LANTHANIDE-PORPHYRINS AND LANTHANIDE-PHTHALOCYANINES: DEVELOPMENT OF STABLE AND EFFECTIVE INFRARED 4F-EMITTIVE COMPOUNDS
This review is devoted to different synthetic approaches for obtaining lanthanide complexes with porphyrins and phthalocyanines, studying their structure and emission features. Lanthanide-tetrapyrroles can be core-coordinated or/and coordinated by additional binding sites in polytopic derivatives. I...
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| author | Semenishyn, Nikolay Rusakova, Nataliia Smola, Serhii |
| author_facet | Semenishyn, Nikolay Rusakova, Nataliia Smola, 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_sort | Semenishyn, Nikolay |
| baseUrl_str | https://ucj.org.ua/index.php/journal/oai |
| collection | OJS |
| datestamp_date | 2026-07-22T08:23:51Z |
| description | This review is devoted to different synthetic approaches for obtaining lanthanide complexes with porphyrins and phthalocyanines, studying their structure and emission features. Lanthanide-tetrapyrroles can be core-coordinated or/and coordinated by additional binding sites in polytopic derivatives. It is noteworthy that the polytopic tetrapyrroles allow obtaining polyheteronuclear compounds, which is quite interesting in terms of their particular 4f-sensitization mechanism. A general structural difference between core-coordinated lanthanide-porphyrins and lanthanide-phthalocyanines is the ability of the latter to easily form poly-decker compounds, which leads to interesting changes in photochemical processes including 4f-sensitization. The review also shows the main directions for the solution of the stability issue as well as different approaches for increasing the 4f-luminescence effectiveness. |
| doi_str_mv | 10.33609/2708-129X.89.04.2023.73-89 |
| first_indexed | 2025-09-24T17:43:50Z |
| format | Article |
| fulltext |
73
УДК 535.355.4:546.881 doi: 10.33609/2708-129X.89.04.2023.73-89
LANTHANIDE-PORPHYRINS AND LANTHANIDE-PHTHALOCYANINES:
DEVELOPMENT OF STABLE AND EFFECTIVE INFRARED
4F-EMITTIVE COMPOUNDS.
N.N. Semenishyn*, S.S. Smola, N.V. Rusakova
A.V. Bogatsky Physico-Chemical Institute, National Academy of Sciences of Ukraine,
86 Lustdorfs’ka doroga, 65080 Odesa, Ukraine
Email: ssmbikola@yahoo.com
This review is devoted to different synthetic approaches for obtaining lanthanide complex-
es with porphyrins and phthalocyanines, studying their structure and emission features. Lan-
thanide-tetrapyrroles can be core-coordinated or/and coordinated by additional binding sites
in polytopic derivatives. It is noteworthy that the polytopic tetrapyrroles allow obtaining poly
heteronuclear compounds, which is quite interesting in terms of their particular 4f-sensitiza-
tion mechanism. A general structural difference between core-coordinated lanthanide-por-
phyrins and lanthanide-phthalocyanines is the ability of the latter to easily form poly-decker
compounds, which leads to interesting changes in photochemical processes including 4f-sen-
sitization. The review also shows the main directions for the solution of the stability issue as
well as different approaches for increasing the 4f-luminescence effectiveness.
Keywords: lanthanides; porphyrins; phthalocyanines; 4f-luminescence; sensitization.
INTRODUCTION. Extensive research on
tetrapyrrole macroheterocycles (hereinafter
just “tetrapyrroles”) and their lanthanide com-
plexes is driven by their high demand in vari-
ous fields such as medicine [1–5], catalysis [6],
luminescence spectroscopy [7] and solar ener-
gy conversion technologies [8]. It is notewor-
thy that a remarkable range of structures has
been synthesized within a relatively short time.
These structures range from basic alkyl- and
arylporphyrins to derivatives that incorporate
fragments capable of molecular recognition,
polarity regulation, control of redox potentials,
solubility, and other properties crucial for the
practical application of nitrogen-containing
macrocycles [9].
Among all lanthanides, only Nd(III), Er(III),
and Yb(III) demonstrate 4f-emission in the
near-infrared (NIR) (Fig. 1) range when co-
ordinated with macrocyclic tetrapyrroles. This
limitation arises from the relatively low ener-
gy levels of the triplet states of tetrapyrroles in
the phosphorescence region (approximately
800 nm), and only the mentioned lanthanide
ions possess resonance levels that match the
excitation energy transfer requirements.
74 ISSN 2708-129X. Укр. хім. журн., 2023
LANTHANIDE-PORPHYRINS AND LANTHANIDE-PHTHALOCYANINES:
DEVELOPMENT OF STABLE AND EFFECTIVE INFRARED 4F-EMITTIVE COMPOUNDSINORGANIC CHEMISTRY
The addition of organic molecule fragments
capable of coordinating extra metal ions en-
hances the potential for self-organization in
modified tetrapyrroles and it opens oppor-
tunities to form stable peripheral complexes.
Tetrapyrroles that have been modified with
flexible crown- and/or azacrown ether substi
tuents, cyclic and acyclic aminopolycarbonic
acids possess two distinct types of polydentate
fragments. These modified tetrapyrroles serve
as convenient building blocks for the construc-
tion of polynuclear metal complexes with ex-
ceptional spectral-luminescent properties. The
stacking interaction between aromatic rings
allows tetrapyrrole molecules to self-organize,
while their unique spectroscopic, electrochemi
cal, semiconductor, and catalytic properties, in
combination with the distinctive spectral-lu-
minescence properties of lanthanide ions,
promote the exploration of new applications
for polynuclear tetrapyrroles. The design of
multicomponent systems holds great promise
for achieving effective 4f-luminescence in lan-
thanide ions (Ln(III)) due to the availability of
multiple sources of excitation energy, exclud-
ing of quenching components from the inner
coordination sphere, etc.
The addition of organic molecule fragments capable of coordinating extra metal ions enhances
the potential for self-organization in modified tetrapyrroles and it opens opportunities to form stable
peripheral complexes. Tetrapyrroles that have been modified with flexible crown- and/or azacrown
ether substituents, cyclic and acyclic aminopolycarbonic acids possess two distinct types of
polydentate fragments. These modified tetrapyrroles serve as convenient building blocks for the
construction of polynuclear metal complexes with exceptional spectral-luminescent properties. The
stacking interaction between aromatic rings allows tetrapyrrole molecules to self-organize, while
their unique spectroscopic, electrochemical, semiconductor, and catalytic properties, in combination
with the distinctive spectral-luminescence properties of lanthanide ions, promote the exploration of
new applications for polynuclear tetrapyrroles. The design of multicomponent systems holds great
promise for achieving effective 4f-luminescence in lanthanide ions (Ln(III)) due to the availability of
multiple sources of excitation energy, excluding of quenching components from the inner
coordination sphere, etc.
Fig. 1. Profiles of 4f-luminescence spectra of Nd(III), Er (III), and Yb (III) ions and the
corresponding electron transitions.
PORPHYRINS. Synthetic procedures for Ln-porphyrinates are generally based on the interaction
of the corresponding porphyrin with an excess of lanthanide salt under the refluxing of a high-boiling
solvent. In general, e.g. 5,10,15,20-tetraphenyl-21H,23H-porphyrin (H2tpp) and several equivalents
of lanthanide β-diketonate are refluxed in 1,2,4-trichlorobenzene (or imidazole) for 3-4 hours and the
crude product is then chromatographed to yield the desired complex. This method is still most
commonly used nowadays [10].
It should be noted that all core-coordinated porphyrinates of lanthanides are relatively labile
systems due to several factors. Firstly, lanthanides cannot undergo d2sp3 hybridization, making it
impossible to form strong covalent bonds with the ligand due to the shielding of d-orbitals. Secondly,
Fig. 1. Profiles of 4f-luminescence spectra of Nd(III), Er (III), and Yb (III) ions and the corresponding
electron transitions.
PORPHYRINS. Synthetic procedures for
Ln-porphyrinates are generally based on the
interaction of the corresponding porphyrin
with an excess of lanthanide salt under the re-
fluxing of a high-boiling solvent. In general,
e.g. 5,10,15,20-tetraphenyl-21H,23H-porphy-
rin (H2tpp) and several equivalents of lantha-
nide β-diketonate are refluxed in 1,2,4-trichlo
robenzene (or imidazole) for 3-4 hours and
the crude product is then chromatographed to
yield the desired complex. This method is still
most commonly used nowadays [10].
It should be noted that all core-coordinated
porphyrinates of lanthanides are relatively la-
bile systems due to several factors. Firstly, lan-
thanides cannot undergo d2sp3 hybridization,
75https://ucj.org.ua
N.N. Semenishyn, S.S. Smola, N.V. Rusakova UCJ № 04 / Vol. 89
making it impossible to form strong covalent
bonds with the ligand due to the shielding of
d-orbitals. Secondly, the shielding of f-elect
rons by external electronic layers leads to the
formation of π-bonds. Additionally, the large
covalent radii of lanthanide ions strongly dis-
place them from the plane of nitrogen atoms
in the macrocycle. Lastly, the coordination
with extra-ligands facilitates the dissociation
of Ln-N bonds.
As a rule, the main reason of relatively low
4f-quantum yields is a quenching effect of C-H
and O-H bonds in coordination environment.
For example energy dissipation in the Nd(III)
ion occurs due to the overlapping of the
4F3/2→4I15/2 transition (5400 cm−1) with the O–H
bond vibrational quanta ν = 2 (6900 cm−1) and
such an excitation of vibration state leads to
the effective quenching of the 4F3/2-state [11].
Up to date, there were a lot of different tech-
niques for improving the effectiveness of 4f-lu-
minescence in the IR range. Such approaches
are based on the elimination of C-H and O-H
bonds from the inner or outer coordination
sphere of the lanthanide ion. Most effective
methods are substitution of hydrogen by deu-
terium or fluorine [12] or using bulky groups
[10]. Recently it was proposed to combine both
mentioned approaches for one molecule [13].
The authors synthesized a molecule with both
a bulky axial ligand and the totally deuterat-
ed (fluorinated) organic part of the molecule
(Fig. 2). They achieved the unprecedented 69%
quantum yield of Yb(III) ion luminescence in a
deuterated solvent. This value should allow the
use of such compounds as strong IR-emitters
for different purposes, but three main prob-
lems hinder it. First of all it is model systems
and the use of deuterated solvents in real prac-
tice (for example in medicine) is almost im-
possible. The second is the above-mentioned
lability of these complexes [2], which severely
limits their use. The third is a huge price for
such kind of modification (β-fluorines, deute-
rium in any positions).
Fig. 2. Structure of fluorinated/deuterated
Yb-porphyrins. Taken from [13].
So, there was proposed a simple approach
to obtain stable Ln-porphyrins by the modi-
fication of starting porphyrin with aminopo-
lycarboxylic (APC) acids, since their stability
constants (lgβ) with lanthanides are >20 for
H5dtpa and >15 for H4edta. Obtained poly-
topic porphyrins react with the ionic form of
lanthanide at normal conditions (even at room
temperature) by its APC site to form periphe
ral complexes (Fig. 3). Such modified porphy-
rins (particularly dtpa-derivatives) allow keep-
ing the lanthanide ion saturated enough, hence
preventing its interaction with the C-H or O-H
bond containing components of the medium.
The coincidence between the absorption
and excitation spectra of these complexes
clearly shows that a ligand-to-lanthanide ion
energy transfer from the triplet levels of por-
phyrins to the resonance levels of Ln(III) takes
place [14]. It has been found that the values
of 4f-luminescence quantum yield for the
the shielding of f-electrons by external electronic layers leads to the formation of π-bonds.
Additionally, the large covalent radii of lanthanide ions strongly displace them from the plane of
nitrogen atoms in the macrocycle. Lastly, the coordination with extra-ligands facilitates the
dissociation of Ln-N bonds.
As a rule, the main reason of relatively low 4f-quantum yields is a quenching effect of C-H and
O-H bonds in coordination environment. For example energy dissipation in the Nd(III) ion occurs
due to the overlapping of the 4F3/2→4I15/2 transition (5400 cm−1) with the O–H bond vibrational
quanta ν = 2 (6900 cm−1) and such an excitation of vibration state leads to the effective quenching of
the 4F3/2-state [11].
Up to date, there were a lot of different techniques for improving the effectiveness of 4f-
luminescence in the IR range. Such approaches are based on the elimination of C-H and O-H bonds
from the inner or outer coordination sphere of the lanthanide ion. Most effective methods are
substitution of hydrogen by deuterium or fluorine [12] or using bulky groups [10]. Recently it was
proposed to combine both mentioned approaches for one molecule [13]. The authors synthesized a
molecule with both a bulky axial ligand and the totally deuterated (fluorinated) organic part of the
molecule (Fig. 2). They achieved the unprecedented 69% quantum yield of Yb(III) ion luminescence
in a deuterated solvent. This value should allow the use of such compounds as strong IR-emitters for
different purposes, but three main problems hinder it. First of all it is model systems and the use of
deuterated solvents in real practice (for example in medicine) is almost impossible. The second is the
above-mentioned lability of these complexes [2], which severely limits their use. The third is a huge
price for such kind of modification (β-fluorines, deuterium in any positions).
Fig. 2. Structure of fluorinated/deuterated Yb-porphyrins. Taken from [13].
So, there was proposed a simple approach to obtain stable Ln-porphyrins by the modification of
starting porphyrin with aminopolycarboxylic (APC) acids, since their stability constants (lgβ) with
lanthanides are >20 for H5dtpa and >15 for H4edta. Obtained polytopic porphyrins react with the
ionic form of lanthanide at normal conditions (even at room temperature) by its APC site to form
76 ISSN 2708-129X. Укр. хім. журн., 2023
LANTHANIDE-PORPHYRINS AND LANTHANIDE-PHTHALOCYANINES:
DEVELOPMENT OF STABLE AND EFFECTIVE INFRARED 4F-EMITTIVE COMPOUNDSINORGANIC CHEMISTRY
dtpa-complexes are higher than for the same
edta-complexes [15], and that homobinuclear
complexes (M=Ln, Fig. 3) have more effective
4f-luminescence than mononuclear complex-
es [16]. The former can be explained by the
greater saturation of the lanthanide ion in dtpa
derivatives in comparison to edta ones, which
results in the appearance of water (or other
solvent) molecules in the inner coordination
sphere of edta-derivatives (it was demonstrat-
ed for similar edta-compounds [17]).
Fig. 3. Structure of peripheral Yb-porphyrins.
Taken from [16].
peripheral complexes (Fig. 3). Such modified porphyrins (particularly dtpa-derivatives) allow
keeping the lanthanide ion saturated enough, hence preventing its interaction with the C-H or O-H
bond containing components of the medium.
The coincidence between the absorption and excitation spectra of these complexes clearly shows
that a ligand-to-lanthanide ion energy transfer from the triplet levels of porphyrins to the resonance
levels of Ln(III) takes place [14]. It has been found that the values of 4f-luminescence quantum yield
for the dtpa-complexes are higher than for the same edta-complexes [15], and that homobinuclear
complexes (M=Ln, Fig. 3) have more effective 4f-luminescence than mononuclear complexes [16].
The former can be explained by the greater saturation of the lanthanide ion in dtpa derivatives in
comparison to edta ones, which results in the appearance of water (or other solvent) molecules in the
inner coordination sphere of edta-derivatives (it was demonstrated for similar edta-compounds [17]).
Fig. 3. Structure of peripheral Yb-porphyrins. Taken from [16].
APC-based polytopic porphyrins allow obtaining homopolynuclear complexes. As a result it is
possible to obtain modified Ln-porphyrins, which can act as MRI agents and photodynamic agents at
the same time. Fig. 4 presents examples of polynuclear f-f and f-d complexes involving Gd(III) ions
and porphyrins and Zn-porphyrins containing diethylenetriaminepentaacetate (dtpa) and
tetraazacyclododecanetetraacetate (dota) fragments. These compounds have shown promising
properties as contrast agents for the diagnosis of neoplasms [3, 18–19].
a b c
Fig. 4. Gd(III) complexes with synthetic porphyrins and Zn-porphyrins modified with dtpa and
dota-fragments. Taken from [3, 18].
Fig. 4. Gd(III) complexes with synthetic porphyrins and Zn-porphyrins
modified with dtpa and dota-fragments. Taken from [3, 18].
a b
c
77https://ucj.org.ua
N.N. Semenishyn, S.S. Smola, N.V. Rusakova UCJ № 04 / Vol. 89
APC-based polytopic porphyrins allow ob-
taining homopolynuclear complexes. As a re-
sult it is possible to obtain modified Ln-por-
phyrins, which can act as MRI agents and
photodynamic agents at the same time. Fig. 4
presents examples of polynuclear f-f and f-d
complexes involving Gd(III) ions and porphy-
rins and Zn-porphyrins containing diethy
lenetriaminepentaacetate (dtpa) and tetraaza-
cyclododecanetetraacetate (dota) fragments.
These compounds have shown promising
properties as contrast agents for the diagnosis
of neoplasms [3, 18–19].
The synthesis of polynuclear complexes
based on functionalized porphyrins typical-
ly occurs in a single step. Depending on the
synthesis conditions, complexation can take
place either at the peripheral substituents
(Fig. 4, a), involve all ligand fragments inclu
ding the porphyrin center (Fig. 4, b), or it is
possible to obtain heteronuclear compounds
by sequential synthesis (Fig. 4, c) based on
different conditions of APC and porphyrin
coordination with different metal ions. As a
rule, in contrast to homonuclear complexes,
the formation of heteronuclear complexes is
more challenging as it requires step-by-step
complexation of metals with polytopic ligands
to avoid producing a mixture of products.
d-f-Heteropolynuclear complexes with
erbium (III) ions were synthesized using a
zinc-containing porphyrin block modified
with fragments of 1,10-phenanthroline or
2,2'-dipyridyl [20]. Aromatic substituents were
chosen for two reasons. Firstly, they offer the
possibility of forming stable d-metal com-
plexes. Secondly, the influence of the nature
of aromatic spacers on the mutual arrange-
ment of porphyrinate units was studied. The
use of non-planar 2,2'-dipyridyl as a spacer led
to a more flexible arrangement compared to
the rigid binding provided by the condensed
1,10-phenanthroline linker (shown in Fig. 5).
The resulting compound exhibits sensi-
tized 4f-luminescence from the Er(III) ion in
the NIR region at 1530 nm (transition 4I13/2 →
4I15/2). This luminescence arises from resonant
energy transfer from Pt(II) porphyrinate to
the emitting levels of the Er(III) ion. This ener
gy transfer mechanism is supported by the
overlap of the luminescence spectra of d-metal
porphyrinate and the f-f absorption spectra of
erbium ions. Specifically, transitions from the
ground level 4I15/2 of the Er(III) ion occur to the
levels 4F9/2 and 4I9/2, with absorption maxima at
652 nm and 801 nm, respectively.
The synthesis of polynuclear complexes based on functionalized porphyrins typically occurs in a
single step. Depending on the synthesis conditions, complexation can take place either at the
peripheral substituents (Fig. 4, a), involve all ligand fragments including the porphyrin center (Fig. 4,
b), or it is possible to obtain heteronuclear compounds by sequential synthesis (Fig. 4, c) based on
different conditions of APC and porphyrin coordination with different metal ions. As a rule, in
contrast to homonuclear complexes, the formation of heteronuclear complexes is more challenging as
it requires step-by-step complexation of metals with polytopic ligands to avoid producing a mixture
of products.
d-f-Heteropolynuclear complexes with erbium (III) ions were synthesized using a zinc-
containing porphyrin block modified with fragments of 1,10-phenanthroline or 2,2'-dipyridyl [20].
Aromatic substituents were chosen for two reasons. Firstly, they offer the possibility of forming
stable d-metal complexes. Secondly, the influence of the nature of aromatic spacers on the mutual
arrangement of porphyrinate units was studied. The use of non-planar 2,2'-dipyridyl as a spacer led to
a more flexible arrangement compared to the rigid binding provided by the condensed 1,10-
phenanthroline linker (shown in Fig. 5).
The resulting compound exhibits sensitized 4f-luminescence from the Er(III) ion in the NIR
region at 1530 nm (transition 4I13/2 → 4I15/2). This luminescence arises from resonant energy transfer
from Pt(II) porphyrinate to the emitting levels of the Er(III) ion. This energy transfer mechanism is
supported by the overlap of the luminescence spectra of d-metal porphyrinate and the f-f absorption
spectra of erbium ions. Specifically, transitions from the ground level 4I15/2 of the Er(III) ion occur to
the levels 4F9/2 and 4I9/2, with absorption maxima at 652 nm and 801 nm, respectively.
Fig. 5. The overlapping area (shaded) where the luminescence spectra of Pt-porphyrinate (1) and
the absorption spectra of the Er(III) ion intersect (transitions 4I15/2 → 4F9/2 (2) and 4I15/2 → 4I9/2 (3).
Taken from [20].
Fig. 5. The overlapping area (shad-
ed) where the luminescence spectra of
Pt-porphyrinate (1) and the absorption
spectra of the Er(III) ion intersect (tran-
sitions 4I15/2 → 4F9/2 (2) and 4I15/2 → 4I9/2 (3).
Taken from [20].
78 ISSN 2708-129X. Укр. хім. журн., 2023
LANTHANIDE-PORPHYRINS AND LANTHANIDE-PHTHALOCYANINES:
DEVELOPMENT OF STABLE AND EFFECTIVE INFRARED 4F-EMITTIVE COMPOUNDSINORGANIC CHEMISTRY
In a heteronuclear complex depicted in
Fig. 6, the 4f-luminescence of Nd(III) and
Yb(III) ions was detected. The complex is
based on a Pd(II) β-mono-aminotetraphenyl-
porphyrinate, which has been modified with
a dota derivative. Notably, in this study [21],
the preparation of the d-metal porphyrinate
occurs prior to the introduction of the lantha-
nide ion into the peripheral binding site.
Fig. 6. Heteronuclear Yb-Pd complex with dota-
functionalized porphyrin. Taken from [21].
Palladium complexes of porphyrins are
known to possess long-lived triplet levels,
which can be effectively quenched in the pres-
ence of oxygen in polar solvents. However,
it has been demonstrated that modification
with a dota fragment helps suppress oxygen
quenching and significantly enhances the
phosphorescence of palladium complexes by
nearly an order of magnitude. The lumines-
cence spectra of Nd(III) and Yb(III) ions were
obtained in solutions of methanol (both deu-
terated and non-deuterated) under aerated
and degassed conditions. It was found that the
4f-luminescent signal in a deuterated solvent
was increased by 4 times for Yb(III) and 2.5
times for Nd(III), indicating the sensitivity of
the excited ion levels to quenching by OH vi-
brations. The excitation spectra of the samples
in degassed solutions closely resembled the
absorption spectra of the individual porphyrin
complexes. This suggests a competitive energy
transfer rate from the triplet levels of the por-
phyrin component to the levels of lanthanide
ions, according to the authors. In neodymium-
containing systems, energy transfer is more
efficient compared to Yb(III)-Pd(II) complex-
es. This can be attributed to the larger over-
lap integrals between the absorption spectra
of Nd(III) ions (with absorption maxima at
740 nm, 794 nm, and 865 nm corresponding
to transitions from the ground level 4I9/2 to
4F7/2 + 4S3/2,
4F5/2 + 4H9/2, and 4F3/2, respectively)
and the emission bands of porphyrinates.
Numerous heteronuclear complexes have
been synthesized using bridging ligands [22–
24]. However, the formation of d-d-hetero-
nuclear complexes through this method is
deemed impossible, likely due to the lower
coordination numbers exhibited by d-metals
compared to lanthanides. In contrast to pre-
vious studies, f-d-compounds are synthesized
using lanthanide porphyrinates as the primary
"building block" in the systems (as illustrated
in Fig. 7).
Fig. 7. Structure of lanthanide-cobalt hetero-
nuclear compounds with bulky axial ligand Taken
from [22].
In a heteronuclear complex depicted in Fig. 6, the 4f-luminescence of Nd(III) and Yb(III) ions
was detected. The complex is based on a Pd(II) β-mono-aminotetraphenylporphyrinate, which has
been modified with a dota derivative. Notably, in this study [21], the preparation of the d-metal
porphyrinate occurs prior to the introduction of the lanthanide ion into the peripheral binding site.
Fig. 6. Heteronuclear Yb-Pd complex with dota-functionalized porphyrin. Taken from [21].
Palladium complexes of porphyrins are known to possess long-lived triplet levels, which can be
effectively quenched in the presence of oxygen in polar solvents. However, it has been demonstrated
that modification with a dota fragment helps suppress oxygen quenching and significantly enhances
the phosphorescence of palladium complexes by nearly an order of magnitude. The luminescence
spectra of Nd(III) and Yb(III) ions were obtained in solutions of methanol (both deuterated and non-
deuterated) under aerated and degassed conditions. It was found that the 4f-luminescent signal in a
deuterated solvent was increased by 4 times for Yb(III) and 2.5 times for Nd(III), indicating the
sensitivity of the excited ion levels to quenching by OH vibrations. The excitation spectra of the
samples in degassed solutions closely resembled the absorption spectra of the individual porphyrin
complexes. This suggests a competitive energy transfer rate from the triplet levels of the porphyrin
component to the levels of lanthanide ions, according to the authors. In neodymium-containing
systems, energy transfer is more efficient compared to Yb(III)-Pd(II) complexes. This can be
attributed to the larger overlap integrals between the absorption spectra of Nd(III) ions (with
absorption maxima at 740 nm, 794 nm, and 865 nm corresponding to transitions from the ground
level 4I9/2 to 4F7/2 + 4S3/2, 4F5/2 + 4H9/2, and 4F3/2, respectively) and the emission bands of
porphyrinates.
Numerous heteronuclear complexes have been synthesized using bridging ligands [22-24].
However, the formation of d-d-heteronuclear complexes through this method is deemed impossible,
likely due to the lower coordination numbers exhibited by d-metals compared to lanthanides. In
contrast to previous studies, f-d-compounds are synthesized using lanthanide porphyrinates as the
primary "building block" in the systems (as illustrated in Fig. 7).
Fig. 7. Structure of lanthanide-cobalt heteronuclear compounds with bulky axial ligand Taken
from [22].
Ln-Co complexes were successfully synthesized through the addition of (cyclopentadienyl)-tris-
(diethylphosphinite)-cobaltate. These complexes feature effective shielding of the lanthanide ion by
the cobalt-containing bulky fragment, resulting in the generation of relatively strong 4f-luminescence
signals from Yb(III), Nd(III), and Er(III) ions. One of the most significant and intriguing aspects of
these compounds is their potential application as components in electroluminescent devices that emit
in the NIR region. The desire to obtain homogeneous thin films for luminescent layers has prompted
significant interest in the development of hybrid materials based on lanthanide porphyrinates [25–
26].
Lanthanide-porphyrin complexes have emerged as highly promising materials for the
development of emission layers for various applications [27–28]. The efficiency of
electroluminescent devices has been significantly enhanced by carefully selecting appropriate extra
ligands in complexes and matrix materials. Kango and colleagues proposed the replacement of
acetylacetonate with a cobalt complex (as illustrated in Fig. 7). A device employing a similar
structure exhibited distinct luminescence even at a low voltage of 4 V, with a radiation power ranging
from approximately 0.2 μW cm-2 to 0.6 μW cm-2 at 10-15 V. Substituting polystyrene with
poly(vinylcarbazole) did not noticeably affect the device characteristics, suggesting that charge
carrier transport is primarily governed by the properties of the Yb(III) complexes. Interestingly, by
substituting the cobalt complex with a pyrazolyl borate ligand, the power output of the device was
increased by nearly an order of magnitude.
The formation of polynuclear porphyrin complexes is possible not only when additional
complexing fragments are present in the ligand's structure, but also when multiple tetrapyrrole
macrocycle rings are linked by spacer groups. While most studies focus on porphyrin complexes with
79https://ucj.org.ua
N.N. Semenishyn, S.S. Smola, N.V. Rusakova UCJ № 04 / Vol. 89
Ln-Co complexes were successfully syn-
thesized through the addition of (cyclopen-
tadienyl)-tris-(diethylphosphinite)-cobaltate.
These complexes feature effective shielding of
the lanthanide ion by the cobalt-containing
bulky fragment, resulting in the generation
of relatively strong 4f-luminescence signals
from Yb(III), Nd(III), and Er(III) ions. One of
the most significant and intriguing aspects of
these compounds is their potential application
as components in electroluminescent devices
that emit in the NIR region. The desire to ob-
tain homogeneous thin films for luminescent
layers has prompted significant interest in the
development of hybrid materials based on lan-
thanide porphyrinates [25–26].
Lanthanide-porphyrin complexes have
emerged as highly promising materials for the
development of emission layers for various
applications [27–28]. The efficiency of elec-
troluminescent devices has been significantly
enhanced by carefully selecting appropriate ex-
tra ligands in complexes and matrix materials.
Kango and colleagues proposed the replace-
ment of acetylacetonate with a cobalt complex
(as illustrated in Fig. 7). A device employing
a similar structure exhibited distinct lumi-
nescence even at a low voltage of 4 V, with a
radiation power ranging from approximately
0.2 μW cm-2 to 0.6 μW cm-2 at 10-15 V. Sub-
stituting polystyrene with poly(vinylcarbazole)
did not noticeably affect the device characte
ristics, suggesting that charge carrier transport
is primarily governed by the properties of the
Yb(III) complexes. Interestingly, by substitut-
ing the cobalt complex with a pyrazolyl borate
ligand, the power output of the device was in-
creased by nearly an order of magnitude.
The formation of polynuclear porphyrin
complexes is possible not only when additio
nal complexing fragments are present in the li-
gand's structure, but also when multiple tetra-
pyrrole macrocycle rings are linked by spacer
groups. While most studies focus on porphy-
rin complexes with d-metals, where the mac-
rocycles are linked using various fragments to
vary the distances between porphyrinates, the
nature of the metal remains unchanged.
The dimerization of metalloporphyrins can
also occur due to the presence of bridging extra
ligands such as hydroxo groups, carboxylates
and ethers [29]. However, these systems readi
ly undergo substitution reactions. Porphyrins
themselves can act as bridging ligands [30],
resulting in equilibrium between mono- and
bimolecular forms and changes in the absorp-
tion spectra of the resulting compounds. Ho-
mopolynuclear f-f complexes of porphyrins,
in which the lanthanide ion is coordinated
by four nitrogen atoms of the macrocycle and
several extra ligands, exemplify this behavior.
Particularly labile compounds are those with
water, methanol, ethanol, dimethylformamide,
halogen and hydroxide anions as extra ligands
[31–32]. Such complexes have been isolated
for the late-series lanthanides (Er, Yb, Lu), as
the larger ionic radii of the early-series ions
make effective binding to porphyrin difficult.
These systems are highly labile, as the extra li
gands can be substituted with molecules such
as acetate, 8-hydroxyquinoline, diethoxyetha
ne, tetrahydrofuran and 7-azabenzotriazole,
etc. [33–34]. Moreover, they are prone to di-
merization through the bridging function of
the extra ligands. The structure shown in Fig.
8b was obtained through a two-phase synthe-
sis involving the interaction of mono-com-
plexes in dichloromethane at room temper-
ature. A structural analysis revealed that the
dimer possesses C2 symmetry and consists of
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LANTHANIDE-PORPHYRINS AND LANTHANIDE-PHTHALOCYANINES:
DEVELOPMENT OF STABLE AND EFFECTIVE INFRARED 4F-EMITTIVE COMPOUNDSINORGANIC CHEMISTRY
two six-coordinate Yb(III) ions, with a dis-
tance of 3.581 Å between them, connected by
two asymmetric bridging oxygen atoms from
hydroxo- and 8-hydroxooxyquinoline extra li
gands [22–24, 35].
The systems depicted in Fig. 8 exhibited a
4f-luminescent signal, with a maximum wave-
length (λmax) ranging from 978 to 982 nm in the
NIR region. This wavelength corresponds to
the characteristic 2F5/2 → 2F7/2 transition of the
Yb(III) ion. Among these systems, the com-
plex with water molecules as bridging ligands
(complex 1) displayed the shortest lifetime
of 1.02 μs, which is approximately 1.5 times
shorter than the lifetime of the mononuclear
counterpart. In contrast, complexes 2 and
3 showed an increase in τ4f, with lifetimes of
3.17 μs and 2.27 μs, respectively. These life-
times were considerably longer than the flu-
orescence lifetime, which was not entirely
quenched in these systems, ranging from 4.3
to 4.8 ns. The authors attributed the decrease
in IR luminescence intensity to an increase in
the number of O-H oscillators in the complex
molecules. More stable systems were obtained
when β-diketones and tridentate ligands like
hydridotris(pyrazol-1-yl)borate and cyclopen-
tadienyl-tris-(dialkoxyphosphite)-cobaltate (I)
were employed as extra ligands.
Fig. 8. Complexes of tetra(p-methoxyphenyl)-porphyrin (TMPP) (a) and the structure
of the complex [Yb(TMFP)(μ-OH)]2(THF)·2H2O (b). Taken from [32].
d-metals, where the macrocycles are linked using various fragments to vary the distances between
porphyrinates, the nature of the metal remains unchanged.
The dimerization of metalloporphyrins can also occur due to the presence of bridging extra
ligands such as hydroxo groups, carboxylates and ethers [29]. However, these systems readily
undergo substitution reactions. Porphyrins themselves can act as bridging ligands [30], resulting in
equilibrium between mono- and bimolecular forms and changes in the absorption spectra of the
resulting compounds. Homopolynuclear f-f complexes of porphyrins, in which the lanthanide ion is
coordinated by four nitrogen atoms of the macrocycle and several extra ligands, exemplify this
behavior. Particularly labile compounds are those with water, methanol, ethanol, dimethylformamide,
halogen and hydroxide anions as extra ligands [31–32]. Such complexes have been isolated for the
late-series lanthanides (Er, Yb, Lu), as the larger ionic radii of the early-series ions make effective
binding to porphyrin difficult. These systems are highly labile, as the extra ligands can be substituted
with molecules such as acetate, 8-hydroxyquinoline, diethoxyethane, tetrahydrofuran and 7-
azabenzotriazole, etc. [33–34]. Moreover, they are prone to dimerization through the bridging
function of the extra ligands. The structure shown in Fig. 8b was obtained through a two-phase
synthesis involving the interaction of mono-complexes in dichloromethane at room temperature. A
structural analysis revealed that the dimer possesses C2 symmetry and consists of two six-coordinate
Yb(III) ions, with a distance of 3.581 Å between them, connected by two asymmetric bridging
oxygen atoms from hydroxo- and 8-hydroxooxyquinoline extra ligands [22–24, 35].
a b
Fig. 8. Complexes of tetra(p-methoxyphenyl)-porphyrin (TMPP) (a) and the structure of the
complex [Yb(TMFP)(μ-OH)]2(THF)·2H2O (b). Taken from [32].
The systems depicted in Fig. 8 exhibited a 4f-luminescent signal, with a maximum wavelength
(λmax) ranging from 978 to 982 nm in the NIR region. This wavelength corresponds to the
PHTHALOCYANINES. Three main appro
aches for the synthesis of lanthanide-phthalo-
cyanines can be described: template synthesis
on phthalonitriles, metallation of free phtha-
locyanine, and axial substitution of the metal
ion.
The template synthesis based on phthalonit
riles is the simplest method for obtaining
monophthalocyaninates of lanthanides [36].
Unsubstituted phthalocyaninates of Sm(III),
Gd(III), Yb(III), Lu(III), as well as tetra-
chloro-, tetrabromo-, tetranitro-, and tetra
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N.N. Semenishyn, S.S. Smola, N.V. Rusakova UCJ № 04 / Vol. 89
crown-substituted complexes of lutetium have
been synthesized using this method [37]. The
compounds were obtained by melting the cor-
responding phthalonitriles with lanthanide
salts in the temperature range of 200–300°C,
followed by extraction with organic solvents.
The synthesis conducted in alcohols in the
presence of bases allows reduction at tempe
ratures of 130–160°C. Both unsubstituted and
cyclopropyl-substituted complexes of luteti-
um, as well as isopropylenedioxyphthalocy-
aninates of Sm(III), Eu(III), Tb(III), Dy(III),
Yb(III), Lu(III), have been obtained using this
method [38].
In contrast to monophthalocyaninates, the
synthesis of sandwich complexes requires hi
gher temperatures and increased synthesis du-
ration. Double-decker phthalocyanines can be
obtained with varying yields by heating a mix-
ture of phthalonitrile and lanthanide acetate in
molar ratios ranging from 1:4 to 1:8 at tempera-
tures of 280–290°C. Conducting the synthesis at
temperatures of 300-310°C, followed by vacuum
sublimation of the products, allows the produc-
tion of diphthalocyaninates with yields of up to
60%, depending on the nature of the central ion.
As the lanthanide series progresses, the yields of
diphthalocyaninates increase, while the yields
of side products such as free phthalocyanines
decrease. Diphthalocyaninates of practically the
entire lanthanide series have been obtained us-
ing this method [38].
Triple-decker complexes are obtained by
the interaction of phthalonitrile melts and lan-
thanide acetates at temperatures of 230-290°C
for 1 hour. Thus, phthalocyanine complexes
of lanthanide and yttrium ions have been ob-
tained using this method [39].
A disadvantage of template synthesis is the
low selectivity of the method, resulting in re
latively low product yields, which necessitates
additional purification of the products using
chromatographic methods.
More advanced methods for the synthesis of
phthalocyaninates are based on the interaction
of the free ligand or its dianion with lanthanide
salts. Planar complexes can be synthesized by
reacting lanthanide chlorides or acetates with
dianions obtained by the action of dibutyl
lithium on the corresponding ligands. When
using DBU or 1,10-phenanthroline as bases,
tetra-crown-substituted and octa-alkyl-substi-
tuted monophthalocyaninates of lanthanides
have been obtained with high yields.
The second variation of this reaction in-
volves the interaction of alkaline metal phtha-
locyaninate (typically lithium) with various
lanthanide derivatives. Unlike free ligands,
lithium phthalocyaninate is highly soluble in
methanol, tetrahydrofuran, acetone, and other
organic solvents, allowing the reactions to be
carried out under homogeneous conditions
at relatively low temperatures. A series of mo
nophthalocyaninate complexes with β-dike
tonates as external anions have been obtained
using this approach [40–41]
Triple-decker phthalocyaninates of lantha
nides are obtained by the interaction of lantha-
nide acetates or acetylacetonates with phtha-
locyanine. The reaction takes place in the
presence of DBU at a temperature of 260°C.
In the absence of a base and at a molar ratio
of lanthanide to ligand of 3:1, complexes of
La(III), Nd(III), and Tb(III) were synthesized
under milder conditions (THF, 210°C) with
yields exceeding 60%. The formed diphthalo-
cyaninates, as side products, are separated by
column chromatography on silica gel (eluent:
CHCl3) or on basic aluminum oxide (eluent:
CH2Cl2 or CHCl3-MeOH) [42].
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LANTHANIDE-PORPHYRINS AND LANTHANIDE-PHTHALOCYANINES:
DEVELOPMENT OF STABLE AND EFFECTIVE INFRARED 4F-EMITTIVE COMPOUNDSINORGANIC CHEMISTRY
Thus, the metallation of free ligands or their
dianions with rare earth metal ions represents
an efficient and selective method for synthe-
sizing various mono-, di-, and triphthalocya-
ninate complexes of lanthanides and their ana-
logues, exhibiting high yields and purity of the
target products.
Axial substitution reactions in the metal
ion are typically employed for obtaining mo
nophthalocyaninate compounds. Currently,
there are known methods for synthesizing mo
nophthalocyaninates of indium, zirconium,
hafnium, as well as lutetium. The use of this
method is promising both for modifying the
composition of metal complexes and for inves-
tigating their stability [43].
The composition of sandwich-type phtha-
locyanine complexes is characterized by the
general formulas [M(Pc)2H], [MPc2•] (the dot
represents the Pc2 group with a charge <4 due
to the oxidation of one ligand to the Pc- state),
[M2Pc3], and [MPc4]. The necessary condi-
tions for the formation of sandwich phthalo-
cyaninates are, firstly, that the covalent radius
of the metal complexing agent should exceed
1.35 Å ( the radius of the coordination cavity of
phthalocyanine ) and secondly, the oxidation
state of the metal ion should be at least +3. The
radii of lanthanide cations exceed the size of
the cavities of phthalocyanine ligands, which
is why, upon interaction, sandwich-type dou-
ble- and triple-decker structures are predomi
nantly formed. Depending on the synthesis
conditions, different colored compounds are
obtained - "green" or "blue" forms.
The question of the structure of the "blue"
and "green" forms of lanthanide phthalocy-
aninates remained controversial for a long
time until data from X-ray structural analy-
sis of compounds were obtained. In particu-
lar, complexes of La(III), Gd(III), and Lu(III)
with crown-substituted phthalocyanines in the
"blue" form showed that lanthanide phthalo-
cyaninates are neutral compounds [44].
For colored diphthalocyaninates, the ab-
sorption spectra are determined by the state of
the chromophores of the two ligands and the
presence or absence of interaction between
them. Complexes in which the ligands are in
an equivalent state, for example, [Pc2-M3+Pc2-],
exhibit a Q-band in the absorption spectrum,
which is split into two components: Q' and
less intense Q''. This splitting is caused by the
resonant dipole-dipole interaction between
the chromophores of equivalent ligands and
is manifested as a blue coloration of the com-
pounds. The magnitude of the splitting and the
relative positions of the Q' and Q'' bands de-
pend on the nature of the complexing ion.
In the case of non-equivalence of chromo-
phores resulting from ion association with a
proton ([MPc2H]), localization of the unpaired
electron on one of the ligands ([MPc2
•]), or
dimerization, a single intense Q-band is ob-
served in the absorption spectrum. Its origin
is attributed to the absence of resonant in-
teraction between the ligands and leads to a
green coloration of the compound. A charac-
teristic feature of sandwich-like compounds is
the presence of a weak absorption band in the
range of 450–480 nm in the absorption spect
rum, which corresponds to the ligand absorp-
tion with a non-equivalent chromophoric sys-
tem of the phthalocyanine macrocycle.
Unlike porphyrins, free phthalocyanine li
gands exhibit only fluorescence in the range of
680–720 nm, and the intensity can exceed that
of porphyrins by up to 10 times [45]. These
values allow for the estimation of the energy
of the singlet levels of phthalocyanines, which
falls within the range of 13800–14500 cm-1.
Therefore, only a limited number of Ln(III)
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N.N. Semenishyn, S.S. Smola, N.V. Rusakova UCJ № 04 / Vol. 89
ions, such as Nd(III), Er(III), and Yb(III),
whose excited levels lie below the ligand levels
and whose spectra exhibit narrow bands in the
infrared (IR) region, can exhibit 4f-lumines-
cence in complexes with phthalocyanines.
The practical use of phthalocyanine com-
pounds is often hindered by their low solubi
lity in organic solvents and water. To address
this issue, various substituted derivatives of
phthalocyanines have been synthesized. For
example, the introduction of bulky substi
tuents like naphthyl or crown ethers into the
benzene rings of the phthalocyanine molecule
can enhance its solubility in organic solvents
[46–48]. Moreover, binding crown ether frag-
ments as substituents to the benzene ring of
the isoindole fragment allows the formation
of heteronuclear supramolecular compounds
with alkali and alkaline earth metal salts. These
supramolecular crown-substituted phthalo
cyanines exhibit unique electrophysical and
optical properties due to the presence of chan-
nels with ionic conductivity (crown ether frag-
ments) and semiconductivity (phthalocyanine
macrocycle). This has led to the development
of supramolecular functional materials for ap-
plications in ionic and molecular electronics.
In the context of lanthanide complex-
es, semi-sandwich complexes of Er(III) with
tert-butyl and pentyloxy-substituted phtha-
locyanines showed 4f-luminescence under
indirect excitation in the solid state and in
DMSO-d6. In contrast, bisphthalocyaninates
did not exhibit intrinsic emission from
Er(III) [46].
Binuclear lanthanide complexes based on
hexa-tert-butyl-substituted phthalocyanines
were also synthesized, where the macrocycles
share one benzene ring as a linker. These com-
plexes, involving Dy(III), Yb(III), and Lu(III)
ions, display intense absorption in the NIR
region, with the nature of lanthanide having
minimal effect on the electronic spectrum and
position of the Q-bands [47].
A series of lanthanide complexes with
tetra(15-crown-5)phthalocyanine (H2R4Pc) of
various types luminescent in the IR region
were reported [49–51]. These include unsub-
stituted phthalocyaninates, monophthalocya-
ninates with different axial ligands, and di- and
triphthalocyaninates (Fig. 9).
In all these complexes, the Ln(III) lan-
thanide ion is coordinated to four nitrogen
atoms of the tetrapyrrole macroring. In the
case of monophthalocyaninates, coordination
also occurs to donor atoms of acetate ions,
1,10-phenanthroline or DBU. It was observed
that the presence of a second ligand with re-
spect to the tetrapyrrole ring influences the
4f-luminescence of monophthalocyaninate
complexes, with a nearly two-fold increase in
luminescence observed in the presence of phe-
nanthroline (or DBU). Yb(III) complexes of all
types exhibit near-infrared 4f-luminescence
at 980 nm. The mechanism behind this lumi-
nescence is proposed to involve Dexter energy
transfer or photoinduced electron transfer re-
sulting in the reduction of Yb(III) to Yb(II) in
the excited state of the complex.
Di- and triphthalocyaninates exhibit intense
fluorescence in the range of 690-770 nm when
excited in the UV region. The magnitude of the
short-wavelength shift for the double- and tri-
ple-decker compounds depends on the nature
of the complexing agent and decreases from
Nd(III) to Lu(III). In sandwich-type phthalo-
cyaninates, the 4f-luminescence of Yb(III) is
absent in the double -decker complex and is
observed in the triple-decker complex. This is
likely due to the resonance interaction between
the complexing agents and a greater number of
closely spaced macrocyclic chromophores.
84 ISSN 2708-129X. Укр. хім. журн., 2023
LANTHANIDE-PORPHYRINS AND LANTHANIDE-PHTHALOCYANINES:
DEVELOPMENT OF STABLE AND EFFECTIVE INFRARED 4F-EMITTIVE COMPOUNDSINORGANIC CHEMISTRY
Fig. 9. Mono- (a), double- (b) and triple-decker Ln-phthalocyanines.
It was shown for the first time that 4f-lumi-
nescence in the solid state can only be exhibi
ted by Er(III) and Yb(III) ions in complexes
with tetra(15-crown-5)phthalocyanine. More-
over, for erbium compounds, their intrinsic lu-
minescence is also observed in solutions due
to the low-lying resonance 4I13/2 level of Er(I-
II). The parameters of Er-centered emission at
1540 nm were found to be similar to those of
known inorganic phosphors. This holds great
promise for the development of new infrared
emitters for telecommunication technologies,
as well as applications in biology and medicine.
Analyzing the mentioned works on Ln(III)
phthalocyaninates, two significant drawbacks
cannot be overlooked. Firstly, the low solubi
lity of phthalocyanine compounds in organic
solvents and water complicates their prac-
tical use. Secondly, only a limited number of
phthalocyanines with known composition and
structure have been studied in complexes with
lanthanide ions, and they do not exhibit high
luminescence characteristics. This led to a lit-
tle published research on the 4f- luminescence
of Ln(III) complexes with phthalocyanines.
These limitations highlight the need for fur-
85https://ucj.org.ua
N.N. Semenishyn, S.S. Smola, N.V. Rusakova UCJ № 04 / Vol. 89
ther studies to overcome these drawbacks and
explore new phthalocyanine complexes with
lanthanide ions that possess improved solubi
lity and enhanced fluorescence properties.
CONCLUSIONS. To conclude, the analysis
of the mentioned works on Ln-tetrapyrroles
suggests that the functionalization of macro-
cyclic ligands with chelating fragments holds
promise for achieving high stability and good
luminescence characteristics. Porphyrins and
phthalocyanines are considered convenient
molecular platforms for creating heteronuclear
IR-luminescent complexes. However, there are
two significant shortcomings in the aforemen-
tioned studies.
Firstly, the studies have focused on a limi
ted number of tetrapyrroles, and their inherent
structures may not initially lend themselves to
high luminescent characteristics. This limita-
tion particularly applies to natural porphyrins,
which contain a significant number of C-H
bonds. The vibrations of these bonds can lead
to a reduction in the luminescence of Ln(III)
ions. Exploring alternative or modified tetra-
pyrroles with improved structural features
could be a fruitful direction for future research.
Secondly, the spectral-luminescent studies
of Ln-tetrapyrroles have not been thorough-
ly analyzed in terms of the structural aspects
of these compounds. Understanding the re-
lationship between the structural features of
tetrapyrroles and their luminescent properties
is crucial for designing and optimizing highly
luminescent complexes. Further investigations
should involve comprehensive structural ana
lysis alongside spectral and luminescent cha
racterization to elucidate the structure-proper-
ty relationships and develop guidelines for the
design of efficient Ln-tetrapyrrole complexes.
The authors express their gratitude for
the financial support of the National
Academy of Sciences of Ukraine within
the framework of the state budget
theme «New luminescent near-infra-
red materials based on modified tetra-
pyrrole and complex oxide compounds
of d- and f-elements: synthesis, design,
properties» (0115U002223).
ЛАНТАНІД-ПОРФІРИНИ ТА ЛАНТАНІД-
ФТАЛОЦІАНІНИ: РОЗРОБЛЕННЯ СТАБІЛЬНИХ
ТА ЕФЕКТИВНИХ ІНФРАЧЕРВОНИХ
4F-ВИПРОМІНЮЮЧИХ СПОЛУК
М. М. Семенішин*, С. С. Смола,
Н. В. Русакова
Фізико-хімічний інститут ім. О. В. Богат-
ського НАН України,
Люстдорфська дорога, 86, Одеса 65080,
Україна
*ssmbikola@yahoo.com
Цей огляд присвячено різним синтетич-
ним підходам щодо отримання комплексів
лантанідів із порфіринами та фталоціані-
нами, вивченню їхньої структури та осо-
бливостей випромінювання. Лантанід-те-
трапіроли можуть бути координованими
ядром макроциклу та/або додатковими міс-
цями зв’язування в політопних похідних.
Слід зазначити, що політопні тетрапіроли
дозволяють отримувати полігетероядерні
сполуки, що є досить цікавим з точки зору
їхнього особливого механізму 4f-сенсибілі-
зації. Загальна структурна відмінність між
86 ISSN 2708-129X. Укр. хім. журн., 2023
LANTHANIDE-PORPHYRINS AND LANTHANIDE-PHTHALOCYANINES:
DEVELOPMENT OF STABLE AND EFFECTIVE INFRARED 4F-EMITTIVE COMPOUNDSINORGANIC CHEMISTRY
координованими лантанідами-порфірина-
ми та лантанідами-фталоціанінами полягає
в здатності останніх легко утворювати полі-
палубні сполуки, що призводить до цікавих
змін у фотохімічних процесах, включаючи
4f-сенсибілізацію. В огляді також показа-
но основні напрямки вирішення проблеми
стабільності, а також різні підходи до під-
вищення ефективності 4f-люмінесценції.
Ключові слова: лантаніди, порфірини,
фталоціаніни, 4f-люмінесценція, сенсибілі-
зація.
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Стаття надійшла 16.05.2023.
|
| id | oai:ojs2.1444248.nisspano.web.hosting-test.net:article-544 |
| institution | Ukrainian Chemistry Journal |
| keywords_txt_mv | keywords |
| language | English |
| last_indexed | 2026-07-23T01:09:55Z |
| publishDate | 2023 |
| publisher | V.I.Vernadsky Institute of General and Inorganic Chemistry |
| record_format | ojs |
| resource_txt_mv | ucjorgua/e6/cc8e62b53d1e76ee045ddbe028df8de6.pdf |
| spelling | oai:ojs2.1444248.nisspano.web.hosting-test.net:article-5442026-07-22T08:23:51Z LANTHANIDE-PORPHYRINS AND LANTHANIDE-PHTHALOCYANINES: DEVELOPMENT OF STABLE AND EFFECTIVE INFRARED 4F-EMITTIVE COMPOUNDS Semenishyn, Nikolay Rusakova, Nataliia Smola, Serhii lanthanides; porphyrins; phthalocyanines; 4f-luminescence; sensitization. This review is devoted to different synthetic approaches for obtaining lanthanide complexes with porphyrins and phthalocyanines, studying their structure and emission features. Lanthanide-tetrapyrroles can be core-coordinated or/and coordinated by additional binding sites in polytopic derivatives. It is noteworthy that the polytopic tetrapyrroles allow obtaining polyheteronuclear compounds, which is quite interesting in terms of their particular 4f-sensitization mechanism. A general structural difference between core-coordinated lanthanide-porphyrins and lanthanide-phthalocyanines is the ability of the latter to easily form poly-decker compounds, which leads to interesting changes in photochemical processes including 4f-sensitization. The review also shows the main directions for the solution of the stability issue as well as different approaches for increasing the 4f-luminescence effectiveness. V.I.Vernadsky Institute of General and Inorganic Chemistry 2023-05-25 Article Article Inorganic Chemistry Неорганическая химия Неорганічна хімія application/pdf https://ucj.org.ua/index.php/journal/article/view/544 10.33609/2708-129X.89.04.2023.73-89 Ukrainian Chemistry Journal; Vol. 89 No. 4 (2023): Ukrainian Chemistry Journal; 73-89 Украинский химический журнал; ##issue.vol## 89 ##issue.no## 4 (2023): Ukrainian Chemistry Journal; 73-89 Український хімічний журнал; Том 89 № 4 (2023): Ukrainian Chemistry Journal; 73-89 2708-129X 2708-1281 en https://ucj.org.ua/index.php/journal/article/view/544/276 Copyright (c) 2023 Nikolay Semenishyn, Nataliia Rusakova, Serhii Smola https://creativecommons.org/licenses/by-nc/4.0 |
| spellingShingle | Semenishyn, Nikolay Rusakova, Nataliia Smola, Serhii LANTHANIDE-PORPHYRINS AND LANTHANIDE-PHTHALOCYANINES: DEVELOPMENT OF STABLE AND EFFECTIVE INFRARED 4F-EMITTIVE COMPOUNDS |
| title | LANTHANIDE-PORPHYRINS AND LANTHANIDE-PHTHALOCYANINES: DEVELOPMENT OF STABLE AND EFFECTIVE INFRARED 4F-EMITTIVE COMPOUNDS |
| title_full | LANTHANIDE-PORPHYRINS AND LANTHANIDE-PHTHALOCYANINES: DEVELOPMENT OF STABLE AND EFFECTIVE INFRARED 4F-EMITTIVE COMPOUNDS |
| title_fullStr | LANTHANIDE-PORPHYRINS AND LANTHANIDE-PHTHALOCYANINES: DEVELOPMENT OF STABLE AND EFFECTIVE INFRARED 4F-EMITTIVE COMPOUNDS |
| title_full_unstemmed | LANTHANIDE-PORPHYRINS AND LANTHANIDE-PHTHALOCYANINES: DEVELOPMENT OF STABLE AND EFFECTIVE INFRARED 4F-EMITTIVE COMPOUNDS |
| title_short | LANTHANIDE-PORPHYRINS AND LANTHANIDE-PHTHALOCYANINES: DEVELOPMENT OF STABLE AND EFFECTIVE INFRARED 4F-EMITTIVE COMPOUNDS |
| title_sort | lanthanide-porphyrins and lanthanide-phthalocyanines: development of stable and effective infrared 4f-emittive compounds |
| topic_facet | lanthanides porphyrins phthalocyanines 4f-luminescence sensitization. |
| url | https://ucj.org.ua/index.php/journal/article/view/544 |
| work_keys_str_mv | AT semenishynnikolay lanthanideporphyrinsandlanthanidephthalocyaninesdevelopmentofstableandeffectiveinfrared4femittivecompounds AT rusakovanataliia lanthanideporphyrinsandlanthanidephthalocyaninesdevelopmentofstableandeffectiveinfrared4femittivecompounds AT smolaserhii lanthanideporphyrinsandlanthanidephthalocyaninesdevelopmentofstableandeffectiveinfrared4femittivecompounds |