An efficient route for design of luminescent composite materials based on polyethylene containing europium dibenzoylmethanate

Article abstract of DOI:10.1039/c7nj03055j

Luminescent composite materials based on linear polyethylene doped by a well dispersed tetrakis dibenzoylmethanate europium complex have been developed. The anion of the latter serves as an efficient light harvesting antenna and possesses the desired photophysical properties. The targeted modification of the Eu complex, namely introduction of a long hydrocarbon chain into the tetraalkylammonium cation [RNEt₃]⁺, has ensured the compatibility of the complex with the polyethylene matrix. The [RNEt₃]⁺ cation has been obtained by using long-chained 1-iodoalkanes synthesized via the Nd-catalyzed ethylene oligomerization process. The photophysical properties and the homogeneity of the obtained composites have been controlled by optical spectroscopy, luminescence intensity mapping as well as scanning electron microscopy.

Full text of DOI:10.1039/c7nj03055j

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Vinogradov, M. S. Savchenko and I. E. Nifant'ev, New J. Chem., 2017, DOI: 10.1039/C7NJ03055J.
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Jason B. Benedict et al.
The role of atropisomers on the photo-reactivity and fatigue of
diarylethene-based metal–organic frameworks
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An efficient route for design of luminescent composite materials
based on polyethylene containing europium dibenzoylmethanate
Dmitrii M. Roitershtein,*ab Lada N. Puntus,ac Konstantin A. Lyssenko,d Ilya V. Taidakov,de Evgenia A.
Varaksina,ae Mikhail E. Minyaev,a Victor A. Gerasin,a Maria A. Guseva,a Alexey A. Vinogradov,ab
Maria S. Savchenko,f Ilya E. Nifant’eva,f
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
www.rsc.org/
Luminescent composite materials based on linear polyethylene doped by well dispersed tetrakis dibenzoylmethanate
europium complex have been developed. The anion of the latter serves as an efficient light harvesting antenna and
possesses the desired photophysical properties. The targeted modification of the Eu complex, namely introduction of a
long hydrocarbon chain into the tetraalkylammonium cation [RNEt3]+, has ensured the compatibility of the complex with
the polyethylene matrix. The [RNEt3]+ cation has been obtained by using long-chained 1-iodoalkanes synthesized via the
Nd-catalyzed ethylene oligomerization process. The photophysical properties and the homogeneity of the obtained
composites have been controlled by the optical spectroscopy, luminescence intensity mapping as well as scanning electron
microscopy.
considerable interest. In particular, increasing the proportion
of red light in the spectra of light sources used in agriculture
can intensify the green plant growth. In this case, Eu(III)
chelate complexes with the emission maximum at 610-620 nm
Introduction
The use of lanthanide complexes in the development of
new optical materials has markedly increased in the last
decades. Due to unique photophysical properties,1-3
coordination and organometallic compounds of f-elements are
important for the design of new luminescent materials for
optical amplifiers for telecommunication networks,4 light-
emitting devices,5 lasers,6 luminescent films,7 and organic light
emitting diodes.8 Unlike organic compounds possessing similar
characteristics, lanthanide complexes have low extinction
coefficients, which ensure transparency in the visible region.
Owing to high quantum yields, monochromatic emission (the
line width does not exceed 10 nm), and long luminescence
lifetimes, lanthanide complexes with organic ligands can serve
for the development of luminescent labels9 and anti-
counterfeiting taggants.10
are appropriate for the purpose.12
Of particular interest are luminescent composite materials
based on various polymers. When the homogeneous
distribution of luminescent materials in the polymer matrix is
achieved, the intensity and efficiency of luminescence can be
substantially increased.13,
14
Moreover, the composite
materials based on polymers doped by the lanthanide
complexes are very attractive for different applications since
the high luminance of composite can be achieved by relatively
low concentration of complexes that remarkably decreases the
cost of such materials.
The most intriguing challenge is to obtain luminescent
composite materials based on polyethylene, which possesses
excellent photostability under UV/blue irradiation, required
from modern luminescent materials.13
Meanwhile, obtaining
of a homogenous distribution of a luminescent complex in the
polyethylene matrix is associated with well-known
difficulties.8, 15-17
Lanthanide complexes with organic ligands providing an
“antenna effect”9 have a great Stokes shift, which allows to
effectively convert UV radiation (200-400 nm) to visible light.
Therefore, such complexes can be successfully used to prepare
optical materials.11 Radiation converters that transform the UV
part of the solar spectrum to visible radiation are of
The known luminescent polymer composites fabricated, for
example, using polyvinylpyrrolidone,18 polyvinylpyridine and
polyethylene methacrylate copolymer,19 and silicone rubber20
either do not utilize polyethylene, or use a polyethylene as a
surface coating for luminescent materials rather than as a
matrix in which they are distributed.21 There is only one
reported example of formation of polyethylene composites
based on europium complexes, including hexanoic, octanoic,
lauric, and stearic acid salts.22 The composites thus obtained
showed the typical Eu luminescence; however, the authors did
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not elucidate the degree of homogeneity of europium
distribution in the polyethylene matrix.
Our preliminary experiments demonstrated excellent
compatibility of polyethylene (PE) with the
Compatibility of the matrix materials and lanthanide tetraalkylammonium salt (RNEt3)+I. The [(RNEt3)]+[Eu(dbm)4]-
complex is the key problem arising in the design of hybrid complex, consisting of the tetraalkylammonium cation
materials composed of polymers doped by the lanthanide compatible with the polyethylene matrix and the [Eu(dbm)4]-
complexes. In particular, well known brightly luminescent anion expected to provide high luminescence.
complex Na[Eu(tta)4], (Htta is 2-thenoyltrifluoroacetone) is
In order to evaluate advantages and the scope of the
sparingly soluble in low-polarity polymers like polystyrene, and method applicability, we used three sorts of luminescent
is well compatible only with more polar polyesters (e.g. complexess for composite preparation, namely, three
PMMA).23 The presence of perfluorinated substituents may europium tetrakis-β-diketonate complexes: Na[Eu(dbm)4]
induce the aggregation and phase separation of the complex in
the matrix.
(
(
1
3
),24 [(C12H25NMe3)]2[Eu(dbm)4]I (
). Complex , which served as a precursor for compounds
, was used for comparison as a standard europium
design of luminescent composite materials based on linear complex with ligands that provide an "antenna effect".
polyethylene (PE) (Scheme 1), including synthesis of three Complex was an individual compound, intended to be used
tetrakis- Eu complexes containing dibenzoylmethane as a model of for verification and subsequent optimization of
(1,3diphenylpropane-1,3-dione (Hdbm)): Na[Eu(dbm)4] (
),24 all procedures on the way from the europium complex to the
[(C12H25NMe3)]2[Eu(dbm)4]I ( [(RNEt3)] [Eu(dbm)4] ( ). polyethylene-based composite. Compound was not a single
2), and [(RNEt3)] [Eu(dbm)4]
1
2
We here report a straightforward and efficient route for and
3
2
3
1
2)
,
3
3
The dibenzoylmethane is known as the ligand serving as compound, but a mixture of europium dibenzoylmethanate
efficient light harvesting antenna for Eu ion. Also, the complexes with the [(RNEt3)]+ cations (R = CnH2n+1, n = 18–44).
dibenzoylmethanate complexes of europium exhibit both Synthesis of europium complexes
photoluminescent and triboluminescent properties25-27. The
Complex
1
was prepared by
and were synthesized by the reactions of
) and (RNEt3)+I- (
a
known procedure,24
anionic tetrakis- type of complex was determined by the
general assumption that the using of luminescent complex
containing two parts, namely luminescent anion and cation
with long hydrocarbon chain can prevent the separation of the
polymer and complex and ensure homogeneity of the
composite. The introduction of a long chain cation into the
compounds
with the ammonium salts (C12H25NMe3)+I- (
2
3
1
4
5),
which were prepared by the reaction of dimethyldodecylamine
with CH3I and by the reaction of oligomeric RI mixture with
triethylamine, respectively (Scheme 2). The structure of
(C12H25NMe3)+I- was established by X-ray diffraction (see
Structural studies for details).
tetrakis complexes 2 and 3 should lead to better distribution of
these complexes into PE. The photophysical properties of both
the tetrakis complexes and composites containing these
complexes were studied systematically by optical
spectroscopy. The homogeneity of the distribution of the
luminescent centres in the polymer matrix was controlled by
luminescence intensity mapping
microscopy.
and scanning electron
Scheme 2
It was found that the reaction of oligomeric iodoalkane RI
mixture does not proceed to 100% conversion under typical
conditions of tertiary amine quaternization with alkyl halides29
even upon considerable increase in the reaction time and with
a large excess of Et3N (8 to 20 equivalents). Therefore, samples
of the (RNEt3)+I- salt contained higher iodoalkanes RI as an
irremovable impurity.
Na[Eu(dbm)4]
1. Nd-cat/ Bu2Mg
Et3N
I
CH2
RNEt3
I
H2C
H
2. I2
x
(RI) x = 9 - 22
Polyethylene
[RNEt3] [Eu(dbm)4]
[RNEt3]
[Eu(dbm)4]
Compounds
between complex
upon refluxing in THF. The reaction of
2
and
and the corresponding ammonium salts
with the
3 were synthesized by ion exchange
Scheme 1
1
1
(C12H25NMe3)+I- salt did not give the expected compound,
[(C12H25NMe3)][Eu(dbm)4], but yielded its ate-complex with the
Results and discussion
The tetraalkylammonium salt, (RNEt3)I, was prepared by
the reaction of RI with triethylamine28. Hereinafter,
initial ammonium salt, [(C12H25NMe3)]2[Eu(dbm)4]I (2) instead
R
1
(according to elemental analysis and H NMR data). The NMR
spectrum of the resulting ate-complex was quite informative,
despite the presence of the paramagnetic Eu3+ cation. It is
interesting that the [Eu(dbm)4]- anion behaves as a shift-
reagent relative to the (C12H25NMe3)+ cation, inducing only a
slight line broadening and a small downfield signal shift. As
compared with the initial ammonium salt, (C12H25NMe3)+I-, the
designates a set of CnH2n+1 oligomers with n = 18–44, where n
is an even number (with the weight-average molecular weight
corresponding to n = 30–32). The sample of RI 1-iodoalkanes
used to prepare the ammonium salt was synthesized by
catalytic oligomerization of ethylene followed by treating the
reaction mixture with iodine28 (Scheme 2).
(CH3)3N- signals in the Eu complex 2 have more pronounced
2 | J. Name., 2012, 00, 1-3
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downfield shifts (4.81 ppm vs. 3.47 ppm) than the (CH3)3N-CH2
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-
Structural studies
Although all attempts to obtain single crystals of
unsuccessful we were able to analyze the crystal structures of
(Na+(EtOH)2[Eu(dbm)4]-) and (C12H25NMe3)+I-).
The europium cation in is eight-coordinated and adopts
signals (4.44 ppm vs. 3.63 ppm). The presence of iodide ions
was confirmed by HRMS data (negative ion m/z = 126.9051). A
twofold increase in the reaction time (from 40 to 80 hours) did
not change the composition of reaction products.
2
were
1
4
1
the distorted square antiprism polyhedron. Its distortion and
variation of Eu-O bond lengths (2.346(2)-2.401(2) Å is clearly
the consequence of the cation…anion interactions in crystal.
Indeed, the salt
1 crystallizes as the contact ion pair in which
the coordination number of sodium cation is equal to five and
its sphere is composed of three oxygen atoms of the dbm
ligand that correspond to the same base of the europium
antiprism polyhedron (the Eu(1)….Na(1) distance is 3.381(2) Å),
and of two oxygen atoms of ethanol molecules. The Na…O
distances for oxygen atoms of dbm ligands and ethanol vary in
the ranges 2.339(3)
respectively.
- 2.620(4) and 2.246(5)-2.251(6)Å,
It should be noted that for oxygen atoms of dbm that are
involved in additional coordination with sodium, the Eu-O
distances are systematically longer (av. 2.40 Å) than those
which are not (av. 2.37 Å).
Scheme 3
The reaction of (RNEt3)I (
also carried out by refluxing in THF. The RI impurity present in
the (RNEt3)+I- salt can also react with complex
(see
supplementary materials S2). To control the completeness of
reaction between and , the reaction time was varied from
5) with complex 1 (Scheme 4) was
The above contact ion pairs are assembled in crystal into
the infinite chains by means of O-H…O hydrogens bonds with
O…O separation being equal to 2.806(5) and 2.831(6) Å.
(Fig.2).
1
5
1
50 to 100 hours. After 50 hours of refluxing, the composition
of the reaction products remained unchanged, according to
chemical analysis data.
Fig. 2 The general view of H-bonded chain directed along crystallographic
axis b in crystal of 2
Ph
O
NEt3 I
Na
Eu
H
x
O
Ph
4
x = 9 - 22
1
5
Ph
Ph
O
O
NEt3
x
Eu
H
4
x = 9 - 22
Scheme 4
3
Fig. 1 The general view of 1 in representation of atoms by thermal ellipsoids
(p=50%). The sodium and ethanol molecules with occupancies equal to 0.32
are omitted for clarity
Fig.3 The cation…anion interactions in the crystal of 4
In the crystal of
4 (Figure3), cations form a typical packing,
namely, chains in which the neighboring cations are arranged
in a head-to-tail pattern and are assembled by means of weak
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C-H…I contacts with H…I distances of ca. 3.0 Å. The C12-сhain environments. Moreover all the luminescence decays of the
is characterized by almost all trans-conformations, although excited 5D0 level of the Eu ion were treated as a single
some of C-C-C-C torsion angles are as small as 130-140o.
To some extent, the crystal data for and
the possible structure of the ate-complex
exponential function and the corresponding lifetimes confirm
shed some light on the presence of only one type of the luminescence center for
. For example, in every complex as well (Table 1, Fig. 5).
1
4
2
both salts, contact ion pairs are formed via the Na…O and C-
H…I interactions. Analysis of the CSD30, 31 demonstrates that
ammonium salts of lanthanide-containing anions form similar
contact ion pairs, in which the alkyl substituents at nitrogen
are involved in С-Н...О contacts with oxygens of β-diketonate
ligands, CSD refcodes: (FIDNIP01),32 (FIDNOV),33 (LOLWEQ),
(LOLWIU), (LOLWAM)27 and (GUVWAW).34 The iodide anion in
5D0 - 7FJ, J=0-4
complex
2 can also (by analogy with salt 4) be involved in the
a
additional cation binding, which should considerably change
the charge distribution in the lanthanide coordination sphere
and, hence, should affect the luminescent characteristics of
the lanthanide ion.
Preparation of Composite Films
For the preparation of Eu-containing composites, samples
b
c
1
- 3 were mixed with PE in 1:10 ratio (w/w) by melt mixing
technique using a laboratory micro-extruder. A 0.3 mm-thick
film was formed from the composite materials obtained. The
subsequent measurements were performed with film samples.
Initially, samples of compounds
by TGA and DSC for their thermal stability. According to TGA,
compound is stable up to 200 C and undergoes reversible
phase transition in the temperature range of 45-90 C (Fig. S8).
Compound which was isolated as an ate-complex
[(C12H25NMe3)]2[Eu(dbm)4]I-, starts to decompose at 138
(Fig. S9). Since the film is formed at higher temperature,
evidently, a substantial part of complex may decompose and
contaminate the composite with the products of thermolysis.
Therefore, compound , which was initially intended for the
2 and 3 were investigated
3
°
°
2,
°
C
600
700
2
Wavelength (nm)
2
investigation of the behavior of europium complexes in the
polymer matrix, is inapplicable for modeling of the composite
luminescence base, because of low thermal stability. However,
obtained results are suitable for evaluation of the limitations
of this approach.
Fig. 4 Luminescence spectra of complexes 1 (a), 2 (b) and 3 (c) at 300K,
exc=380 nm
λ
The integrated intensity of this transition is maximum in the
5
case of complex
2 (Table 1, Fig. 5). The electric dipole D0→
7F2
As the luminescent compound introduced into matrix, we
chose the complex [(RNEt3)]+[Eu(dbm)4]-, consisting of the
tetraalkylammonium cation, which meets the compatibility
requirement with the polyethylene matrix, and the [Eu(dbm)4]-
anion, which is expected to ensure high luminescence
Metal-centered luminescence of tetrakis complexes
transition (region 600-620 nm) is extremely sensitive to the
symmetry of the europium surrounding and called
hypersensitive and so the ratio of integrated intensity of the
5D0
measure for the symmetry of the coordination sphere. In a
centrosymmetric environment the magnetic dipole 5D0 7F1
→ →
7F2 transition to one of the 5D0 7F1 transition is a
→
The luminescence spectra of the europium complexes 1-3 transition is dominating and above ratio < 1 while the
were recorded from both ligand-centered excitation at 350 nm distortion of the symmetry around the ion causes an intensity
and metal-based excitation at 465 nm, which give rise to enhancement of the 5D0
→
7F2 transition. In these complexes
similar characteristic Eu3+ emission peaks (Fig. 4). These this ratio equals 15, 28 and 21 for complexes 1-3, respectively,
spectra show the typical narrow bands corresponding to the and indicates relatively strong deviation of the Eu3+ site
Eu3+ 5D0
Stark splittings of the 5D0
strength and symmetry of the ligand filed. A forbidden maximum value obtained for complex
5D0 7F0 transition (region 570-585 nm) of the Eu3+ ion is maximum value of integrated intensity discussed for the
presented by a weak symmetric nondegenerated line in all 5D0
7F0 transition evidences about the strongest deviation of
cases that indicates the presence of only one type of the Eu the site symmetry of the Eu ion from the inversion center. The
→
7FJ (J=0-4) transitions. Generally the intensities and symmetry from the inversion center as well as a highly
→
7FJ transitions are influenced by the polarizability chemical environment around the ion. The
(28) along with
2
→
→
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of medium electron-phonon interaction). The longest
wavelength maximum of this band in the case of complexes
is centered at 400 nm and assigned to the S1 state of
dbm ligand. Vibronic satellites appearing in the excitation
spectra of complexes and are assigned to the symmetric
comparison performed of integrated intensities together with
analysis of fine structure of the luminescence spectra as well
1
as lifetime of 5D0 level of the europium ion point out the and
3
similar site symmetry of the Eu3+ ion in the complexes
The difference observed for all these parameters for the
complex can be explained by the fact that this complex exists
as ate-complex [(C12H25NMe3)]2[Eu(dbm)4]I ( ) and contains
1 and 3.
1
3
2
vibration of the β-diketonate chelating ring with a large
contribution of the C=O bond stretching with a frequency of
1470 cm–1. The longest wavelength band is slightly blue shifted
2
two [RNR3’]+, cations and additional anion (I-). As one was
discussed above, ammonium salts of lanthanide anions can
form tight ion pairs, in which alkyl substituents linked with
nitrogen atom forms the С-Н...О short contacts with oxygen
atoms of the β-diketonate. Previously we have shown that
noncoordinated anions (chlorides and triflates) can effect on
Stark splitings of the electronic transitions of the Eu ion as well
as on the formation charge transfer states which are involved
in the case of complex
broad pedestal in the region 420-500 nm, which is most clearly
observed in the excitation spectrum of complex . This
2 up to 390 nm. It is worth to mention a
3
covered weak band can be tentatively assigned to the charge
transfer state. Generally the energy of charge transfer state is
determined by such parameter as optical electronegativety of
the ligand and so the higher the energy of charge transfer
state the higher the value of this parameter. Taking into
account the structure peculiarities of the complexes one can
conclude that presence of two ammonium cations due to C-
in the Eu luminescence sensitization.35-37
5
The high intensity of the first Stark component of the D0
→
7F2
transition at 300 K potentially can be successfully used for
obtaining a relatively high color purity (for example in complex
H…O interactions and steric repulsion in complex
the elongation of the Eu-Ligand bonds. As a result the optical
electronegativity of dbm is the highest in complex
37, 39, 40 The
2 promotes
1
the line at 610 nm, ~45% of total integrated intensity, fwhm
(full width-at-half-maximum) = 34 cm-1).
The efficiency observed of energy transfer processes in the
2.
tetrakis complexes has been estimated by the calculation of
relatively low energy of this charge-transfer band (its long
wavelength edge is ~20500 cm-1) can be the reason of not very
the intrinsic quantum yield of the europium centered
Eu
,
by means of Werts’ formula.38 In the
L
emission,
Q
high value of the overall absolute quantum yield
.
QLn
Eu
considered europium complexes 1-3 the value of intrinsic
quantum yield is quite similar and equal to 49%, 42% and 63%,
respectively (Table 1) that indicates the intense dependence
on nonradiative deactivation processes as well as on structural
peculiarities as was discussed above. The highest value of the
intrinsic quantum yield is observed in 3 that is also in the line
with the lowest site symmetry of europium surroundings. The
L
overall absolute quantum yield
upon ligand excitation
QLn
was measured for the most luminescent complex
amounts to 26 0.3% and so the efficacy with which
electromagnetic energy is transferred from the surroundings
onto the Eu ion ( sens) amounts to ~55 %.
1 and it
±
η
Table 1 Integrated Intensity Ratios I5D0-7FJ/I5D0-7F1 of electronic transitions (J = 1, 2, 4) in
the luminescence spectra of complexes 1-3 as well as ratios Itot/IMD,0, lifetimes and EuIII
quantum yields
Fig. 5 Photoluminescence decay curves for complexes 1, 2, 3 (ꢀ͙͡
615 nm, ꢀ͙ͬ = 380 nm, T = 300 К
=
Eu
Eu
Lig
Eu
τobs/ms
All prepared polyethylene films exhibit a characteristic
luminescence of the Eu3+ ion with maximum at 610 nm (Fig. 7).
The luminescence spectra of these polyethylene films differ
from the spectra of initial complexes. The observed spectra
suggest that the composite formation has induced some
changes in the coordination sphere of the Eu ion but the
nature of the changes will be the subject of further studies.
Q
Q
± 2%
± 5%
1
2
3
0.04
0.1
15
28
21
1
3
3
18 0.54 ± 0.02 49
33 0.26 ± 0.01 42
26 0.49 ± 0.02 63
26
2.5
10
0.04
The excitation spectra of the europium complexes 1-3
measured at 300 K display in addition to the narrow f-f
7F0, (Fig. 6), a broad band expanded in the
5
transitions D4,2,1,0
←
range 250-500 nm with broadened vibronic structure (a case
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a
a)
b)
b
c
300
400
500
600
Wavelength (nm)
Fig. 6 Luminescence excitation spectra of complexes 1 (a), 3 (b) and 2 (c) at
300K, λreg=612 nm
с)
d)
Fig. 8 Images of luminescence intensity mapping (ꢀ =620 nm, ꢀ =375 nm),
͙͡
͙ͬ
Sample sizes 80x80 μm. Composite films: a) PE – 3 (10%), b) PE –3 (1%), с)
PE – 1 (10%), d) PE – 2 (10%).
5D0 - 7FJ, J=0-4
Comparison of the luminescence intensity mapping results
(Fig. 8) for films made of the three composite materials (PE–3
(a), PE–
distribution of the luminescent dopant in PE has been attained
for the composite based on (Fig. 8 (a)). The use of inorganic
complex (Fig. 8 (c)) gives rise to a considerable film
inhomogeneity, while the use of (Fig. 8 (d)) results in the
1 (c), PE–2 (d)) indicates that the most homogeneous
a
3
1
2
b
formation of aggregates in which the luminescent dopant is
concentrated. The latter may be attributable to the formation
of micelle-like aggregates in the composite containing
2. In the
composite doped with , the formation of such aggregates is
3
prevented by inhomogeneity of the [RNEt3]+ cations, which
differ in the chain length of the organic group R, or because its
hydrocarbon chain is (on average) much longer. One more
c
600
700
possible reason for the inhomogeneous distribution of
2 is its
Wavelength (nm)
noticeable thermal decomposition during the film formation
caused by low thermal stability of the complex. The film with a
Fig. 7 Luminescence spectra of PE films doped by 10% of complexes 2 (a),
3(b) and 1 (c) at 300 K
lower europium content (1% of
3) obtained by dilution of the
PE–10% 3 was also characterized by
a
homogeneous
distribution of luminescence centers over the film area (Fig. 8
(b)).
Of the most interest was to elucidate the homogeneity of the
europium distribution in the polymer matrix. Luminescence
intensity mapping experiments (Fig. 8а) demonstrated a
homogeneous distribution of the luminescence centers in the
PE matrix.
The SEM images of composite film surfaces (Fig. 9) also show a
marked inhomogeneity of the composites prepared using
, as compared with the film made of the composite doped
with
1 or
2
3.
6 | J. Name., 2012, 00, 1-3
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a small amount of lanthanide complexes (10 mol-%) can be
highly luminescent.
To improve the photophysical characteristics of the
composite within the proposed methodology, it is necessary to
optimize the synthesis of alkylammonium salt used, and to test
other lanthanide complexes concerning the thermostability of
luminescent compound.
a)
b)
c)
Experimental
General details
Tetrahydrofuran and diethyl ether were predried over NaOH
and distilled from potassium/benzophenone ketyl. Hexane was
distilled from Na/K alloy. Na[Eu(dbm)4](C2H5OH)2 (1
),24 were
prepared according to the literature procedures, synthesis of
oligomer mixture “RI” (was performed according to published
procedure28 with some modifications, described in
supplementary materials (S 1). The matrix polymer used to
prepare the composite was PE, Мw=3·105, Мn=1·105, d=0.940
g/cm3, Mp. = 126˚С. Metal analyses were performed by direct
complexometric titrations with EDTA-disodium salt, using
Xylenol Orange indicator. TGA analyses were conducted using
ТGA/DSC1 Mettler Toledo system at a rate of 10 K/min under
argon flow of 10 mL/min in the range from 303 K to 673 K.
Standard differential scanning calorimetry (DSC) thermograms
were recorded on a DSC823 Mettler Toledo system at a rate of
10 K/min under argon atmosphere in the range from 293 K to
553 K. The 1H NMR spectra of were recorded with Bruker
AV400 (400MHz) or Bruker AV600 (600 MHz) instruments in
CDCl3. MALDI mass spectra were recorded with a Bruker
autoflex speed instrument in positive ion reflectron mode
using a solid-state UV-laser (λ=355 nm). ESI mass spectra were
recorded with a MALDI-TOF Bruker ultraflex III.
Fig. 9 SEM images of composite films: a) PE – 3 (10%), b) PE – 1 (10%), c) PE –
2
(10%)
X-ray crystallography
Conclusions and outlooks
X-ray diffraction data were collected on a APEX II DUO CCD
diffractometer using molybdenum radiation [λ(MoKα) =
0.71072 Å, ω-scans] for and . The substantial redundancy in
To find a straightforward route to the PE-compatible
complexes of rare earths, the reaction of alkylammonium
iodides (RNR’3)+I, (R = CnH2n+1, n = 18÷44) with Na[Eu(dbm)4]
was applied and led to the exchange of sodium with organic
cation, containing a long linear hydrocarbon chain.
1
4
data allowed empirical absorption correction to be applied
with SADABS by multiple measurements of equivalent
reflections. The structures were solved by direct methods and
refined by the full-matrix least-squares technique against F2 in
the anisotropic-isotropic approximation. Assuming the
The chosen approach allows to introduce a long linear
hydrocarbon chain into the lanthanide complex, possessing
the desired photophysical properties. This finding provided
high compatibility with polyethylene and allowed to obtain
polyethylene based optical composite materials with pre-
determined properties.
proximity of β angle in
1 to 90° upon the refinement it was
treated as the merohedral twin (monoclinic cell emulating
orthorhombic one). The usage of TWIN -1 0 0 0 -1 0 0 0 1
instruction lead to the BASF parameter being equal to 0.39832
and to significant decrease of R1 value. In the case of
4 despite
A high degree of homogenity in the distribution of the
luminescent centers in polyethylene has been achieved by the
proposed method. The developed procedure opens up the way
to obtain the composite materials emitted in different regions
of the spectrum from visible (Tb, Sm, Dy ions) to NIR part (Nd,
Yb, Er ions) by using the different lanthanide ions. Moreover,
unlimited row of existed lanthanide complexes also allows
optimizing the optical properties of forthcoming luminescent
composite materials based on polyethylene and, that is very
attractive for practical applications, these materials containing
of pseudosymmtery (P21/m space group) we have solved it and
refined in P21. The choice of the latter space group was due to
the significant deviation from planarity for C12-chain (see
torsion angles) as well as due to unrealistic anisotropic
displacement parameters of carbon atoms in the case of
P21/m. space group
The positional and anisotropic displacement parameters of the
disordered Na(HOC2H5)2 fragment in
1 (see Fig. S3 in
Supplementary Information) were refined with the constraints
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Journal Name
on the O-C and C-C bond length (DFIX) and anisotropic dry ethanol and dried under dynamic vacuum for 30 min. The
displacement parameters (EADP).
yield 10.350 g (96%).
MS MALDI-TOF [m/z (I/I0)]: found for C15H34N+: 228.26 (100%),
229.27 (22%), 230.28 (2%). Calcd.: 228.27 (100.0%), 229.27
Table 2 Crystal data and structure refinement parameters for 1 and 4.
1
(17%), 230.28 (1%). NMR H (600 MHz, CDCl3), δ: 0.88 (t, 3H, -
1
C64H56EuNaO10
1160.03
120
4
Brutto formula
Formula weight
T, K
C15H34IN
355.33
120
P21
2(1)
5.7367(6)
7.4012(8)
21.041(2)
91.012(2)
893.25(17)
1.321
CH2CH3), 1.26 (br. s, 14H, -NC3H6 –C8H16-CH3), 1.28 (m, 2H, -
NC2H4-CH2-C8H17), 1.77 (m, 2H, -NCH2CH2-) 3.47 (s, 9H, -
N(CH3)), 3.63 (m, 2H, -NCH2-).
Space group
Z(Z’)
a/Å
P21/c
4(1)
RNEt3I RI (3.288 g), Et3N (2.80 mL, 20.1 mmol), and
anhydrous ethanol (150 mL) were placed into a 250 mL round-
bottomed flask and stirred under reflux for 12 h in an argon
atmosphere. Et3N (2.80 mL, 20.1 mmol), and anhydrous
ethanol (50 mL) were added. The reaction mixture was stirred
reflux for additional 10 h under argon. The solvent was
removed on a rotary evaporator. The residue was washed with
diethyl ether (2 x 15 mL), (30 mL), hexane (3 x 60 mL), and
dried under vacuum. The yield 1.819 g. According to the 1H-
NMR spectrum ca. 70% conversion of RI was observed.
MALDI-TOF detected ions Et3N+(CH2-CH2)nH with n=9-22 (with
the highest peaks for n=13-16). Mn=526, Mw=536. (Figure
25.835(2)
8.3357(8)
25.370(2)
90.1060(19)
5463.3(9)
1.410
b/Å
c/Å
β/°
Volume/Å3
ρcalcg/cm3
μ/cm-1
12.16
2376
58
17.79
368
17.79
14807 (0.0378)
F(000)
2θmax, °
Reflections collected 55473 (0.0554)
(Rint
)
Independent
reflections
Reflections with
4748
4266
1
14499
12081
S10) NMR H (400 MHz, CDCl3), δ: 0.85 (t. -CH2CH3), 1.24 (br. s
–(CH2)n-CH3), 1.39 (t, -N(CH2-CH3))3), 1.70 (m, -NCH2-CH2-), 1.80
(m., 4H, I-CH2-CH2-), 3.17 (t, I-CH2-), 3.25 (br. m, -N-CH2-), 3.50
(q. , -N(CH2-CH3))3).
I>2
Parameters
R1 [I>2 (I)]
σ(I)
710
160
The product may contain an admixture of linear low molecular
weight polyethylene, which is difficult to trace due to
overlapping of signals at the NMR-spectrum.
0.0276
0.0622
1.040
0.0381
0.0824
0.977
σ
wR2
GOF
Residual electron
density, e·Å-3
[C12H25NMe3]2[Eu(dbm)4]I Na[Eu(dbm)4](C2H5OH)2 (0.575 g
0.5 mmol), (C12H25NMe3)I (0.176 g 0.5 mmol), dry THF (50 mL)
were placed in 100 mL Schlenk flask and stirred under reflux
for 40h in an argon. Solution was evaporated under vacuum
and solid residue was extracted with CH2Cl2. Extract was
filtered through a celite pad and evaporated under vacuum.
The residue was stirred with 20 mL of hexanes and then
centrifuged. The residual solids were dried under vacuum,
-0.460/ 0.752
-1.001/1.336
(
ρmin/ρmax )
The occupancies for Na(1) and Na(1’) atoms were equal to
0.680(3) and 0.320(3) respectively. C-H hydrogen atoms in all
structures were placed in calculated positions and refined
within the riding model. Hydroxy H-atoms in
1 were located
from the Fourier density synthesis. All calculations were
performed with the SHELXTL software package.41 Crystal data
and structure refinement parameters are listed in Table 2.
Crystallographic data for the structures reported in this paper
have been deposited to the Cambridge Crystallographic Data
yielded 0. 442 g (2) C90H112EuIN2O8 (1628.73) calculated: C,
66.37; H, 6.93; N, 1.72; Eu, 9.33; found: C, 62.77; H, 5.83; N,
1.21; Eu, 10.10.
ESI-MS [m/z (I/I0)]: (+ve) 228.268 (100%)
338.341(6%), 449.127 (7%)
(C15H34N+),
Centre as supplementary no.: CCDC- 1567021 (for
1) and
ESI-MS [m/z (I/I0)]: (-ve) 126.905 (100%) (I-), 223.076 (13%),
255.233 (15%), 281.248 (10%), 355.095 (11%).
CCDC- 1567020 (for 4). These data can be obtained free of
charge from The Cambridge Crystallographic Data via
www.ccdc.cam.ac.uk/data_request/cif.
Syntheses
1H NMR (500 MHz, CDCl3), δ: 0.92 (br. s, 6H, -CH2CH3), 1.31
(br. s, 28H, -NC4H8 –C7H14-CH3), 1.43 (br. s, 4H, -NC3H6-CH2-
C8H17), 1.61 (br. s, 4H, -NC2H4-CH2-C9H19), 2.19 (br. s, 4H, -
NCH2-CH2-), 4.44 (br. m, 4H, -NCH2-), 4.81 (br. s, 18 H, -N(CH3)),
7.00-7.20 (m. 20H), 7.35-7.60, (m. 20H); 13C NMR (150.9 MHz,
CDCl3), δ: 13.6596, 22.2241, 23.3479, 26.0541, 28.9025,
29.1870, 31.4607, 54.8117, 67.6191, 125.52, 125.85, 126.66,
128.19, 130.23, 181.33, 185.28.
n-C12H25NMe3I Vacuum distilled n-C12H25NMe2 (6.438 g,
30.17 mmol), freshly distilled CH3I (11.0 mL, 177 mmol), and
anhydrous ethanol (100 mL) were placed into a 250 mL round-
bottomed flask. The reaction mixture was stirred under reflux
for 15 h under argon. Additional amount of CH3I (5.0 mL,
80 mmol) was added. The mixture was then stirred under
reflux for 10 h. CH3I and ethanol were removed on a rotary
evaporator. Water (80 mL) was added to the solid residue. The
product was extracted with dichloromethane (6 x 50 mL). The
organic layer was dried over anhydrous Na2SO4. Almost all
CH2Cl2 was removed on a rotary evaporator. The precipitate
formed was separated from the solution and washed with
diethyl ether (2 x 15 mL), hexane (30 mL), recrystallized from
[RNEt3][Eu(dbm)4] Na[Eu(dbm)4](C2H5OH)2 (1.045 g 0.90
mmol), RNEt3I 0.652 g (approx. 0.98 mmol), dry THF (50 mL)
were placed in a 100 mL Schlenk flask and reaction mixture
was stirred under reflux for 50h under argon. Solution was
evaporated under vacuum and solid residue was extracted
with CH2Cl2. The extract was filtered through the celite pad
and evaporated under vacuum. The solid residue was
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n the refractive index, Itot the total area of the emission
spectrum (5D0 7FJ, J = 0-6), and IMD,0 the 5D0 7F1 band area.38
triturated with hexane and dried under vacuum. 0.915g of 3
were obtained as yellowish powder.
→
→
ESI MS detected ions Et3N+(CH2-CH2)nH with n=12-20 (the
highest peaks for n=15-16), negative range: ESI-MS [m/z (I/I0)]:
(-ve) 126.905 (100%) (I-), 223.076 (13%), 255.233 (15%),
281.248 (10%), ESI-MS and NMR spectra are presented at
supplementary section Fig. S13, Fig. S6 and S7, respectively.
Elemental analysis: Found: C, 63.70; H, 6.98; N, 0.56; Eu, 9.48,
the difference in the results of the analysis between samples
from two independent synthetic experiments did not exceed
0.5%.
The refractive index was taken as 1.5 for all cases.
Luminescence intensity mapping experiments were carried out
with the use of a MicroTime 200 time-correlated single photon
counting system (PicoQuant, Germany) coupled to an inverted
fluorescent microscope IX71 (Olympus, Japan). The samples of
flat films were placed on the microscope stage and excited by
PDL 828 pulsed laser (376 nm emission, 50 ps pulse duration,
100 kHz pulse repetition rate). Emission spectral band was
selected by interference band-pass filters (Chroma, USA) with
a bandwidth of 10 nm. The filter band was centered at 620 nm.
Preparation of the composite and composite films
Composites PE-1, PE-2 and PE-3 were prepared by a single-
Luminescent signal was acquired by τ-SPAD photon-counting
stage mixing in a melt under the action of shear stresses. The
laboratory twin-screw micro-extruder HAAKE MiniLab
Rheomex CTW5 was loaded with PE 4.500 g and 0.500g of
corresponding europium complexes. The mixing was carried
avalanche photodiode and a PicoHarp 300 correlation system
of the MicroTime 200. Horizontal positioning accuracy of the
piezopositioner mounted into the microscope stage was about
10 nm. Spatial resolution of 300 nm was achieved with the use
of the confocal scheme together with a UPlanSApo 100
microscope objective. The maximum size of the region of
interest (ROI) was 80*80 microns.
out at a temperature of 155
° C and at screw speed of 100
rpm for 15 minutes. The composite with a lower content of Eu
(1% of 3) was obtained by "diluting" of PE-3 Eu with
polyethylene to the required concentration. After unloading
from the extruder, the composites were pressed on a press
with heating plates at a temperature of 155 C and a pressure
of 5 MPa for 5 minutes, and then were cooled in air.
Composite films with a diameter of ca. 5 cm and a thickness of
0.3 mm were obtained.
Conflicts of interest
There are no conflicts to declare.
Scanning Electron Microscopy
Acknowledgements
Target-oriented approach was utilized for the optimization of
the analytic measurements.42 Before measurements the
samples were mounted on a 25 mm aluminum specimen stub,
fixed by conductive silver paint and coated with a thin film (15
nm) of carbon. The observations were carried out using Hitachi
SU8000 field-emission scanning electron microscope (FE-SEM).
Images were acquired in backscattered electron mode at 15 kV
accelerating voltage and at working distance 10-11 mm.
Morphology of the samples was studied taking into account
possible influence of carbon coating on the surface.
This research was supported by Russian Science Foundation (grant
No. 17-13-01357). The authors are grateful to the Department of
Structural Studies of Zelinsky Institute of Organic Chemistry,
Moscow, for Electron microscopy characterization. The X-ray
diffraction and optical data were obtained using the equipment of
Center for molecules composition studies of INEOS RAS.
Photo-physical study
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Eu-doped luminescent composite material based on polyethylene have been developed and studied by
the optical spectroscopy, luminescence intensity mapping, SEM