4f-LUMINESCENCE OF LANTHANIDE IONS IN REGIOISOMERIC CORROLE COMPLEXES
Isomeric ditopic corroles and complexes of Yb (III), Nd (III) and Er (III) based on them were synthesized  and corrole-photosensitized 4f-luminescence in near infrared region was revealed. The structure of isomeric complexes allows adjusting the distance between the corrole core and lan...
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V.I.Vernadsky Institute of General and Inorganic Chemistry
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Ukrainian Chemistry Journal| _version_ | 1871465753221267456 |
|---|---|
| author | Semenishyn, Nikolay Smola, Serhii Rusakova, Mariia Rusakova, Natalia |
| author_facet | Semenishyn, Nikolay Smola, Serhii Rusakova, Mariia Rusakova, Natalia |
| author_institution_txt_mv | [
{
"author": "Nikolay Semenishyn",
"institution": "A.V. Bogatsky Physico-chemical Institute National Academy of Sciences of Ukraine."
},
{
"author": "Serhii Smola",
"institution": "A.V. Bogatsky Physico-chemical Institute National Academy of Sciences of Ukraine"
},
{
"author": "Mariia Rusakova",
"institution": "Odessa I.I. Mechnikov National University"
},
{
"author": "Natalia Rusakova",
"institution": "A.V. Bogatsky Physico-chemical Institute National Academy of Sciences of Ukraine"
}
] |
| author_sort | Semenishyn, Nikolay |
| baseUrl_str | https://ucj.org.ua/index.php/journal/oai |
| collection | OJS |
| datestamp_date | 2026-07-22T08:23:47Z |
| description | Isomeric ditopic corroles and complexes of Yb (III), Nd (III) and Er (III) based on them were synthesized  and corrole-photosensitized 4f-luminescence in near infrared region was revealed. The structure of isomeric complexes allows adjusting the distance between the corrole core and lanthanide ion. The obtained results show that the sensitization mechanism changes drastically for both different lanthanides and isomeric forms. |
| doi_str_mv | 10.33609/2708-129X.87.09.2021.35-44 |
| first_indexed | 2025-09-24T17:43:41Z |
| format | Article |
| fulltext |
35
UDC 535.372:541.49:546.65 doi: 10.33609/2708-129X.87.09.2021.35-44
4f-LUMINESCENCE OF LANTHANIDE IONS IN REGIOISOMERIC
CORROLE COMPLEXES
N.N. Semenishyn1, S.S. Smola1, M.Yu. Rusakova2, N.V. Rusakova1
1 A.V. Bogatsky Physico-Chemical Institute, National Academy of Sciences of Ukraine, 86, Lust-
dorfs’ka doroga, Odessa 65080, Ukraine
2 I.I. Mechnikov National University of Odessa, Dvoryanska 2, Odessa 65026, Ukraine
Email: ssmbikola@yahoo.com
Isomeric ditopic corroles and complexes of Yb (III), Nd (III) and Er (III) based on them were
synthesized and corrole-photosensitized 4f-luminescence in near infrared region was revealed.
The structure of isomeric complexes allows adjusting the distance between the corrole core and
lanthanide ion. The obtained results show that the sensitization mechanism changes drastically
for both different lanthanides and isomeric forms.
Keywords: lanthanides; corroles; isomers; 4f-luminescence; sensitization.
INTRODUCTION. In recent years, corroles
and porphyrins, as separate classes of macro-
cyclic tetrapyrrole compounds, and their metal
complexes are widely studied due to the cha
racteristic and very intense light absorption
and emission; they are also interesting as ef-
fective catalysts, as a basis for various sensors,
solar panels, etc [1]. On the other hand, lantha-
nide compounds are in high demand prima
rily due to their emission features. 4f-Lumines-
cence (as a result of f-f radiative transitions) is a
particular kind of emission due to its strongly
specific wavelengths for each lanthanide ion, to
its lifetime (as a rule 4f-luminescence is a slow
kind of emission and can be admitted as phos-
phorescence) and to a variety of regions of its
appearance (UV, VIS, IR).
One of the main features of lanthanide
spectroscopy is the impossibility of direct ex-
citation of the lanthanide ion, because the f-f
absorption of any lanthanide ion is very weak
according to the Laport rule [2]. This limita-
tion can be easily overcome by using organic
chromophores, which have efficient light ab-
sorption and the ability to transfer energy to
lanthanide ions.
Macrocyclic tetrapyrroles were the first
among macrocyclic compounds to reveal
4f-luminescence sensitization in the ear-
ly 1970s [3–4]. Lanthanide complexes with
macrocyclic tetrapyrroles are promising as
agents for luminescent diagnostics (LD) [5],
photodynamic therapy (PDT) [6] and magne
tic resonance imaging (MRI) [7] due to their
4f-LUMINESCENCE OF LANTHANIDE IONS IN REGIOISOMERIC CORROLE COMPLEXES
36 ISSN 2708-129X. Укр. хім. журн., 2021
PHYSICAL CHEMISTRY
specific luminescent and magnetic properties.
Note that 4f-luminescence in these complexes
is possible in near-infrared (NIR) region only.
Lower triplet state (T1), which is responsible
for the sensitization mechanism, can serve as
an energy donor for lanthanide ions Yb3+, Nd3+
and Er3+, which have low-lying resonant ener-
gy levels. Sensitized 4f-luminescence is a quite
important phenomenon, which is already used
in medicine (drugs, markers, assay) [8], tech-
nology (fiber-optics, OLED), etc. NIR 4f-lu-
minescence is highly demanded for several
important reasons: the light of NIR region
can penetrate biological tissues much more
effectively in comparison to UV/VIS ranges
(UV = ultraviolet, VIS = visual) due to very
poor overlapping with absorption of bioob-
jects; NIR light is absolutely safe for human in
comparison to UV/VIS ranges whose action
can generate dangerous radical species; NIR
photons undergo much less scattering in com-
parison to UV/VIS light [9].
Since the core-coordinated complexes of lan-
thanides with porphyrins, corroles and phthalo-
cyanines are somewhat less stable in compari
son with cyclic and acyclic lanthanide amino
polycarboxylates, it was proposed to obtain
tetrapyrrole-based ditopic compounds, which
allow the lanthanide ion to be substantially co-
ordinated by aminopolycarboxylate site [10,11].
This approach gave two very important achieve-
ments – outstanding stability of lanthanide-por-
phyrins and lanthanide-corroles and similarity
in the effectiveness of both core-coordinated
and side-coordinated lanthanide complexes,
despite noted difference in distance between
chromophore and lanthanide ion.
EXPERIMENT AND DISCUSSION OF
THE RESULTS. The spectra of molecular
fluorescence, 4f-luminescence and excitation
spectra were recorded on a spectrofluorime
ter Fluorolog FL 3–22 (Horiba Jobin Yvon)
using a 450 W Xe-lamp. The spectra of 4f-lu-
minescence of Er(III) complexes were regis-
tered in the 1500–1600 nm range (transition
4I13/2→4I15/2). The spectra of molecular fluores-
cence of porphyrins, corroles and phthalocy-
anines were registered at 550–800 nm (S1-S0
transitions). The integral intensity of lumines-
cence was measured using the software of the
device. The relative quantum yield of molecu-
lar fluorescence (φML) was determined using a
solution of Zn-tpp (H2tpp = 5,10, 15, 20-tet-
raphenylporphyrin) in ethanol as a primary
standard (0.022). The determination of φML
(accuracy ±10%) was made using the 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 sol-
vent and of the sample solvent respectively.
Fluorescence lifetime (τ) was measured un-
der excitation at the Soret band.
The synthesis of starting corroles 1, 2, 4 and
complexes 6, 8 and 10 was performed previ-
ously [10, 12]. The purity of the obtained
compounds was checked by TLC Sorbfil plates
(grain 5–17 μm, UV-254, thickness 0.1 mm) by
Imid Ltd. 1H NMR and 19F NMR spectra were
recorded using Bruker Avance 600 or 400 MHz
in CD3OD. Mass spectra (MS) were registered
on the spectrometer Waters ESI TOF Premier
N.N. Semenishyn, S.S. Smola, M.Yu. Rusakova, N.V. Rusakova
37https://ucj.org.ua
UCJ № 9 / Vol. 87
and the Varian MAT CH-112 spectrometer.
The elemental analysis was performed on the
CHNS analyzer Flash 2000 Thermo Scientific.
{ C a r b o x y m e t h y l - [ 2 - ( c a r b o x y m e -
thyl-{[3-(5,10-diphenyl-corrol-5-yl)-phenylcar-
bamoyl]-methyl}-amino)-ethyl]-amino}-acetic
acid (m-H3edta-corrole 3).
A solution of 1 (150 mg, 0.14 mmol) in dry
DMF (5 ml) was added dropwise to a stirred
solution (80°C) of H4edta dianhydride (52 mg,
0.2 mmol) in dry DMF (5 ml), containing a cata
lytic amount of triethylamine (1 drop), during
10 minutes. After adding, the reaction was con-
tinued at the same conditions for 1 hour until the
starting corrole was determined by TLC in the
reaction mixture. Crude product was precipi
tated with water, filtered and dried to provide
the title compound as a purple powder in 90%
yield (185 mg). 1H NMR (MeOD) δ 9.03 (d, 2H,
J=4.16Hz), 8.83 (d, 2H, J=4.4Hz), 8.69 (d, 2H,
J=4.65Hz), 8.60 (d, 2H, J=4.16Hz), 8.58 (s, 1H),
7.93 (d, 1H, J=8.07Hz), 7.91 (d, 1H, J=7.46Hz),
7.64 (t, 1H, J=7.83Hz), 3.67 (s, 4H), 3.58 (s, 2H),
3.47 (s, 2H), 3.21 (s, 2H), 3.05 (s, 2H). 19F NMR
(MeOD) -140.67 (d, 2F, J=23.16Hz), -140.93 (d,
2F, J=18Hz), -155.67 (t, 2F, J=17.7Hz), -164.65
(t, 2F, J=17.7Hz), -164.79 (t, 2F, J=20.44Hz).
ESI-MS obsd 994 [M-H+]; λabs. (nm(lgε), metha
nol) 410(5.08), 568(4.38), 615(4.26). Calc for
C47H31N7O7F10: C 56.69%, H 3.14%, N 9.85%.
Found: C 56.52%, H 3.03%, N 9.68%.
Inspired by our recent findings regarding
the structure features of corroles [12] and our
discovery of 4f-sensitizing activity of corroles
[10], in the present work we continue the syn-
thesis and study of lanthanide complexes with
these porphyrinoids, which contain strongly
bound Ln3+ ion by aminopolycarboxylic site.
Thus, the main idea of the present investigation
is synthesis of stable lanthanide-porphyrinoids
with acceptable photo-physical parameters
avoiding the challenging synthesis of per-deu-
terated and/or per-fluorinated compounds.
NIR 4f-luminescence in coordination com-
pounds always has poor effectiveness. Tradi-
tionally, this problem is caused by the external
quenching of NIR luminescence – the overlap
of NIR luminescence bands with vibrating
quanta of CH and OH bonds, which are al-
ways present in the structure of the complex
and the environment [13]. It is very difficult
to create a system that does not contain the al-
ready mentioned chemical bonds in both the
structure of the molecule and the solvent. On
the other hand it is important to note that the
complete removal of CH and OH bonds from
the coordination environment of the lantha-
nide ion does not notably solve this problem
[14]. The use of fully deuterated solvents does
not solve this problem, too. Moreover, solu-
tions of Er compounds in dmso and dmso-d6
do not reveal any difference in luminescence
effectiveness [15]. The simultaneous use of
both fully deuterated chromofores (cryptates)
and fully deuterated solvents provides medio-
cre quantum yields of 6.1−6.6% for Yb3+ and
0.66−1.7% for Nd3+ [16]. On the other hand,
fluorinated or/and deuterated ytterbium-por-
phyrins reveal very imposing 4f-luminescence
quantum yields of up to 23% even in non-deu-
terated solvents (there is no data for deutera
ted ones) [17]. This finding does not solve the
above-mentioned problem regarding stabi
lity issues. According to this study, ytterbium
porphyrins decompose under irradiation with
405 nm light and this fact is still a remaining
obstacle for in vivo use.
Since stability and luminescence effec-
tiveness are two major requirements for lan-
thanide-tetrapyrroles, the above-mentioned
4f-LUMINESCENCE OF LANTHANIDE IONS IN REGIOISOMERIC CORROLE COMPLEXES
38 ISSN 2708-129X. Укр. хім. журн., 2021
PHYSICAL CHEMISTRY
approach [10–11] is the only way of solving
stability issues for in vivo use.
The corrole analogue of 5,10,15,20-tetra
phenylporphyrin (H2tpp, which is widely used
as synthetically accessible and most stable) –
5,10,15-triphenylcorrole (H3tpc) is a very pho-
tosensitive compound and since electron-with-
drawing aryl groups increase the photostability
of corroles [18], so we used a corrole with two
C6F5 groups and one aryl group, which could be
further easily modified (Scheme 1).
5,15-Bis-(pentafluorophenyl)-10-(3-ami-
nophenyl)-corrole 1 and 5,15-bis-(pentafluo
rophenyl)-10-(4-aminophenyl)-corrole 2 were
obtained according to the previous data [10,
12]. Aсylation of 1 and 2 with dianhydride of
H4edta, provides compounds 3 and 4 respec-
tively in about 90% yield. The last step of the
synthesis did not require column chromato
graphy (Fig. 1). Ethylenediaminetetraacet-
ic acid was chosen as binding site, since it
forms very stable complexes with lanthanides,
lgβ=15-19 [19].
The complexation reactions of 3 and 4 with
lanthanides were performed quantitatively.
Note that MALDI MS and ESI MS revealed
two peaks in the molecular ion region that cor-
respond to molecules with mono- and bis-ad-
ducts of H2O [10], hence corrole-edta forms
peripheral complexes with two coordinated
water molecules to provide the total coordi-
nation number (CN) of lanthanide ion CN=7.
It is important to know the quantity of water
molecules coordinated to the lanthanide ion
since direct coordination of water to Ln3+ leads
to the above energy dissipation due to overlap-
ping of the 4F3/2→4I15/2 transition (5400 cm-1)
of Nd3+ emission with O-H bond vibrational
quanta ν=2 (6900 cm-1), and such excitation
of vibrational state leads to effective quench-
ing of the 4F3/2-state of Nd3+
ion. Overlapping
of O-H bond vibrational quanta ν=3 with
the 2F5/2→2F7/2 transition (10200 cm−1) of Yb3+
emission leads to the same energy dissipation.
Compounds 1 and 2 have absorption spec-
tra that are characteristic of regular corroles
like 5,10,15-tris-(pentafluorophenyl)corrole
(H3tpfc). The near-UV Soret band maxima for
both 1 and 2 are presented at 415 (5.08) nm
(lgε in parentheses), two Q-bands are in the
visual range: 568 (4.38) and 615 (4.26) nm
(spectra were measured in methanol). Note,
that methanol solutions provide only free base
forms of corroles [20].
Scheme 1. Synthesis of isomeric ditopic corroles and the corresponding lanthanide complexes. i) DMF
anh., NEt3 anh., Ar, H4edta dianhydride, 70–80 °C, 90% yield; ii) methanol, RT, LnCl3aq.
with O-H bond vibrational quanta ν=2 (6900 cm-1), and such excitation of vibrational state leads
to effective quenching of the 4F3/2-state of Nd3+ ion. Overlapping of O-H bond vibrational quanta
ν=3 with the 2F5/2→2F7/2 transition (10200 cm−1) of Yb3+ emission leads to the same energy
dissipation.
Scheme 1. Synthesis of isomeric ditopic corroles and the corresponding lanthanide
complexes. i) DMF anh., NEt3 anh., Ar, H4edta dianhydride, 70–80°C, 90% yield; ii) methanol,
RT, LnCl3aq.
Compounds 1 and 2 have absorption spectra that are characteristic of regular corroles like
5,10,15-tris-(pentafluorophenyl)corrole (H3tpfc). The near-UV Soret band maxima for both 1
and 2 are presented at 415 (5.08) nm (lgε in parentheses), two Q-bands are in the visual range:
568 (4.38) and 615 (4.26) nm (spectra were measured in methanol). Note, that methanol
solutions provide only free base forms of corroles [20].
Ditopic compounds 3 and 4 have exactly the same spectra: the Soret band maxima are the
same for both compounds and presented at 410 nm. Two Q-bands are the same for both
compounds, too, and presented at 568 and 615 nm. All peripheral lanthanide complexes based on
3 and 4 have the same absorption spectra: Soret band is presented at 410 nm and two Q-bands at
568 and 615 nm. These similarities in light absorption features follow from the unchangeable
electronic structure of chromophore. So, peripheral modification at the meta-and para-positions
of phenyl at the 10-th position by edta fragments does not affect the corrole electronic structure.
All compounds 1–10 have similar molecular fluorescence parameters: spectra, kinetic data
and effectiveness. All compounds in DMF solutions provide deprotonated forms only. The
maxima of S-S-emission bands are around 640–650 and 690–700 nm. The molecular
fluorescence quantum yields (φML) of the studied compounds are 6–10%. The fluorescence
lifetimes (τ) of both corroles and lanthanide-corroles in DMF and methanol solutions are 3–5 ns.
4f-Luminescence was observed in DMF and methanol solutions for all Nd, Yb and Er
complexes (Table 1, Fig. 1). The emission maxima are correlated with the fundamental
properties of lanthanides. The 980 nm band of Yb complexes 5 and 6 were analyzed as a
N.N. Semenishyn, S.S. Smola, M.Yu. Rusakova, N.V. Rusakova
39https://ucj.org.ua
UCJ № 9 / Vol. 87
Ditopic compounds 3 and 4 have exactly
the same spectra: the Soret band maxima are
the same for both compounds and presented
at 410 nm. Two Q-bands are the same for both
compounds, too, and presented at 568 and
615 nm. All peripheral lanthanide complexes
based on 3 and 4 have the same absorption
spectra: Soret band is presented at 410 nm
and two Q-bands at 568 and 615 nm. These
similarities in light absorption features follow
from the unchangeable electronic structure of
chromophore. So, peripheral modification at
the meta-and para-positions of phenyl at the
10-th position by edta fragments does not af-
fect the corrole electronic structure.
All compounds 1–10 have similar mole
cular fluorescence parameters: spectra, kine
tic data and effectiveness. All compounds in
DMF solutions provide deprotonated forms
only. The maxima of S-S-emission bands are
around 640–650 and 690–700 nm. The mole
cular fluorescence quantum yields (φML) of the
studied compounds are 6–10%. The fluores-
cence lifetimes (τ) of both corroles and lantha-
nide-corroles in DMF and methanol solutions
are 3–5 ns.
4f-Luminescence was observed in DMF and
methanol solutions for all Nd, Yb and Er com-
plexes (Table 1, Fig. 1). The emission maxima
are correlated with the fundamental properties
of lanthanides. The 980 nm band of Yb com-
plexes 5 and 6 were analyzed as a 2F5/2→2F7/2
transition. Nd complexes 7 and 8 displayed
bands corresponding to 4F3/2→4I9/2 (≈890 nm)
and 4F3/2→4I11/2 transitions (≈1060 nm), the
Er-complexes 9 and 10 emitted at 1540 nm due
to a 4I13/2→4I15/2 transition (1540 nm).
Both Yb complexes reveal relatively weak
4f-luminescent signals, and it is hard to deter-
mine their φ4f. An erbium signal at 1540 nm
was also detected for 9 and 10, but because of
the absence of references for such a far region
only arbitrary units are presented.
The molecular fluorescence lifetime measu
rements showed that the values in methanol
solutions were consistently found to be smaller
than in DMF (for compounds 7 and 8, Table 1),
which may be attributed to more effective vi-
brational accepting modes for nonradiative
decay in methanol. Methanol contains strong
luminescence quenching O-H bonds, whose
importance has earlier been emphasized for
coordinated H2O molecules.
The obtained results indicate that the stu
died lanthanide-corroles are dual-range emit-
ters (Fig.1): visual corrole-based molecular
fluorescence with the most intense band at
λmax ≈ 640–650 nm and 4f-luminescence in the
NIR. This dual emission was observed at room
temperature and in aerated solutions, in con-
trast with most other tetrapyrroles that exhibit
NIR emission as phosphorescence emission
only at deoxygenated conditions and usually
in the frozen state (as a rule, at liquid nitrogen
temperature). The distance between the para-
magnetic ion and the chromophore macrocy-
cle is so large that there is no perturbing effect
of the former on the properties of the latter.
Note, that this is different from the previously
described core-metallated tetrapyrroles with
lanthanide ions, where energy transfer from
the excited chromophore to the lanthanide is
quantitative and no residual fluorescence is ob-
tained [21]. Thus, the studied side-coordinated
lanthanide-corroles have non-quenched mo-
lecular fluorescence.
Strong support for the above analysis comes
from the coincidence between the 4f-lumines-
cence excitation spectra (Fig. 1) and the ab-
sorption spectra of the complexes. This clearly
4f-LUMINESCENCE OF LANTHANIDE IONS IN REGIOISOMERIC CORROLE COMPLEXES
40 ISSN 2708-129X. Укр. хім. журн., 2021
PHYSICAL CHEMISTRY
shows that IET (intramolecular energy trans-
fer) from the donor levels of corroles (i.e., the
antenna-effect) to the resonance levels of lan-
thanide ions takes place. One of the most im-
portant features in sensitizing 4f-luminescence
is the energy of the lowest triplet level (T1) of
the organic chromophore – traditionally, ex-
actly this energy level serves as a donor in IET
to lanthanide ion. It can be calculated from
phosphorescence spectra, and some phospho-
rescent metallocorroles were already reported
[22–24]. Unfortunately, it was impossible to
determine the T1 levels of our compounds be-
cause free-base corroles do not phosphoresce.
[25] This is also the reason that estimating the
IET quantum yield is not possible at this stage.
Fig.1. Excitation and emission of Nd-complexes.
Table 1
Photophysical data for studied compounds
#
UV-vis, nm
(first – Soret
band)
λML(4f), nm ES1, cm-1 τ, ns φML×102* φ4f×103*
1 415,568,615 643,698 15550 4.5±0.01 6.8 -
2 415,568,615 650 15380 3.47±0.01 8.4 -
3 415,568,615 643,698 15550 4.48±0.01 6.7 -
4 410,568,615 642,697 15580 3.72±0.01 7.7 -
5 415,568,615 643,698 15550 4.51±0.01 6.9 <0.1
2F5/2→2F7/2 transition. Nd complexes 7 and 8 displayed bands corresponding to 4F3/2→4I9/2 (≈890
nm) and 4F3/2→4I11/2 transitions (≈1060 nm), the Er-complexes 9 and 10 emitted at 1540 nm due
to a 4I13/2→4I15/2 transition (1540 nm).
Both Yb complexes reveal reltively weak 4f-luminescent signals, and it is hard to
determine their φ4f. An erbium signal at 1540 nm was also detected for 9 and 10, but because of
the absence of references for such a far region only arbitrary units are presented.
The molecular fluorescence lifetime measurements showed that the values in methanol
solutions were consistently found to be smaller than in DMF (for compounds 7 and 8, Table
1), which may be attributed to more effective vibrational accepting modes for nonradiative
decay in methanol. Methanol contains strong luminescence quenching O-H bonds, whose
importance has earlier been emphasized for coordinated H2O molecules.
The obtained results indicate that the studied lanthanide-corroles are dual-range
emitters (Fig.1): visual corrole-based molecular fluorescence with the most intense band at
λmax ≈ 640–650 nm and 4f-luminescence in the NIR. This dual emission was observed at
room temperature and in aerated solutions, in contrast with most other tetrapyrroles that
exhibit NIR emission as phosphorescence emission only at deoxygenated conditions and
usually in the frozen state (as a rule, at liquid nitrogen temperature). The distance between
the paramagnetic ion and the chromophore macrocycle is so large that there is no perturbing
effect of the former on the properties of the latter. Note, that this is different from the
previously described core-metallated tetrapyrroles with lanthanide ions, where energy
transfer from the excited chromophore to the lanthanide is quantitative and no residual
fluorescence is obtained [21]. Thus, the studied side-coordinated lanthanide-corroles have
non-quenched molecular fluorescence.
Fig.1. Excitation and emission of Nd-complexes.
0
200
400
600
800
1000
1200
1400
1600
340 540 740 940 1140
I, a.u.
λ, nm
Nd-para
Nd-meta
molecular
fluorescence
4f-excitation
spectrum
N.N. Semenishyn, S.S. Smola, M.Yu. Rusakova, N.V. Rusakova
41https://ucj.org.ua
UCJ № 9 / Vol. 87
#
UV-vis, nm
(first – Soret
band)
λML(4f), nm ES1, cm-1 τ, ns φML×102* φ4f×103*
6 410,568,615 638,696 15670 3.21±0.02 9.7 <0.1
7 415,568,615 638,696 15670 4.2±0.01 6.8 4.7
7** 415,568,615 638,696 15670 4.1±0.01 5.9 1.0
8 410,568,615 639,695
(891,1061) 15650 3.43±0.02 7.6 2.79
8** 410,568,615 636
(890,1061) 15720 3.20±0.01 4.7 0.5
9 415,568,615 638,696 15670 4.5±0.01 6.7 18500****
10 410,568,615 639,695
(1540) 15650 3.53±0.01 9.2 20000****
Zn-tpp# 425 604,659 16560 2.07±0.01 2.2 -
All solutions with oxygen, DMF, RT, λexc. = 410 nm, C=10-5M.
* ± 10%; ** methanol solution; *** φ4f for Nd3+ was calculated for only 4F3/2→4I9/2 transition;
**** arbitrary units; # Data from [26–27].
Table 1
It can be assumed that in theory, the 4f-sen-
sitization of Yb3+ ion can pass through two
transitions: the traditional Т1→2F5/2 and pre-
sumably S1→2F5/2. [28]. The low level of the Yb3+
4f-luminescent signal in such compounds is at-
tributed to poor contribution of the Т1→4F3/2
transition in 4f-sensitization mechanism for
both compounds 5 and 6. On the other hand,
both the molecular fluorescence and intersys-
tem crossing lifetime of corroles (as well as
for porphyrins) is too short and the transition
S1→2F5/2 seems to be not competitive compared
to S1→S0 (τ is around 3–5 ns) and S1→Tn (τ is
around 10 ns) at least because of the absence of
any kind of direct chemical bonding between
donor and acceptor (direct binding allows very
fast transitions – just picoseconds). Another
very important reason of the very low contri-
bution of this transition is the almost full ab-
sence of overlapping of donor emission (λ range
580–780 nm) and acceptor absorption (λ range
870–1020 nm). On the other hand neodymi-
um-corroles 7 and 8 have perceptible φ4f values.
In this case, the contribution of the S1→4F3/2
resonant transition should rise because of the
good overlapping of donor emission (λ range
580–780 nm) ES1=15670 cm-1 and acceptor ab-
sorption (λ range 570–590 nm). We’d like to
underline that like in the case of Yb3+, the reso-
nant transition S1→4F3/2 is thermodynamically
allowed since corrole ES1=15670 cm-1 and neo-
dymium E4F3/2=11700 cm-1. The contribution of
Т1→4F3/2 stays unknown, but we can speculate
that similarly to Yb complexes, it is very low.
4f-LUMINESCENCE OF LANTHANIDE IONS IN REGIOISOMERIC CORROLE COMPLEXES
42 ISSN 2708-129X. Укр. хім. журн., 2021
PHYSICAL CHEMISTRY
Isostructural lanthanide-porphyrins (and all
other complexes with lanthanides) have an op-
posite feature: the φ4f values of ytterbium com-
plexes are always higher than their isostructur-
al neodymium analogues.
The spatial position of the energy acceptor
ion relative to the corrole chromofore in the
case of ytterbium (para- or meta-regioisomers)
does not matter in terms of its emission effec-
tiveness. Per contra, neodymium emission is
sensitive to the spatial arrangement of ion re
lative to the chromofore, in other words, neo
dymium emission is sensitive to the distance
between donor and acceptor. It is an additional
proof for the domination of the S1→4F3/2 sen-
sitizing transition in neodymium-corroles.
Thus, the meta-isomer of neodymium-corrole
has a φ4f value, which is 2 times higher than
that for para-isomer.
CONCLUSIONS. Isomeric ditopic corroles
and isostructural complexes of Yb (III), Nd
(III) and Er (III) based on them were synthe-
sized. The obtained results show that neodym-
ium luminescence is particular in neodymi-
um-corroles complexes. This work additional-
ly confirms the previous assumption regarding
the 4f-sensitization mechanism pathway in
these compounds. Neodymium emission is
notably sensitive to the spatial position of the
ion relative to the chromofore.
ACKNOWLEDGEMENTS
The authors acknowledge the support
from the Targeted Program of Basic
Research of the National Academy of
Sciences of Ukraine (State registration
№ 0120U100133).
4f-ЛЮМІНЕСЦЕНЦІЯ ІОНІВ ЛАНТАНІДІВ У РЕ-
ГІОІЗОМЕРНИХ КОМПЛЕКСАХ ІЗ КОРОЛАМИ
М. М. Семенішин1*, С. С. Смола1,
М. Ю. Русакова2, Н. В. Русакова1
1 Фізико-хімічний інститут ім. О. В. Бо-
гатського НАН України, 86, вул. Люстдорф-
ська дорога, м. Одеса 65080, Україна
2 Одеський національний університет ім.
І. І. Мечникова, вул. Дворянська 2, м. Одеса
65026, Україна
*e-mail: ssmbikola@yahoo.com
Синтезовано ізомерні дитопні короли
та комплекси Yb (III), Nd (III) та Er (III) на
їхній основі та виявлено корол-фотосен-
сибілізовану 4f-люмінесценцію в ближній
інфрачервоній області. Структура ізомер-
них комплексів дозволяє регулювати від-
стань між ядром королу та іоном ланта-
ноїду. Отримані результати показують, що
механізм сенсибілізації різко змінюється
як для різних лантаноїдів, так і для різних
ізомерних форм.
Ключові слова: лантаноїди; короли; ізо-
мери; 4f-люмінесценція; сенсибілізація.
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Стаття надійшла 30.09.2021.
|
| id | oai:ojs2.1444248.nisspano.web.hosting-test.net:article-352 |
| institution | Ukrainian Chemistry Journal |
| keywords_txt_mv | keywords |
| language | English |
| last_indexed | 2026-07-23T01:07:02Z |
| publishDate | 2021 |
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| spelling | oai:ojs2.1444248.nisspano.web.hosting-test.net:article-3522026-07-22T08:23:47Z 4f-LUMINESCENCE OF LANTHANIDE IONS IN REGIOISOMERIC CORROLE COMPLEXES Semenishyn, Nikolay Smola, Serhii Rusakova, Mariia Rusakova, Natalia lanthanides; corroles; isomers; 4f-luminescence; sensitization. Isomeric ditopic corroles and complexes of Yb (III), Nd (III) and Er (III) based on them were synthesized&nbsp; and corrole-photosensitized 4f-luminescence in near infrared region was revealed. The structure of isomeric complexes allows adjusting the distance between the corrole core and lanthanide ion. The obtained results show that the sensitization mechanism changes drastically for both different lanthanides and isomeric forms. V.I.Vernadsky Institute of General and Inorganic Chemistry 2021-10-25 Article Article Inorganic Chemistry Неорганическая химия Неорганічна хімія application/pdf https://ucj.org.ua/index.php/journal/article/view/352 10.33609/2708-129X.87.09.2021.35-44 Ukrainian Chemistry Journal; Vol. 87 No. 9 (2021): Ukrainian Chemistry Journal; 35-44 Украинский химический журнал; ##issue.vol## 87 ##issue.no## 9 (2021): Ukrainian Chemistry Journal; 35-44 Український хімічний журнал; Том 87 № 9 (2021): Український хімічний журнал; 35-44 2708-129X 2708-1281 en https://ucj.org.ua/index.php/journal/article/view/352/187 Copyright (c) 2021 Nikolay Semenishyn, Serhii Smola, Mariia Rusakova, Natalia Rusakova https://creativecommons.org/licenses/by-nc/4.0 |
| spellingShingle | Semenishyn, Nikolay Smola, Serhii Rusakova, Mariia Rusakova, Natalia 4f-LUMINESCENCE OF LANTHANIDE IONS IN REGIOISOMERIC CORROLE COMPLEXES |
| title | 4f-LUMINESCENCE OF LANTHANIDE IONS IN REGIOISOMERIC CORROLE COMPLEXES |
| title_full | 4f-LUMINESCENCE OF LANTHANIDE IONS IN REGIOISOMERIC CORROLE COMPLEXES |
| title_fullStr | 4f-LUMINESCENCE OF LANTHANIDE IONS IN REGIOISOMERIC CORROLE COMPLEXES |
| title_full_unstemmed | 4f-LUMINESCENCE OF LANTHANIDE IONS IN REGIOISOMERIC CORROLE COMPLEXES |
| title_short | 4f-LUMINESCENCE OF LANTHANIDE IONS IN REGIOISOMERIC CORROLE COMPLEXES |
| title_sort | 4f-luminescence of lanthanide ions in regioisomeric corrole complexes |
| topic_facet | lanthanides corroles isomers 4f-luminescence sensitization. |
| url | https://ucj.org.ua/index.php/journal/article/view/352 |
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