VISIBLE AND NEAR INFRARED EMISSION OF POLYMER MATERIALS CONTAINING PORPHYRIN AND ITS YTTERBIUM DERIVATIVE
A series of porphyrin containing polymer materials of various structure was developed. Free 5-(p-aminophenyl)-10,15,20-triphenylporphyrinand its ytterbium derivative were used to prepare materials of different structure and they were obtained by different approaches.Thus, two polymers were used in t...
Збережено в:
| Дата: | 2024 |
|---|---|
| Автори: | , , , , , |
| Формат: | Стаття |
| Мова: | Англійська |
| Опубліковано: |
V.I.Vernadsky Institute of General and Inorganic Chemistry
2024
|
| Онлайн доступ: | https://ucj.org.ua/index.php/journal/article/view/641 |
| Теги: |
Додати тег
Немає тегів, Будьте першим, хто поставить тег для цього запису!
|
| Назва журналу: | Ukrainian Chemistry Journal |
| Завантажити файл: |  |
Репозитарії
Ukrainian Chemistry Journal| _version_ | 1871466026069131264 |
|---|---|
| author | Semenishyn, Nikolay Rusakova, Nataliia Smola, Serhii Linnyk, Valeriia Kiose, Olesya Savin, Serhii |
| author_facet | Semenishyn, Nikolay Rusakova, Nataliia Smola, Serhii Linnyk, Valeriia Kiose, Olesya Savin, Serhii |
| author_institution_txt_mv | [
{
"author": "Nikolay Semenishyn",
"institution": "A.V. Bogatsky Phys.-Chem. Institute NAS of Ukraine"
},
{
"author": "Nataliia Rusakova",
"institution": "A.V. Bogatsky Physico-Chemical Institute of the National Academy of Sciences of Ukraine"
},
{
"author": "Serhii Smola",
"institution": "A.V. Bogatsky Physico-Chemical Institute of the National Academy of Sciences of Ukraine"
},
{
"author": "Valeriia Linnyk",
"institution": "A.V.BogatskyPhysico-chemical Institute, National Academy of Sciences of Ukraine"
},
{
"author": "Olesya Kiose",
"institution": "I.I. MechnikovOdesa National University"
},
{
"author": "Serhii Savin",
"institution": "I.I. MechnikovOdesa National University"
}
] |
| author_sort | Semenishyn, Nikolay |
| baseUrl_str | https://ucj.org.ua/index.php/journal/oai |
| collection | OJS |
| datestamp_date | 2026-07-22T08:23:53Z |
| description | A series of porphyrin containing polymer materials of various structure was developed. Free 5-(p-aminophenyl)-10,15,20-triphenylporphyrinand its ytterbium derivative were used to prepare materials of different structure and they were obtained by different approaches.Thus, two polymers were used in this study – the poly(methyl methacrylate) (PMMA), polystyrene (PS) as well as their copolymers of different composition (the molar ratio of 0.25/0.75, 0.5/0.5 and 0.75/0.25). Also part of materials were obtained by coprecipitation of polymer(s) with corresponding porphyrin derivative. The latter material ismore transparent, which allows obtaining an absorption spectrum with good resolution. All materials have notable emission characteristics – they emit in visible or near infrared (IR) range. Increasing of PMMA content in the final material causes the increase of fluorescence quantum yield for bothcopolymers and coprecipitatedmaterials.It can be explained by a higher light transmission coefficient of PMMA compared to PS.It was found out that 4f-luminescence in ytterbium-containing materialsdoes not depend on the type of polymer matrix and the variability of its compositionin contrast to fluorescence in the visible range.Almost 100% transparency of the studied polymers in the area of ytterbium ion radiation (980 nm)explains this phenomenon. It was also shown that obtainedmaterialsarestablefora long period of time and they keep the permanence oftheir emission parameters.This phenomenon can be explained by the extraordinary stability of PMMA even to UV radiation and by the high stability of porphyrin molecules. The use of a low concentration (0.1%) of lanthanide-porphyrin in the final material allows the IR emission efficiency of the Yb(III) ion to remain at the same level as in the corresponding methanol solution. |
| doi_str_mv | 10.33609/2708-129X.90.2.2024.81-90 |
| first_indexed | 2025-09-24T17:43:55Z |
| format | Article |
| fulltext |
81
UDC 535.372:541.49:546.65 doi: 10.33609/2708-129X.90.2.2024.81-90
VISIBLE AND NEAR INFRARED EMISSION OF POLYMER
MATERIALS CONTAINING PORPHYRIN AND
ITS YTTERBIUM DERIVATIVE.
N.N. Semenishyn*1, V.V. Linnyk1,2, S.S. Smola1, O.O. Kiosse2, S.N. Savin2, N.V. Rusakova1
1A.V. Bogatsky Physico-Chemical Institute, National Academy of Sciences of Ukraine,
86 Lustdorfs’ka doroga, 65080 Odesa, Ukraine;
2I.I. Mechnikov Odesa National University,
2 Vsevoloda Zmiienka St, 65082 Odesa, Ukraine
*email: ssmbikola@yahoo.com
A series of porphyrin containing polymer materials of various structure was developed.
Free 5-(p-aminophenyl)-10,15,20-triphenylporphyrinand its ytterbium derivative were used
to prepare materials of different structure and they were obtained by different approaches.
Thus, two polymers were used in this study – the poly(methyl methacrylate) (PMMA), poly-
styrene (PS) as well as their copolymers of different composition (the molar ratio of 0.25/0.75,
0.5/0.5 and 0.75/0.25). Also part of materials were obtained by coprecipitation of polymer(s)
with corresponding porphyrin derivative. The latter material ismore transparent, which allows
obtaining an absorption spectrum with good resolution. All materials have notable emission
characteristics – they emit in visible or near infrared (IR) range. Increasing of PMMA content
in the final material causes the increase of fluorescence quantum yield for bothcopolymers
and coprecipitated materials.It can be explained by a higher light transmission coefficient
of PMMA compared to PS.It was found out that 4f-luminescence in ytterbium-containing
materialsdoes not depend on the type of polymer matrix and the variability of its composi-
tionin contrast to fluorescence in the visible range.Almost 100% transparency of the studied
polymers in the area of ytterbium ion radiation (980 nm)explains this phenomenon. It was
also shown that obtainedmaterialsare stablefora long period of time and they keep the perma-
nence oftheir emission parameters.This phenomenon can be explained by the extraordinary
stability of PMMA even to UV radiation and by the high stability of porphyrin molecules.
The use of a low concentration (0.1%) of lanthanide-porphyrin in the final material allows the
IR emission efficiency of the Yb(III) ion to remain at the same level as in the corresponding
methanol solution.
Keywords: polymers; lanthanides; porphyrins; fluorescence; 4f-luminescence.
82 ISSN 2708-129X. Укр. хім. журн., 2024
VISIBLE AND NEAR INFRARED EMISSION OF POLYMER MATERIALS CONTAINING PORPHYRIN AND
ITS YTTERBIUM DERIVATIVE.INORGANIC CHEMISTRY
INTRODUCTION. Tetrapyrrole derivati
ves such as porphyrins, phthalocyanines and
porpholactones are highly stable macrocyclic
compounds that play an important role in
many biochemical phenomena related to the
development of life [1–3]. Their complexes
with lanthanides have special properties, such
as paramagnetism, nonlinear optical parame
ters and intense light emission in the visible
and near-IR ranges[4]. Many studies focuses
on their bioimaging capabilities and as sensors.
[5]. Also, recently there has been an increase
of works devoted to the sensitization of lan-
thanide ions emitting in the near-IR region of
the spectrum [6–8]. In addition, IR radiation
is an extremely effective tool for protecting
securities and banknotes from counterfeiting
[9]. The increase in the quantum yield of 4f-lu-
minescence of Yb(III)-tetrapyrrole complexes
in the IR range achieved in recent years[10]
reflects the viability of these studies and open
up opportunities for their use not only in the
medical and biological aspect, but also as ma-
terials for optoelectronics.
In the modern context, porphyrin polymers
are widely used to solve different problems in
various fields of science and technology [11–
13]. Immobilization of porphyrins on a poly-
mer provides several advantages that are not
present in free compounds. Among them, it is
worth noting cooperative interactions in po
lymer chains, separation of active centers, the
possibility of specific binding of various sub-
strates on active centers, increasing the stabi
lity of tetrapyrrole pigment, as well as reducing
its toxicity relative to biological environments.
These systems are promising as highly se-
lective catalysts, organic semiconductors, po
lymer films with high electrical conductivity,
light-sensitive materials for recording holo-
graphic images, as well as sensors for oxygen
and toxic gases [14, 15]. Currently, medicine
and pharmacology are among the promising
fields of application of porphyrin polymers. In
recent years, therehas appeared an information
about the possibility of using polymer porphy-
rin systems for the diagnosis and treatment of
various forms of cancer, disinfection of blood
and its components from pathogenic viruses,
as well as as artificial oxygen carriers [16].
One of the main classification features of
systems formed by high molecular weight
compounds and porphyrins is the method of
binding tetrapyrrole macrocycles to the carrier
polymer. According to this feature, two large
groups of polymer-bound systems are distin-
guished: physically fixed and chemically bound
porphyrins.Porphyrins, which are chemically
bound to the polymer, are of particular interest
from the point of view of stability of polymer
systems, specific properties and variety of ap-
plications [17].
EXPERIMENT AND DISCUSSION OF THE
RESULTS. Monoaminotetraphenylporphyrin
(H2аtpp) was used as a starting porphyrin to
obtain a complex with Yb(III) ions, as well as a
component of polymeric materials.The synthe-
sis of the complex was carried out according to
the improved method in the medium of boil-
ing imidazole, which ensured easier isolation
and high yields of the complexes.
Scheme 1 – Structure of studied porphyrins.
Scheme 1 – Structure of studied porphyrins.
The radical polymerization method was used to make samples in the form of films: a solution
of porphyrin or metalloporphyrin was prepared in freshly distilled methylmethacrylate with a
concentration of 10-3 mol/l and 0.01 mol/l of benzoyl peroxide was added.The polymerization
process was carried out for 2–3 hours at a temperature of 70–80 °C.Based on measurements of area,
density and mass, their thickness was calculated.This technique allowsobtaining films with a
thickness from 5 to 1000 μm; films with a thickness of 10 μm were used for spectral analysis.
Attempts to synthesize the Yb-atpp copolymer failed.Complex is demetalated because of the
action of benzoyl peroxide, so IR luminescence will no longer be observed in the final material.
Spectra of molecular fluorescence, 4f-luminescence and excitation spectra were recorded on a
spectrofluorimeter "Fluorolog FL 3–22" ("Horiba JobinYvon") using 450 W Xe-lamp. Spectra of 4f-
luminescence of Yb(III) complexes were registered in 900–1100 nm range (transition 2F5/2→2F7/2).
Spectra of molecular fluorescence of porphyrins were registered at 550–800 nm (S1-S0 transitions).
Integral intensity of luminescence was measured using software of the device. The relative quantum
yield of molecular fluorescence (φML) was determined using solution of Zn-tpp (H2tpp – 5,10,15,20-
tetraphenylporphyrin) in ethanol as a primary standard (0.022). Determination of the φML (accuracy is
±10%) was made using formula:
ΦML= φ0IxA0nx
2/(I0Axn0
2),
where φ0 and φх – luminescence quantum yield of the standard and of the sample respectively,
A0 and Ax – absorption at the wavelength of Soret band of the standard and of the sample
respectively,
Ix and I0 – integral luminescence intensity of the standard and of the sample respectively,
n0 and nx – refractive index of the standard medium and of the sample medium respectively.
Technologies for producing materials, which can emit in a given range and given intensity or
capable of transforming light from one range to another, require polymer matrices of high strength
and photostability. An important aspect is that almost all technologies require the optical
83https://ucj.org.ua
N.N. Semenishyn, V.V. Linnyk, S.S. Smola, O.O. Kiosse, S.N. Savin, N.V. Rusakova UCJ № 2 / Vol. 90
The radical polymerization method was
used to make samples in the form of films: a
solution of porphyrin or metalloporphyrin
was prepared in freshly distilled methylmeth-
acrylate with a concentration of 10-3 mol/l and
0.01 mol/l of benzoyl peroxide was added. The
polymerization process was carried out for
2–3 hours at a temperature of 70–80 °C. Based
on measurements of area, density and mass,
their thickness was calculated.This technique
allowsobtaining films with a thickness from
5 to 1000 μm; films with a thickness of 10 μm
were used for spectral analysis.
Attempts to synthesize the Yb-atpp copoly-
mer failed.Complex is demetalated because of
the action of benzoyl peroxide, so IR lumines-
cence will no longer be observed in the final
material.
Spectra of molecular fluorescence, 4f-lumi-
nescence and excitation spectra were recorded
on a spectrofluorimeter “Fluorolog FL 3–22”
(“Horiba JobinYvon”) using 450 W Xe-lamp.
Spectra of 4f-luminescence of Yb(III) com-
plexes were registered in 900–1100 nm range
(transition 2F5/2→
2F7/2). Spectra of molecular
fluorescence of porphyrins were registered at
550–800 nm (S1-S0 transitions). Integral in-
tensity of luminescence was measured using
software of the device. The relative quantum
yield of molecular fluorescence (φML) was de-
termined using solution of Zn-tpp (H2tpp –
5,10,15,20-tetraphenylporphyrin) in ethanol
as a primary standard (0.022). Determination
of the φML (accuracy is ±10%) was made using
formula:
ΦML= φ0IxA0nx
2/(I0Axn0
2),
where φ0 and φх – luminescence quantum yield of
the standard and of the sample respectively,
A0 and Ax – absorption at the wavelength of Soret
band of the standard and of the sample respectively,
Ix and I0 – integral luminescence intensity of the
standard and of the sample respectively,
n0 and nx – refractive index of the standard medi-
um and of the sample medium respectively.
Technologies for producing materials,
which can emit in a given range and given in-
tensity or capable of transforming light from
one range to another, require polymer matrices
of high strength and photostability. An impor-
tant aspect is that almost all technologies re-
quire the optical transparency of the final po
lymer product. The absence of color is achieved
by the introduction of modifiers for some po
lymers, but, for example, the polymethyl meth-
acrylate (PMMA)homopolymer retains optical
transparency in the visible and part of the UV
and IR ranges of light without the addition of
any components, so it is an interesting model
polymer matrix for the construction of photo-
active materials.
PMMA, polystyrene (PS) and a copoly-
mer of PS with PMMA in the molar ratio of
0.25/0.75, 0.5/0.5 and 0.75/0.25 were studied as
polymer matrices in the work for the manufac-
ture of thin films with a thickness of 10 μm.
Thin-layer films for the study of porphy-
rin-sensitized 4f-luminescence in a polymer
matrix were obtained from PMMA containing
such porphyrin derivatives as: 5-(p-aminophe-
nyl)-10,15,20-triphenylporphyrin and its com-
plex with the Yb(III) ion (acetylacetonate in as
an axial ligand).
The most interesting results were obtained
on PMMA films, and the advantages of this
material can be highlighted as follows: 1. Resis
tance to UV radiation and high transmittance:
PMMA polymer has a high light transmittance
(92%), which exceeds the indicators of other po
lymer materials. Its resistance to UV radiation
84 ISSN 2708-129X. Укр. хім. журн., 2024
VISIBLE AND NEAR INFRARED EMISSION OF POLYMER MATERIALS CONTAINING PORPHYRIN AND
ITS YTTERBIUM DERIVATIVE.INORGANIC CHEMISTRY
makes it effective for applications exposed to
solar radiation. 2. Filtration of hard ultravio-
let light: Polymethyl methacrylate does not
transmit ultraviolet light at wavelengths below
300 nm, similar to ordinary glass. 3. Infrared
light: Polymethyl methacrylate transmits in-
frared light up to 2,800 nm and blocks longer
wavelength infrared light up to 25,000 nm,
making it excellent for applications involving
near-IR radiation zones. 4. Wide application:
Compared to materials like polystyrene and
polyethylene, PMMA is widely used for out-
door applications due to its optical properties
and resistance to environmental influences.
Copolymers
The given properties of the obtained modi
fied films are especially valuable considering
the fact that porphyrins are very stable macro-
cyclic compounds due to the 18π-aromatic sys-
tem, which is a strong argument for obtaining
materials with excellent operational charac-
teristics and shelf life. In addition, due to high
molar absorption coefficients, the required
concentration of porphyrins in the starting ma-
terial is extremely low, which ensures its avai
lability. Note, that the nature of the matrix and
the method of preparation affect the emission
characteristics, as can be seen from the data in
the Table 1. For example, the samples of lan-
thanide-porphyrin copolymersfilms actually
do not contain Yb complexes, instead they are
only porphyrin-containing because of deme
talation (control of UV-vis absorption spectra)
and their characteristics are almost the same as
for the corresponding materials with H2atpp.
The properties of materials H2atpp-
PMMA, H2atpp-PS and copolymer materials
1 (PMMA/PS = 0.25/0.75), 2 (PMMA/PS =
0.5/0.5), 3 (PMMA/PS= 0.75/0.25) are shown
in Table 1. Note, that the final materials, which
obtained under copolymerization conditions
are not perfectly transparent, therefore, unlike
solutions, the absorption spectrum of the final
material cannot be recorded with good reso-
lution and its observable profile actually con-
sists of the two most intense bands with maxi-
ma at approximately 420 nm (Soret band) and
516 nm (fourth Q-band).
Table 1.
Photophysical parameters of copolymer materials (298 K, C=1×10-5M).
Compound λabs, nm λF, nm ES1,cm -1 φF×102*
H2аtpp-PS 420,516 654 15290 6
1 420,514 655 15270 7
2 419,514 653 15310 7
3 419,514 653,720 15310 7
H2аtpp-PMMA 419,514 653,718 15310 8
Yb-аtpp-PS 420,516 – 15290 6
Yb-1 420,514 – 15270 8
Yb-2 419,514 – 15310 8
Yb-3 419,514 – 15310 10
Yb-аtpp-PMMA 419,514 – 15310 11
* ± 10%
85https://ucj.org.ua
N.N. Semenishyn, V.V. Linnyk, S.S. Smola, O.O. Kiosse, S.N. Savin, N.V. Rusakova UCJ № 2 / Vol. 90
For porphyrin-containing films, the ratio
of intensities of both bands of molecular flu-
orescence (MF) in the spectrum profile is pre-
served despite the variability of the composi-
tion of PS and PMMA in the copolymer. Also,
which is very important, a weak hyperchromic
shift of both MF bands is observed when the
PMMA component increases. The increase in
the quantum yield in the sequence 1<2<3 can
be explained by a higher light transmission co-
efficient for PMMA compared to PS.
transparent, therefore, unlike solutions, the absorption spectrum of the final material cannot be
recorded with good resolution and its observable profile actually consists of the two most intense
bands with maxima at approximately 420 nm (Soret band) and 516 nm (fourth Q-band).
Table 1.
Photophysical parameters of copolymer materials (298 K, C=1×10-5M).
Compound λabs, nm λF, nm ES1,cm -1 φF×102*
H2аtpp-PS 420,516 654 15290 6
1 420,514 655 15270 7
2 419,514 653 15310 7
3 419,514 653,720 15310 7
H2аtpp-PMMA 419,514 653,718 15310 8
Yb-аtpp-PS 420,516 – 15290 6
Yb-1 420,514 – 15270 8
Yb-2 419,514 – 15310 8
Yb-3 419,514 – 15310 10
Yb-аtpp-PMMA 419,514 – 15310 11
* ± 10%
For porphyrin-containing films, the ratio of intensities of both bands of molecular
fluorescence (MF) in the spectrum profile is preserved despite the variability of the composition of
PS and PMMA in the copolymer. Also, which is very important, a weak hyperchromic shift of both
MF bands is observed when the PMMA component increases. The increase in the quantum yield in
the sequence 1<2<3 can be explained by a higher light transmission coefficient for PMMA compared
to PS.
Fig. 1 – Fluorescence spectrum of 5-(p-aminophenyl)-10,15, 20-triphenylporphyrinin a film based on PMMA.
0
2
4
6
8
10
12
14
600 700 800
I,
a.
u.
λ, nm
Fig. 1 – Fluorescence spectrum of
5-(p-aminophenyl)-10,15,20-tri
phenylporphyrinin a film based
on PMMA.
The positions of maxima at 653 and 718 nm
in the molecular fluorescence spectra of films
containing H2atpp (Fig. 1) correspond to the
spectra of porphyrin solutions. Thus, the use
of porphyrin compounds with unquenched
fluorescence makes it possible to transform
the light of the near UV and blue visible region
into red light.
Doped polymers
Absorption spectra of porphyrin-contain-
ing materials H2atpp-PMMA, H2atpp-PS and
mixed-polymer materials 4 (PMMA/PS = 0.25/
0.75), 5 (PMMA/PS = 0.5/0.5), 6 (PMMA/PS =
0.75/0.25) and their lanthanide-porphyrin ana
logsare shown in Table 2. In contrast to copo-
lymerization, the films obtained by coprecipi
tation are formed transparent, which allows
obtaining an absorption spectrum with good
resolution. Its profile fits with the spectrum of
the DMF solution and consists of five bands
with maxima at approximately 420 nm (Soret
band), 514, 551, 593, and 648 nm (visible re-
gion Q-bands).
Similar to absorption spectra, fluorescence
spectra of porphyrin-containing materials also
have a clear spectrum with characteristic bands
at 650 and 720 nm. The higher fluorescence ef-
ficiency of the obtained samples, in compari
son with their copolymer analogues, is due to
the quality of the film, which minimally scatters
both the photoexcitation light and the porphy-
rin fluorescence arising in the material (Table
2). The tendency of increasing the fluorescence
quantum yield as the PMMA content increases
remains similar to the materials obtained by the
first method, which, in our opinion, is also re-
lated to the degree of transparency, which is di-
rectly proportional to the quantum yield value.
86 ISSN 2708-129X. Укр. хім. журн., 2024
VISIBLE AND NEAR INFRARED EMISSION OF POLYMER MATERIALS CONTAINING PORPHYRIN AND
ITS YTTERBIUM DERIVATIVE.INORGANIC CHEMISTRY
Table 2.
Photophysical parameters of doped polymer materials obtained by coprecipitation (298K,
C=1×10-5M).
# λabs, nm
λmax, nm
ES1, см -1
φ×102*
MF 4f MF 4f-lum
H2аtpp-PS 419,514,551,593,648 654,720 – 15290 9 –
4 419,514,551,593,648 655,721 – 15270 9 –
5 419,514,551,593,648 653,719 – 15310 10 –
6 419,514,551,593,648 653,720 – 15310 11 –
H2аtpp-PMMA 419,514,551,593,648 653,718 – 15310 12 –
Yb-аtpp-PS 426,557,593 – 980 – – 2.1
Yb-4 427,558,594 – 980 – – 2.1
Yb-5 427,558,594 – 978 – – 2.2
Yb-6 427,558,594 – 978 – – 2.1
Yb-аtpp-PMMA 427,558,594 – 978 – – 2.3
* ± 10%;
It is known that in the solid state the fluo-
rescence of porphyrins is very weak compared
to solutions. This is explained by concentra-
tion quenching. It consists in the fact that
the first intense emission band of porphyrin
with a maximum at 650 nm almost perfect-
ly coincides with the last absorption band
with a maximum at approximately the same
650 nm. Due to the large value of the molar
extinction coefficient (lgε>4) of the specified
absorption band, neighboring tetrapyrrole
molecules effectively absorb the emitted light,
and this chain process, combined with ener-
gy dissipation at each step, leads to extreme-
ly low quantum yield values. But in the case
of the proposed materials, the concentration
was selected in such a way that the effect of
concentration quenching was minimal with
sufficient radiation efficiency.
Porphyrin-sensitized 4f-luminescence of
the Yb(III) ion at 978 nm (transition 2F5/2 →
2F7/2) was recorded in polymer matrices of va
rious nature (Fig. 2).
It is observed that the quantum yield va
luesof 4f-luminescence in ytterbium-contain-
ing materials does not depend on the type of
polymer matrix and the variability of its com-
position (Table 2). An important argument
in explaining such a phenomenon is almost
100% transparency of the studied polymers in
the area of ytterbium ion radiation (980 nm)
compared to its approximately 90% transpa
rency for the visible range, so in contrast to the
latterthe quantum yield of NIR-luminescence
ofytterbiumshould be less sensitive to the type
of polymer. Another important factor is the
peculiarity of the IR light itself, which consists
in the almost complete absence of light scat-
tering compared to the visible and UV ranges.
That is, IR light is more stable in such materials
in contrast to visible light, and its efficiency re-
mains under any conditions that were studied.
87https://ucj.org.ua
N.N. Semenishyn, V.V. Linnyk, S.S. Smola, O.O. Kiosse, S.N. Savin, N.V. Rusakova UCJ № 2 / Vol. 90
Fig. 2 – 4f-Luminescence spectrum
of the Yb(III) ion in a PMMA-based
film doped with a complex in the
IR region.
It is known that in the solid state the fluorescence of porphyrins is very weak compared to
solutions. This is explained by concentration quenching. It consists in the fact that the first intense
emission band of porphyrin with a maximum at 650 nm almost perfectly coincides with the last
absorption band with a maximum at approximately the same 650 nm. Due to the large value of the
molar extinction coefficient (lgε>4) of the specified absorption band, neighboring tetrapyrrole
molecules effectively absorb the emitted light, and this chain process, combined with energy
dissipation at each step, leads to extremely low quantum yield values. But in the case of the proposed
materials, the concentration was selected in such a way that the effect of concentration quenching
was minimal with sufficient radiation efficiency.
Porphyrin-sensitized 4f-luminescence of the Yb(III) ion at 978 nm (transition 2F5/2 → 2F7/2)
was recorded in polymer matrices of various nature (Fig. 2).
Fig. 2 – 4f-Luminescence spectrum of the Yb(III) ion in a PMMA-based film doped with a complex in
the IR region.
It is observed that the quantum yield valuesof 4f-luminescence in ytterbium-containing
materials does not depend on the type of polymer matrix and the variability of its composition (Table
2). An important argument in explaining such a phenomenon is almost 100% transparency of the
studied polymers in the area of ytterbium ion radiation (980 nm) compared to its approximately 90%
transparency for the visible range, so in contrast to the latterthe quantum yield of NIR-luminescence
ofytterbiumshould be less sensitive to the type of polymer. Another important factor is the peculiarity
of the IR light itself, which consists in the almost complete absence of light scattering compared to
the visible and UV ranges. That is, IR light is more stable in such materials in contrast to visible
light, and its efficiency remains under any conditions that were studied.
0
1
2
3
4
900 950 1000 1050 1100
I,
a.
u.
λ, nm
Thus, it was established that the Yb(III) com-
plex with 5-(p-aminophenyl)-10,15,20-triphe-
nylporphyrin is a modifier of PMMA, to give
it the ability to transform visible light into IR
light, due to the 4f-sensitizing activity of the
porphyrin.
It is also important that the first samples
of the obtained films do not change their op-
tical characteristics during one year from the
moment of their formation. Fig. 3 showsstable
both molecular fluorescence and 4f-lumines-
cence efficiency (within equipment error).
Fig. 3 – Changes in the intensity of different types of emission of PMMA-based materials
(H2atpp-PMMA – fluorescence, grey color; Yb-atpp-PMMA – IR-luminescence,
black color) over the course of a year.
Thus, it was established that the Yb(III) complex with 5-(p-aminophenyl)-10,15,20-
triphenylporphyrin is a modifier of PMMA, to give it the ability to transform visible light into IR
light, due to the 4f-sensitizing activity of the porphyrin.
It is also important that the first samples of the obtained films do not change their optical
characteristics during one year from the moment of their formation. Fig. 3 showsstable both
molecular fluorescence and 4f-luminescence efficiency (within equipment error).
Fig. 3 – Changes in the intensity of different types of emission of PMMA-based materials (H2atpp-
PMMA – fluorescence, grey color; Yb-atpp-PMMA – IR-luminescence, black color) over the course of a year.
This effect can be explained by the extraordinary stability of PMMA even to UV radiation
and the high stability of porphyrin molecules. On the other hand, lanthanide porphyrins are relatively
labile structures and can be easily demetalated under the action of many components of air or liquids
that may contact with them. This applies, for example, to solutions or compounds in their pure form,
however, in this case, complexes that are completely surrounded by a polymer have no possibility of
interaction with the external environment. This does not apply to molecules located on the surface of
the material, but their number compared to others in the material is extremely small, so even the
absorption spectrum does not change in any way with the appearance of demetalated compounds on
the surface.
CONCLUSIONS. It is shown that Yb-centered IR emission in PMMA-, PS-based films is
much less susceptible to changes in the chemical composition of the material base than fluorescence
in the visible range. It was also demonstrated not only the preservation of the mechanical stability of
the materials over a long period of time, but also their emission parameters. In particular, when using
0
10
20
30
40
50
60
1 2 3 4 5 6 7 8 9 10 11 12
I(
lu
m
),
a.
u.
Months
88 ISSN 2708-129X. Укр. хім. журн., 2024
VISIBLE AND NEAR INFRARED EMISSION OF POLYMER MATERIALS CONTAINING PORPHYRIN AND
ITS YTTERBIUM DERIVATIVE.INORGANIC CHEMISTRY
This effect can be explained by the extraor-
dinary stability of PMMA even to UV radia-
tion and the high stability of porphyrin mole-
cules. On the other hand, lanthanide porphy-
rins are relatively labile structures and can be
easily demetalated under the action of many
components of air or liquids that may contact
with them. This applies, for example, to solu-
tions or compounds in their pure form, how-
ever, in this case, complexes that are complete-
ly surrounded by a polymer have no possibility
of interaction with the external environment.
This does not apply to molecules located on
the surface of the material, but their number
compared to others in the material is extreme-
ly small, so even the absorption spectrum does
not change in any way with the appearance of
demetalated compounds on the surface.
CONCLUSIONS. It is shown that Yb-cen-
tered IR emission in PMMA-, PS-based films
is much less susceptible to changes in the
chemical composition of the material base
than fluorescence in the visible range. It was
also demonstrated not only the preservation of
the mechanical stability of the materials over a
long period of time, but also their emission pa-
rameters. In particular, when using a low con-
centration of lanthanide-porphyrin of 0.1% in
the final material, the efficiency of the infrared
emission of the Yb(III) ion remains at the level
of the corresponding methanol solution.
ACKNOWLEDGEMENTS.
The authors acknowledge the s upport
from the Targeted Program of Basic
Research of the National Academy of
Sciences of Ukraine (State registration
№ 0122U000415).
ВИПРОМІНЮВАННЯ У ВИДИМІЙ ТА БЛИЖНІЙ
ІНФРАЧЕРВОНІЙ ОБЛАСТІ ПОЛІМЕРНИХ МА-
ТЕРІАЛІВ, ЩО МІСТЯТЬ ПОРФІРИН ТА ЙОГО
ПОХІДНУ ІТЕРБІЮ
Н. Н. Семенишин*1, В. В. Ліннік1,2,
С. С. Смола, O. O. Kioсс2,
С. Н. Савін2, Н. В. Русакова1
1Фізико-хімічний інститут імені О. В. Бо-
гатського НАН України,
Люстдорфська дорога, 86, Одеса 65080,
Україна;
2Одеський національний університет імені
І. І. Мечникова,
вул. Всеволода Змієнка, 2, Одеса 65082, Укра-
їна
E-mail: ssmbikola@yahoo.com
Отримано серію порфіринвмісних полі-
мерних матеріалів різної структури. На ос-
нові 5-(п-амінофеніл)-10,15,20-трифеніл
порфірину та його ітербієвої похідної одер-
жано матеріали різної будови, які отримано
за різних підходів. Для всіх отриманих ма-
теріалів характерна люмінесценція – вони
випромінюють у видимому або ближньому
інфрачервоному (ІЧ) діапазоні. З’ясовано,
що ІЧ-випромінювання є значно менш чут-
ливим до змін хімічного складу полімерної
основи, ніж флуоресценція у видимому діа
пазоні. Також було показано, що отримані
матеріали є стабільними та зберігають свої
емісійні параметри протягом тривалого
часу. Використання низької концентрації
(0,1%) ітербій-порфірину в кінцевому мате-
ріалі дозволяє залишати ефективність інф-
рачервоного випромінювання іона Yb(III)
89https://ucj.org.ua
N.N. Semenishyn, V.V. Linnyk, S.S. Smola, O.O. Kiosse, S.N. Savin, N.V. Rusakova UCJ № 2 / Vol. 90
на тому ж рівні, що й у відповідному роз-
чині метанолу.
Ключові слова: полімери, лантаноїди,
порфірини, флуоресценція, 4f-люмінесцен-
ція.
REFERENCES
1. Vonlanthen M., Cuétara-Guadarrama F., Sor-
roza-Martínez K., González-Méndez I., Es-
trada-Montaño A.S., Rivera E. A review of
porphyrin dendrimers as light-harvesting
versatile platforms. Dyes and Pigments. 2024.
222:111873.
https://doi.org/10.1016/j.dyepig.2023.111873
2. Kumar A., Kim D., Kumar S., Mahammed A.,
Churchill D.G., Gross Z. Milestones in cor-
role chemistry: historical ligand syntheses and
post-functionalization. Chemical Society Re-
views. 2023. 52(2): 573–600.
http://dx.doi.org/10.1039/d1cs01137e
3. Li D., Cai S., Wang P., Cheng H., Cheng B.,
Zhang Y., Liu G. Innovative Design Strategies
Advance Biomedical Applications of Phthalo
cyanines. Advanced Healthcare Materials.
2023. 12(22): 2300263.
https://doi.org/10.1002/adhm.202300263
4. Chan Wai-Lun, Xie Chen, Lo Wai-Sum, Bünzli
J.-C. G., Wong Wai-Kwok, Ka-Leung W. Lan-
thanide–tetrapyrrole complexes: synthesis, re-
dox chemistry, photophysical properties, and
photonic applications. Chem. Soc. Rev. 2021.
50(21): 12189–12257.
http://dx.doi.org/10.1039/c9cs00828d
5. Wang J., Xia M., Wei J., Jiao T., Chen Q.,
Chen Q., Chen X. Dual-signal amplified ca-
thodic electrochemiluminescence aptsensor
based on a europium-porphyrin coordination
polymer for the ultrasensitive detection of
zearalenone in maize. Sensors and Actuators B:
Chemical. 2023. 382: 133532.
https://doi.org/10.1016/j.snb.2023.133532
6. Luo X., Zhang C., Yu Z., Wen S., Xian Y. Re-
cent advances in responsive lanthanide-doped
luminescence nanoprobes in the near-infra-
red-II window. TrAC Trends in Analytical
Chemistry. 2023. 169: 117368.
https://doi.org/10.1016/j.trac.2023.117368
7. Du Y., Ni S., Ma Q., Song X., Yang H. Engineer-
ing NIR-II luminescent lanthanide nanopro-
bes for imaging brain diseases in vivo. Coordi-
nation Chemistry Reviews. 2023. 496: 215401.
https://doi.org/10.1016/j.ccr.2023.215401
8. Malhotra K., Hrovat D., Kumar B., Qu G.,
Houten J.V., Ahmed R., Piunno P.a.E., Gun-
ning P.T., Krull U.J. Lanthanide-Doped Up-
conversion Nanoparticles: Exploring A Trea
sure Trove of NIR-Mediated Emerging Appli-
cations. ACS Applied Materials & Interfaces.
2023. 15(2): 2499–2528.
http://dx.doi.org/10.1021/acsami.2c12370
9. Przybylska D., Grzyb T., Erdman A., Olejnik
K., Szczeszak A. Anti-counterfeiting system
based on luminescent varnish enriched by
NIR- excited nanoparticles for paper security.
Scientific Reports. 2022. 12(1): 19388.
http://dx.doi.org/10.1038/s41598-022-23686-9
10. Hu J.-Y., Ning Y., Meng Y.-S., Zhang J., Wu Z.-
Y., Gao S., Zhang J.-L. Highly near-IR emissive
ytterbium(iii) complexes with unprecedented
quantum yields. Chemical Science. 2017. 8(4):
2702–2709.
http://dx.doi.org/10.1039/c6sc05021b
11. Altmann A., Eden M., Hüttmann G., Schell C.,
Rahmanzadeh R. Porphyrin-based sensor
films for monitoring food spoilage. Food Pa
ckaging and Shelf Life. 2023. 38: 101105.
https://doi.org/10.1016/j.fpsl.2023.101105
12. Habermeyer B., Chilingaryan T., Guilard R.
Bactericidal efficiency of porphyrin systems.
Journal of Porphyrins and Phthalocyanines.
2021. 25(05n06): 359–381.
http://dx.doi.org/10.1142/s1088424621500358
13. Ferreira D.P., Conceição D.S., Calhelha R.C.,
Sousa T., Socoteanu R., Ferreira I.C.F.R., Vieira
Ferreira L.F. Porphyrin dye into biopolymeric
90 ISSN 2708-129X. Укр. хім. журн., 2024
VISIBLE AND NEAR INFRARED EMISSION OF POLYMER MATERIALS CONTAINING PORPHYRIN AND
ITS YTTERBIUM DERIVATIVE.INORGANIC CHEMISTRY
chitosan films for localized photodynamic the
rapy of cancer. Carbohydrate Polymers. 2016.
151: 160–171.
https://doi.org/10.1016/j.carbpol.2016.05.060
14. Paolesse R., Nardis S., Monti D., Stefanelli
M., Di Natale C. Porphyrinoids for Chemical
Sensor Applications. Chemical Reviews. 2017.
117(4): 2517–2583.
http://dx.doi.org/10.1021/acs.chemrev.6b00361
15. Wang Y., Cui X., Zhang P., Wang Y., Lu W. Syn-
thesis of porphyrin porous organic polymers
and their application of water pollution treat-
ment: A review. Environmental Technology &
Innovation. 2023. 29: 102972.
https://doi.org/10.1016/j.eti.2022.102972
16. Tian J., Huang B., Nawaz M.H., Zhang W.
Recent advances of multi-dimensional por-
phyrin-based functional materials in photo-
dynamic therapy. Coordination Chemistry Re-
views. 2020. 420: 213410.
https://doi.org/10.1016/j.ccr.2020.213410
17. Ji W., Wang T.-X., Ding X., Lei S., Han B.-H.
Porphyrin- and phthalocyanine-based porous
organic polymers: From synthesis to applica-
tion. Coordination Chemistry Reviews. 2021.
439: 213875.
https://doi.org/10.1016/j.ccr.2021.213875
Стаття надійшла 01.02.2024.
|
| id | oai:ojs2.1444248.nisspano.web.hosting-test.net:article-641 |
| institution | Ukrainian Chemistry Journal |
| keywords_txt_mv | keywords |
| language | English |
| last_indexed | 2026-07-23T01:11:23Z |
| publishDate | 2024 |
| publisher | V.I.Vernadsky Institute of General and Inorganic Chemistry |
| record_format | ojs |
| resource_txt_mv | ucjorgua/1d/d38e8c2e1abb537276be0cfc8cb1101d.pdf |
| spelling | oai:ojs2.1444248.nisspano.web.hosting-test.net:article-6412026-07-22T08:23:53Z VISIBLE AND NEAR INFRARED EMISSION OF POLYMER MATERIALS CONTAINING PORPHYRIN AND ITS YTTERBIUM DERIVATIVE Semenishyn, Nikolay Rusakova, Nataliia Smola, Serhii Linnyk, Valeriia Kiose, Olesya Savin, Serhii polymers; lanthanides; porphyrins; fluorescence; 4f-luminescence. A series of porphyrin containing polymer materials of various structure was developed. Free 5-(p-aminophenyl)-10,15,20-triphenylporphyrinand its ytterbium derivative were used to prepare materials of different structure and they were obtained by different approaches.Thus, two polymers were used in this study – the poly(methyl methacrylate) (PMMA), polystyrene (PS) as well as their copolymers of different composition (the molar ratio of 0.25/0.75, 0.5/0.5 and 0.75/0.25). Also part of materials were obtained by coprecipitation of polymer(s) with corresponding porphyrin derivative. The latter material ismore transparent, which allows obtaining an absorption spectrum with good resolution. All materials have notable emission characteristics – they emit in visible or near infrared (IR) range. Increasing of PMMA content in the final material causes the increase of fluorescence quantum yield for bothcopolymers and coprecipitatedmaterials.It can be explained by a higher light transmission coefficient of PMMA compared to PS.It was found out that 4f-luminescence in ytterbium-containing materialsdoes not depend on the type of polymer matrix and the variability of its compositionin contrast to fluorescence in the visible range.Almost 100% transparency of the studied polymers in the area of ytterbium ion radiation (980 nm)explains this phenomenon. It was also shown that obtainedmaterialsarestablefora long period of time and they keep the permanence oftheir emission parameters.This phenomenon can be explained by the extraordinary stability of PMMA even to UV radiation and by the high stability of porphyrin molecules. The use of a low concentration (0.1%) of lanthanide-porphyrin in the final material allows the IR emission efficiency of the Yb(III) ion to remain at the same level as in the corresponding methanol solution. V.I.Vernadsky Institute of General and Inorganic Chemistry 2024-03-29 Article Article Inorganic Chemistry Неорганическая химия Неорганічна хімія application/pdf https://ucj.org.ua/index.php/journal/article/view/641 10.33609/2708-129X.90.2.2024.81-90 Ukrainian Chemistry Journal; Vol. 90 No. 2 (2024): Ukrainian Chemistry Journal; 81-90 Украинский химический журнал; ##issue.vol## 90 ##issue.no## 2 (2024): Ukrainian Chemistry Journal; 81-90 Український хімічний журнал; Том 90 № 2 (2024): Ukrainian Chemistry Journal; 81-90 2708-129X 2708-1281 en https://ucj.org.ua/index.php/journal/article/view/641/320 Copyright (c) 2024 Nikolay Semenishyn, Nataliia Rusakova, Serhii Smola, Valeriia Linnyk, Olesya Kiose, Serhii Savin https://creativecommons.org/licenses/by-nc/4.0 |
| spellingShingle | Semenishyn, Nikolay Rusakova, Nataliia Smola, Serhii Linnyk, Valeriia Kiose, Olesya Savin, Serhii VISIBLE AND NEAR INFRARED EMISSION OF POLYMER MATERIALS CONTAINING PORPHYRIN AND ITS YTTERBIUM DERIVATIVE |
| title | VISIBLE AND NEAR INFRARED EMISSION OF POLYMER MATERIALS CONTAINING PORPHYRIN AND ITS YTTERBIUM DERIVATIVE |
| title_full | VISIBLE AND NEAR INFRARED EMISSION OF POLYMER MATERIALS CONTAINING PORPHYRIN AND ITS YTTERBIUM DERIVATIVE |
| title_fullStr | VISIBLE AND NEAR INFRARED EMISSION OF POLYMER MATERIALS CONTAINING PORPHYRIN AND ITS YTTERBIUM DERIVATIVE |
| title_full_unstemmed | VISIBLE AND NEAR INFRARED EMISSION OF POLYMER MATERIALS CONTAINING PORPHYRIN AND ITS YTTERBIUM DERIVATIVE |
| title_short | VISIBLE AND NEAR INFRARED EMISSION OF POLYMER MATERIALS CONTAINING PORPHYRIN AND ITS YTTERBIUM DERIVATIVE |
| title_sort | visible and near infrared emission of polymer materials containing porphyrin and its ytterbium derivative |
| topic_facet | polymers lanthanides porphyrins fluorescence 4f-luminescence. |
| url | https://ucj.org.ua/index.php/journal/article/view/641 |
| work_keys_str_mv | AT semenishynnikolay visibleandnearinfraredemissionofpolymermaterialscontainingporphyrinanditsytterbiumderivative AT rusakovanataliia visibleandnearinfraredemissionofpolymermaterialscontainingporphyrinanditsytterbiumderivative AT smolaserhii visibleandnearinfraredemissionofpolymermaterialscontainingporphyrinanditsytterbiumderivative AT linnykvaleriia visibleandnearinfraredemissionofpolymermaterialscontainingporphyrinanditsytterbiumderivative AT kioseolesya visibleandnearinfraredemissionofpolymermaterialscontainingporphyrinanditsytterbiumderivative AT savinserhii visibleandnearinfraredemissionofpolymermaterialscontainingporphyrinanditsytterbiumderivative |