy dissipation by solvent molecules in the solid

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A.A. Knyazev et al. Dyes and Pigments 201 (2022) 110233

Table 3
Photoluminescence parameters of europium (III) complexes with different chemical structures in the solution and solid films excited by the peak wavelength of
excitation wavelength light.
Complex τobs[μs] τrad[μs] AR[s− 1] ANR[s− 1] QEuEu[%] QLEu[%] ηsens[%]
Eu(CPDk3-cyclo)3Phen
Hexane 112 1953 512 8417 5.7 0.6 0.1
Solid film 316 1491 671 2494 21.2 8.1 38.2
Eu(CPDk3-C3F7)3Phen
Hexane 613 2095 477 1154 29.2 3.7 12.7
Solid film 535 1541 649 1220 34.7 27.4 78
Eu(CPDk3-Tol)3Phen
Hexane 130 1629 614 7078 8.0 0.5 6.25
Solid film 387 1420 704 1880 27.3 13.3 48.7
Eu(CPDk3-Ph-F)3Phen
Hexane 145 1545 647 6249 9.4 0.8 8.5
Solid film 390 1455 687 1877 26.8 15.4 59.7
Eu(CPDk3-Ph)3Phen
Solid film 380 1145 873 1758 33.0 17.5 53.0
Eu(CPDk3-5)3Phen
Solid film 516 1605 623 1315 32.2 16.5 51.2

Fig. 5. Light transmittances of films of the Eu(III) complexes (6.1 μm).

Fig. 7. Luminescence spectra of the synthesized Eu(III) complexes (a); lumi­

Fig. 6. Luminescence excitation spectra of the synthesized Eu(III) complexes. nescence quenching curves (b).

state. τrad of complexes in the solid state is smaller than that in the so­ solid state. This should be specially mentioned because these results
lution. τrad is proportional to the ratio of the intensities of magnetic indicate that the ligand field can be more asymmetric in the solid state
transitions IMD/ITOT, with smaller τrad meaning smaller IMD/ITOT in the than in the solution. Strong steric repulsion between bulky substituents

5
A.A. Knyazev et al. Dyes and Pigments 201 (2022) 110233

of β-diketonate ligands could be the cause of this phenomenon [50]. Mass spectra were obtained by a Bruker Esquire LC ion-trap mass
spectrometer. Thin films of europium complexes with various β-diket­
onates were produced by placing samples of complexes between quartz
2.6. Temperature-sensitive luminescent properties
glasses. The thickness of this quartz cell was controlled by polystyrene
microspheres with a diameter of 6.1 μm. The 20 × 20 mm quartz glass
A possibility of using the produced films as materials for luminescent
was used as a substrate for the films. Optical textures and temperatures
temperature sensors was examined. The film of the Eu(CPDk3-
of the phase transitions were determined by an Olympus BX-51 polar­
C3F7)3Phen complex demonstrates the most intensive luminescence with
izing microscope equipped with a Linkam high-precision heating sys­
the longest lifetime. Therefore, it was selected for the luminescence
tem. DSC measurements were performed with a NETZSCHDSC 204 F1
thermometry studies.
Phoenix in a heating–cooling mode at a scan rate of 10 K/min. Ab­
Table 5 shows the comparison between the operational characteris­
sorption and transmission spectra were measured by a Perkin–Elmer
tics of the Eu(CPDK3-C3F7)3Phen film probe presented in this work and
Lambda-35 UV/Vis spectrophotometer. Excitation, luminescence
the representatives of the best film probes based on known europium
spectra and lifetime were measured by a Varian Cary Eclipse spectro­
(III) β-diketonate complexes that perform effective absorption of light in
fluorometer. The phosphorescence spectra of the vitrified Gd(CPDk3-
the blue-violet range. The vitrified film exhibits a detectable tempera­
ture dependence of the luminescence decay time in the range of R)3(H2O)2 films were recorded at 77 K by an optical spectrometer based
on the MDR-23 monochromator with time delay of 1 μs? An LGI-21
298–363 K (Fig. S6 – S7, Tables S2 and SI). The absolute temperature
pulsed nitrogen laser (337 nm wavelength, 1.5 mW average output
sensitivity of the luminescence quenching time Sτ and the relative
(a)
power, 10 ns pulse duration, 50 Hz repetition rate) was used as an
temperature sensitivity Sτ of the vitrified film containing the Eu(CPDk3-
(r)
excitation source.
C3F7)3Phen complex are shown in Fig. S8. The Eu(CPDk3-C3F7)3Phen film The analysis of the luminescence decay curves based on a mono-
is equal to the best available film probes based on Ln(III) β-diketonates exponential function:
in terms of its relative sensitivity (− 0.87% K− 1) and the absolute
sensitivity (− 5.35 μs K− 1). I(t) = A⋅exp( − t / τ) (1)

where I(t) is the luminescence intensity, A is the pre-exponential factor

3. Conclusions
and τ is the luminescence decay time.

We synthesized a new series of Eu(III) tris-(β-diketonate) adducts

with 1,10-phenanthroline and studied the impact of the β-diketone 4.2. Synthesis
structure on thermodynamic and photophysical properties of the Eu(III)
complexes. All the synthesized compounds maintain their melt texture All the β-diketones (1-cyclohexyl-3-(4-(4-propylcyclohexyl)phenyl)
when vitrified by cooling down to room temperature. Therefore, they propane-1,3-dione (CPDk3-cyclo), heptafluoropropyl-3-(4-(4-
allow to produce optically isotropic microscale vitrified films. These propylcyclohexyl)phenyl)propane-1,3-dione (CPDk3-C3F7), 1-(4-(4-pro­
films possess efficient luminescent properties and demonstrate a light pylcyclohexyl)phenyl)-3-(p-tolyl)propane-1,3-dione (CPDk3-tol), 1-(4-
transmittance above 90%. Sensitization of Eu(III) ions by β-diketones fluorophenyl)-3-(4-(4-propylcyclohexyl)phenyl)propane-1,3-dione
was evaluated for various ligand structures. Substitution of C–H bonds (CPDk3-Ph-F), 1-phenyl-3-(4-(4-propylcyclohexyl)phenyl)propane-1,3-
with C–F bonds in the ligand environment is found to increase the dione (CPDk3-Ph), and 1-(4-(4-propylcyclohexyl)phenyl)octane-1,3-
quantum yield and the intermolecular energy transfer efficiency in the dione (CPDk3-5)) were synthesized according to the modified literature
complexes. The properties of the Eu(CPDk3-C3F7)3Phen films were procedures [56].
assessed for possible luminescent temperature sensor applications. Such 1-cyclohexyl-3-(4-(4-propylcyclohexyl)phenyl)propane-1,3-dione
film sensors were found to be thermally stable and photostable struc­ (CPDk3-cyclo): Yield: 40.3%. ESI-MS (m/z): 354 [M]+. 1H NMR (300
tures. They demonstrated high absolute (− 5.35 μs K− 1) and relative MHz, CDCl3): δ = 0.92 (t, J = 7.2 Hz, 3H, CH3), 1.01–1.54 (m, 15H,
(− 0.87%⋅K− 1) sensitivities in the 298–363 K temperature range. Such CH2), 1.70–1.96 (m, 8H, CH2), 2.27–2.37 (m, 1H, СOC6H11), 2.48–2.59
characteristics are comparable with the performance of the best-known (m, 1H, CHC6H4), 4.11 (s, 0.1H, keto CH2), 6.16 (s, 0.9H, enol CH),
analogues. 7.27–7.30 (m, 2H, C6H4), 7.80–7.83 (m, 2H, C6H4), 16.36 (s, 0.9H, enol
OH; keto/enol, 1:9) ppm. C24H34O2 (354.5). Calcd: C, 81.31; H, 9.67.
4. Experimental section Found: С, 81.24; H, 9.66.
Heptafluoropropyl-3-(4-(4-propylcyclohexyl)phenyl)propane-1,3-
4.1. Instruments and chemicals dione (CPDk3-C3F7): Yield: 44.1%. ESI-MS (m/z): 439 [M]+. 1H NMR
(300 MHz, CDCl3): δ = 1.69 (t, J = 7.3 Hz, 3H, CH3), 1.77–2.34 (m, 10H,
Europium(III) chloride hexahydrate and 1,10-phenanthroline were CH2), 2.6–2.73 (4H, C6H10), 3.28–3.41 (m, 1H, CHC6H6), 7.38 (s, 1H,
purchased from Sigma-Aldrich. CHN elemental microanalysis was per­ keto CH2), 8.05 (s, 0.24H, enol CH), 8.12 (d, J = 8.5 Hz, 2H, C6H4), 8,67
formed by a CE Instruments EA-1110 apparatus. Europium elemental (d, J = 8.5 Hz, 2H, C6H4), 16.20 (s, 0.76H, enol OH; keto/enol, 1:1) ppm.
microanalysis was performed by an X-ray fluorescence Bruker M4 Tor­ C21H23F7O2 (440.3). Calcd: C, 57.27; H, 5.26. Found: C, 57.14; H, 5.33.
nado apparatus. 1H NMR spectra were recorded by Bruker Avance 300 1-(4-(4-propylcyclohexyl)phenyl)-3-(p-tolyl)propane-1,3-dione
and Bruker Avance 400 spectrometers (operating at 300 and 400 MHz). (CPDk3-tol): Yield: 46.5%. ESI-MS (m/z): 361 [M]+. 1НNMR (300 MHz,

Table 5
Comparison between the operational characteristics of the Eu(CPDK3-C3F7)3Phen film probe presented in this work and the examples of best available film probes based
on known europium(III) β-diketonate complexes that perform effective absorption of light in the blue-violet range.
Film probe Matrix λmax (nm) Operating temperature range (K) Decay time range (μs) τref (μs) S(a)τ (μs⋅K− 1) S(r)τ (%⋅K− 1) Ref.

Eu(CPDK3-C3F7)3Phen No 340 298–363 535–170 532 (303 K) - 5.35 - 0.87 This work
Eu(DK12–14)3Phen No 402 270–370 561–37 561 (270 K) - 5.4 - 1.0 [51]
Eu(CPDK3–5)3Phen No 398 298–348 537–210 537 (298 K) - 6.5 - 1.2 [52]
Eu(tta)3DEADIT PMAN 416 274–323 360–130 360 (274 K) - 4.7 - 1.3 [53]
Eu(tta)3 PS-A 395 273–363 350–128 350 (273 K) - 2.5 - 0.7 [54]
Eu(tta)3(dpbt) PVMK 411 274–339 517–200 517 (274 K) − 4.9 − 0.94 [55]

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A.A. Knyazev et al. Dyes and Pigments 201 (2022) 110233

CDCl3): δ = 0.92–0.97 (m, 3H, CH3), 1.03–1.56 (m, 9H, CH2), 1.89–1.95 (m/z): 1312,5 (M + Na)+.
(m, 4H, С6H10), 2.44 (s, 3H, CH3), 2.51–2.60 (m, 1H, CHC6H4), 4.58 (s, Gd(CPDk3-Tol)3(H2O)2 Yield: 69%. Formula: C75H91GdO8. Calcd: C,
0.1H, keto CH2), 7.28–7.35 (m, 4H, C6H5), 7.9–7.94 (m, 4H, C6H5), 70.50; H, 7.18; Gd, 12.31. Found: C, 70.17; H, 7.44; Gd, 12.20. ESI-MS
16.95 (s, 0.9H, enol OH; keto/enol, 1:9) ppm. C25H30O2 (362.5). Calcd: (m/z): 1301,1 (M + Na)+.
C, 82.83; H, 8.34. Found: С, 82.81; H, 8.36. Gd(CPDk3-5)3(H2O)2 Yield: 72%. Formula: C69H103GdO8. Calcd: C,
1-(4-fluorophenyl)-3-(4-(4-propylcyclohexyl)phenyl)propane-1,3- 68.05; H, 8.53; Gd, 12.91. Found: C, 67.68; H, 8.81; Gd, 12.80; ESI-MS
dione (CPDk3-Ph-F): Yield: 42.7%. ESI-MS (m/z): 366 [M]+. 1НNMR (300 (m/z): 1240,7 (M + Na)+.
MHz, CDCl3): δ = 0.92 (t, J = 7.2 Hz, 3H, CH3), 1.01–1.56 (m, 9H, CH2),
1.87–1.93 (m, 4H, CH2), 2.50–2.59 (t, 1H, CHC6H4), 4.59 (s, 0.1H, keto 4.3. Procedures for quantum yield determination
CH2), 6.79 (s, 0.9H, enol CH), 7.14–7.19 (m, 2H, FC6H4), 7.31–7.34 (m,
2H, FC6H4), 7.90 (d, J = 8.4 Hz, 2H), 7.99–8.03 (m, 2H, OCC6H4), 16.95 The relative luminescence quantum yields of the complexes were
(s, 0.9H, enol OH; keto/enol = 1:9) ppm. C24H27FO2 (366.5). Calcd: C, determined in the 10− 5 M hexane solution. The Eu(tta)3Phen complex
78.66; H, 7.43. Found: С, 78.61; H, 7.47. with the quantum yield of 36.5% was used as the standard [58]. The
1-phenyl-3-(4-(4-propylcyclohexyl)phenyl)propane-1,3-dione accuracy of the quantum yield measurements was 10%.
(CPDk3-Ph): Yield: 53.5%. ESI-MS (m/z): 347 [M]+. 1H NMR (300 MHz, The intrinsic quantum yield of Eu(III) is thus obtained from:
CDCl3): δ = 0.91–0.96 (m, 3H, CH3), 1.06–1.56 (m, 9H, CH2), 1.88–1.95
(m, 4H, C6H10), 2.51–2.60 (m, 1H, CHC6H4), 4.62 (s, 0.1H, keto CH2), φLn = τ/τR (2)
6.86 (s, 0.9H, enol CH), 7.33 (d, J = 8.1 Hz, 1H, C6H5), 7.47–7.59 (m,
3H, OCC6H5), 7.92 (d, J = 8.4 Hz, 2H, C6H5), 7.99 (d, J = 9.0 Hz, 2H, where τ is the observed luminescence lifetime of Eu(III). The empirical
C6H5), 16.95 (s, 0.8H, enol OH; keto/enol, 1:9) ppm. C24H28O2 (348.48): radiative lifetime (τr) of Eu(III) is determined:
Calcd: C, 82.72; H, 8.10. Found: C, 82.64; H, 8.15. 1
1-(4-(4-propylcyclohexyl)phenyl)octane-1,3-dione (CPDk3-5): Yield: = AMD ⋅n3 ⋅(Itot / IMD ) (3)
τR
63.0%. ESI-MS (m/z): 342 [M]+. 1НNMR (300 MHz, CDCl3): δ = 0.92
Assuming that the dipole strength of the magnetic dipole transition
(m, 6Н, СН3); 1.29–1.69 (m, 15Н, СН2, C6H10); 1.89 (m, 4H, C6H10);
Eu(III) (5D0→7F1) is independent of the environment, where AMD =
2.42 (m, 3H, СH3); 2.57 (m, 1H, C6H10); 4.06 (s, 0,2H, keto CH2); 6.15
14.65 s− 1 is the spontaneous emission probability of the 5D0→7F1
(s, 0,8H, enol CH); 7.28 (d, 2H, С6H4); 7.83 (d, 2H, С6H4); 16.26 (s, 1H,
transition in vacuum, n is the refractive index of the medium, and Itot/
enol СH) ppm. C23H34O2 (342.5). Calcd: C, 80.65; H, 10.01. Found: С,
IMD is the ratio of the total emission area to the area of the 5D0→7F1
79.86; H, 10.18.
transition. The refractive index of the europium complex was measured
General Procedure for Synthesis of Eu(CPDk3-R)3Phen Complexes:
on a spin-coated thin film deposited on a quartz plate at room temper­
The complexes were synthesized according to the procedures described
ature by a WVASE32TM Ellipsometer.
in literature [57]. The ethanol solution of EuCl3 × 6H2O (0.04 mmol)
The quantum yields φ of the films of the complexes were calculated
was slowly added dropwise to a stirred hot alcohol solution containing
by using Equation (4) [59]:
the respective β-diketone (0.12 mmol), 1,10-phenantroline (0.04 mmol),
and KOH (0.125 mmol). The resulting light-yellow precipitate was iso­ Astd (λstd ) Istd (λstd ) Dunk
φ = φstd × [ ]×[ ]×[ ] (4)
lated by hot filtration, washed with hot alcohol, and dried under vac­ Aunk (λunk ) Iunk (λunk ) Dstd
uum. Further, the product was dissolved in toluene, the obtained
solution was filtered, and the solvent was evaporated under vacuum. The subscripts std and unk indicate the standard and unknown
Eu(CPDk3-Ph)3Phen Yield: 56%. M.p. 142 ◦ C. Formula: samples, respectively; A(λ) corresponds to the absorbance of the films at
C84H89EuN2O6. Calcd: C, 73.40; H, 6.53; Eu, 11.06; N, 2.04. Found: C, the excitation wavelength λ; I(λ) is the intensity of the exciting beam
73.01; H, 6.88; Eu, 11.00; N 2.12. ESI-MS (m/z): 1385.6 (M + Na)+. (assumed to be equal for both measurements); D is the integrated
Eu(CPDk3-cyclo)3Phen Yield: 49%. M.p. 104 ◦ C. Formula: luminescence spectrum. The standard fluorophore for the measurements
C84H107EuN2O6. Calcd: C, 72.44; H, 7.74; Eu, 10.91; N, 2.01. Found: C, was a thin film of poly(methyl methacrylate) (PMMA) co-doped with 1%
72.03; H, 8.01; Eu, 10.85; N, 1.96. ESI-MS (m/z): 1403.7 (M + Na)+. Eu(tta)3(H2O)2 with φstd = 45% [60].
Eu(CPDk3-C3F7)3Phen Yield: 52%. M.p. 224 ◦ C. Formula:
C75H74EuF21N2O6. Calcd: C, 54.58; H, 4.52; Eu, 9.21; N, 1.70. Found: C, CRediT authorship contribution statement
54.28; H, 4.96; Eu, 9.04; N, 1.63. ESI-MS (m/z): 1661.3 (M + Na)+.
Eu(CPDk3-Ph-F)3Phen Yield: 55%. M.p. 127 ◦ C. Formula: Andrey A. Knyazev: Investigation, Conceptualization, Methodol­
C84H86EuF3N2O6. Calcd: C, 70.62; H, 6.07; Eu, 10.64; N, 1.96; Found: C, ogy, Writing - original draft, Funding acquisition. Maksim E. Karyakin:
70.19; H, 6.77; Eu, 10.03; N, 1.90. ESI-MS (m/z): 1439,5 (M + Na)+. Investigation, Conceptualization, Methodology, Writing - original draft,
Eu(CPDk3-Tol)3Phen Yield: 58%. M.p. 151 ◦ C. Formula: Funding acquisition. Alexandr S. Krupin: Investigation, Conceptuali­
C87H95EuN2O6. Calcd: C, 73.76; H, 6.76; Eu, 10.73; N, 1.98. Found: C, zation, Methodology, Writing - original draft, Funding acquisition.
73.13; H, 7.21; Eu, 10.49; N, 1.85. ESI-MS (m/z): 1427,7 (M + Na)+. Yuriy G. Galyametdinov: Investigation, Conceptualization, Method­
Eu(CPDk3-5)3Phen Yield: 70%. M.p. 110 ◦ C. Formula: ology, Writing - original draft, Writing - review & editing, Supervision,
C81H107EuN2O6. Calcd: C, 71.71; H, 7.95; Eu, 11.20; N, 2.06. Found: C, Funding acquisition.
71.66; H, 8.01; Eu, 11.50; N, 2.02. ESI-MS (m/z): 1367,6 (M + Na)+.
Gd(CPDk3-Ph)3(H2O)2 Yield: 61%. Formula: C72H85GdO8. Calcd: C, Declaration of competing interest
69.98; H, 6.93; Gd, 12.73 Found: C, 69.51; H, 7.06; Gd, 12.60. ESI-MS
(m/z): 1258.6 (M + Na)+. The authors declare that they have no known competing financial
Gd(CPDk3-cyclo)3(H2O)2 Yield: 58%. Formula: C72H103GdO8. Calcd: interests or personal relationships that could have appeared to influence
C, 68.97; H, 8.28; Gd, 12.54. Found: C, 68.53; H, 8.52; Gd, 12.45; ESI-MS the work reported in this paper.
(m/z): 1276.7 (M + Na)+.
Gd(CPDk3-C3F7)3(H2O)2 Yield: 61%. Formula: C63H70F21GdO8. Acknowledgments
Calcd: C, 50.06; H, 4.67; Gd, 10.40. Found: C, 49.72; H, 4.96; Gd, 9.95;
ESI-MS (m/z): 1534.3 (M + Na)+. The authors would like to thank the Russian Science Foundation
Gd(CPDk3-Ph-F)3(H2O)2 Yield: 63%. Formula: C72H82F3GdO8. Calcd: (grant No. 20-73-10091) for funding this research work. The study was
C, 67.05; H, 6.41; Gd, 12.19. Found: C, 66.61; H, 6.83; Gd, 12.15; ESI-MS carried out using the equipment of the Center for Collective Use

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