ПОЗАПЛОЩИННО КООРДИНОВАНІ ФТАЛОЦІАНІНАТИ ЦИРКОНІЮ(IV) І ГАФНІЮ(IV)
The article is devoted to methods of synthesis, the structure, and spectral characteristics of zirconium and hafnium phthalocyaninates with out-of-plane coordinated ligands. The general scheme for the synthesis of out-of-plane coordinated Zr and Hf phthalocyanines includes obtaining initial dichlor...
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| Дата: | 2021 |
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| Автори: | , , , , , |
| Формат: | Стаття |
| Мова: | Англійська |
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V.I.Vernadsky Institute of General and Inorganic Chemistry
2021
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Ukrainian Chemistry Journal| _version_ | 1871465735283277824 |
|---|---|
| author | Chernii, Viktor Tretyakova, Iryna Tomachynska, Larysa Gerasymchuk, Yuriy Chernii, Svitlana Pekhnyo, Vasyl |
| author_facet | Chernii, Viktor Tretyakova, Iryna Tomachynska, Larysa Gerasymchuk, Yuriy Chernii, Svitlana Pekhnyo, Vasyl |
| author_institution_txt_mv | [
{
"author": "Viktor Chernii",
"institution": "V.I. Vernadskii Institute of General and Inorganic Chemistry NAS of Ukraine"
},
{
"author": "Iryna Tretyakova",
"institution": "IGIC"
},
{
"author": "Larysa Tomachynska",
"institution": "V.I. Vernadskii Institute of General and Inorganic Chemistry NAS of Ukraine"
},
{
"author": "Yuriy Gerasymchuk",
"institution": "Institute of low temperatures and structural researches of the Polish Academy of Sciences"
},
{
"author": "Svitlana Chernii",
"institution": "V.I. Vernadskii Institute of General and Inorganic Chemistry NAS of Ukraine"
},
{
"author": "Vasyl Pekhnyo",
"institution": "V.I. Vernadskii Institute of General and Inorganic Chemistry NAS of Ukraine"
}
] |
| author_sort | Chernii, Viktor |
| baseUrl_str | https://ucj.org.ua/index.php/journal/oai |
| collection | OJS |
| datestamp_date | 2026-07-22T08:23:47Z |
| description | The article is devoted to methods of synthesis, the structure, and spectral characteristics of zirconium and hafnium phthalocyaninates with out-of-plane coordinated ligands. The general scheme for the synthesis of out-of-plane coordinated Zr and Hf phthalocyanines includes obtaining initial dichloride or dihydroxo complexes, which then undergo substitution reactions with -dicarbonyl compounds, hydroxybenzoic, sulfo- and aliphatic carboxylic acids, etc. In the case of polyphenols, which are bidentate ligands, one ligand is coordinated to the central atom of the macrocycle. If -dicarbonyl compounds or carboxylic acids are introduced into the reaction, two ligands are coordinated. The reactivity of the out-of-plane coordinated ligands of Zr and Hf phthalocyanines was also investigated. In all obtained out-of-plane coordinated Zr and Hf phthalocyanines, the ligands are located in the cis position relative to the plane of the phthalocyanine macrocycle. X-ray diffraction, NMR, and UV-Vis spectroscopy have proved this arrangement of ligands. According to the X-ray diffraction data of Zr and Hf dibenzoylmethanato phthalocyanines, the metal atom is out of the plane of the phthalocyanine macrocycle, which itself is not planar. The central atoms are located almost in the middle between the N4 planes of the phthalocyanine macrocycle and the O4 of the extraplanar ligands. The UV-Vis spectra of out-of-plane coordinated Zr and Hf phthalocyanines in organic solvents have a typical appearance for most metal phthalocyanines, characterized by a B-band of absorption in the region of 335–350 nm, a Q-band at 680-690 nm, and its satellite in the region of 615–620 nm. If the extraplanar ligand is a chromophore (e.g., curcumin or condensed derivatives of dehydroacetic acid), there are additional absorption bands in  UV-Vis spectra located between the B- and Q-bands. The influence of the nature of the central metal atoms, ligands and solvents on the fluorescent properties of the out-of-plane coordinated Zr and Hf phthalocyanines was also discussed. |
| doi_str_mv | 10.33609/2708-129X.87.08.2021.82-98 |
| first_indexed | 2025-09-24T17:43:40Z |
| format | Article |
| fulltext |
82 ISSN 2708-129X. Укр. хім. журн., 2020
UDC 667.287.53, 546.82/.83 doi: 10.33609/2708-129X.87.08.2021.82-98
OUT-OF-PLANE COORDINATED ZIRCONIUM(IV) AND HAFNIUM(IV)
PHTHALOCYANINATES
V.Y. Chernii*, I.M. Tretyakova1, L.A. Tomachynska1, Y.S. Gerasymchuk2,
S.V. Chernii1, V.I. Pekhnyo1
1V.I. Vernadskii Institute of General and Inorganic Chemistry of the National Academy of Sciences
of Ukraine, 32/34 Akad. Palladina Ave., Kyiv, Ukraine
2Institute of LowTtemperatures and Structural Research of the Polish Academy of Sciences, st. Okol-
na 2, 50–422, Wroclaw, Poland
*e-mail: v.chernii@gmail.com
The article is devoted to methods of synthesis, the structure, and spectral characteristics of
zirconium and hafnium phthalocyaninates with out-of-plane coordinated ligands. The gene
ral scheme for the synthesis of out-of-plane coordinated Zr and Hf phthalocyanines includes
obtaining initial dichloride or dihydroxo complexes, which then undergo substitution reac-
tions with β-dicarbonyl compounds, hydroxybenzoic, sulfo- and aliphatic carboxylic acids,
etc. In the case of polyphenols, which are bidentate ligands, one ligand is coordinated to the
central atom of the macrocycle. If β-dicarbonyl compounds or carboxylic acids are introduced
into the reaction, two ligands are coordinated. The reactivity of the out-of-plane coordinated
ligands of Zr and Hf phthalocyanines was also investigated. In all obtained out-of-plane co-
ordinated Zr and Hf phthalocyanines, the ligands are located in the cis position relative to the
plane of the phthalocyanine macrocycle. X-ray diffraction, NMR, and UV-Vis spectroscopy
have proved this arrangement of ligands. According to the X-ray diffraction data of Zr and Hf
dibenzoylmethanato phthalocyanines, the metal atom is out of the plane of the phthalocya-
nine macrocycle, which itself is not planar. The central atoms are located almost in the middle
between the N4 planes of the phthalocyanine macrocycle and the O4 of the extraplanar li
gands. The UV-Vis spectra of out-of-plane coordinated Zr and Hf phthalocyanines in organic
solvents have a typical appearance for most metal phthalocyanines, characterized by a B-band
of absorption in the region of 335–350 nm, a Q-band at 680-690 nm, and its satellite in the re-
gion of 615–620 nm. If the extraplanar ligand is a chromophore (e.g., curcumin or condensed
derivatives of dehydroacetic acid), there are additional absorption bands in UV-Vis spectra
located between the B- and Q-bands. The influence of the nature of the central metal atoms,
ligands and solvents on the fluorescent properties of the out-of-plane coordinated Zr and Hf
phthalocyanines was also discussed.
Keywords: phthalocyanines, zirconium, hafnium, synthesis, spectroscopy.
V.Y. Chernii, I.M. Tretyakova, L.A. Tomachynska, Y.S. Gerasymchuk, S.V. Chernii, V.I. Pekhnyo
83https://ucj.org.ua
UCJ № 8 / Vol. 87
INTRODUCTION. The phthalocyanine
macrocycle was first obtained by chance in
1907 [1] and its copper salt in 1927 [2] as a
by-product of reactions of phthalic acid deri
vatives. The new unknown substance attracted
attention because it had deep blue color, was
thermally stable, and did not decompose in al-
kalies and acids. In 1934, Linstead showed that
phthalocyanines are formed at high tempera-
tures from various phthalic acid derivatives via
the stage of formation of 1,2-dicyanobenzene,
and that phthalocyanine itself is its tetramer
and may contain a metal ion [3]. The following
year, Robertson confirmed the structure and
aromaticity of the phthalocyanine macrocycle
by X-ray diffraction [4]. Subsequently, Lin-
stead developed general methods for the syn-
thesis of various phthalocyanine precursors,
in particular, o-dinitriles [5–8], metal phtha-
locyanines [9–13], substituted phthalocya-
nines [14, 15], and their analogues [16–23].
To date, complexes of phthalocyanines with
most metals and some nonmetals have been
described [24].
Phthalocyanines are aromatic systems whe
rein the number of π-electrons in the conjugate
system corresponds to Huckel’s rule (4n + 2)
and is 42 electrons. Their aromaticity is con-
firmed by the proximity of the bond lengths
in the molecule: the bond length (C-N) in the
macrocycle (1.35 Å) is close to the bond length
in benzene nuclei (1.40 Å). At the same time,
the bond length (C-C) between the macrocy-
cle and benzene rings is significantly longer; it
is 1.50 Å, which is close to the length of the
σ-bond (1.54 Å). This indicates that the cou-
pling between the π-electron systems of the
macrocycle and benzene nuclei is weak. Thus,
there are two quasi-autonomous aromatic sys-
tems of benzene nuclei and an aromatic mac-
roring system in the molecule [25]. The π-elec-
tron system of the phthalocyanine molecule is
quite large; the difference in the energy level of
HOMO and LUMO corresponds to the photon
energy of the long-wavelength part of the spec-
trum. This causes a deep blue or green color of
these compounds.
The aromaticity of phthalocyanines ex-
plains their high thermal and chemical sta-
bility and low tendency to open the conjugate
macrocycle system [24]. The phthalocyanine
macrocycle, as an aromatic system, undergoes
electrophilic substitution reactions: chlorina
tion, bromination, sulfochlorination, sulfo
nation, etc. However, these reactions result
in a nonstoichiometric mixture of different
isomeric compounds. Therefore, appropriate
substituted o-dinitriles are generally used to
produce peripherally substituted phthalocy-
anines. Nevertheless, individual compounds
are formed only from symmetric o-dinitriles
(for example, 4,5- or 3,6-substituted 1,2-dicy-
anobenzenes). In all other cases, mixtures of
isomeric products are formed.
Phthalocyanine ligand is a dibasic, tet-
radentate acid. The cavity diameter of the
phthalocyanine macrocycle is 3.65–4.50 Å
[24], which is suitable for the coordination
of most metal ions. If the valence of the me
tal ion in the phthalocyanine complex is more
than two, or its coordination number is more
than four, then such a central metal atom (CA)
contains (or may contain) additional axial or
out-of-plane ligands. In [24], some possible
types of out-of-plane ligands coordinating to
the phthalocyanine macrocycle are presented
(Fig. 1).
OUT-OF-PLANE COORDINATED ZIRCONIUM(IV) AND HAFNIUM(IV) PHTHALOCYANINATES
84 ISSN 2708-129X. Укр. хім. журн., 2021
INORGANIC CHEMISTRY
Fig. 1. Molecular structures of different types of phthalocyanine complexes PclMmXn [24].
Fig. 1. Molecular structures of different types of phthalocyanine complexes PclMmXn [24].
The high coordination numbers of the CA make it possible to form out-of-plane coordinated
complexes of various compositions and structures. For example, carboxylate complexes are described
for phthalocyanines of tin with coordination numbers (CN) 7 or 8 [26, 27] and phthalocyanines of Zr
and Hf with CN 8, in which the carboxylate ligand can be bridged between two macrocyclic systems
[28]. (Fig. 2). For phthalocyanines of Zr and Hf, out-of-plane coordinated complexes with a
reasonably wide range of ligands are described.
The high coordination numbers of the CA
make it possible to form out-of-plane coordi-
nated complexes of various compositions and
structures. For example, carboxylate complex-
es are described for phthalocyanines of tin
with coordination numbers (CN) 7 or 8 [26,
27] and phthalocyanines of Zr and Hf with
CN 8, in which the carboxylate ligand can
be bridged between two macrocyclic systems
[28]. (Fig. 2). For phthalocyanines of Zr and
Hf, out-of-plane coordinated complexes with a
reasonably wide range of ligands are described.
Methods of synthesis of zirconium and haf-
nium phthalocyaninates with out-of-plane co-
ordinated ligands. Zr and Hf phthalocyanine
dichloride complexes were first obtained by
fusing 1,2-dicyanobenzene with the corre-
sponding metal tetrachlorides [29]. However,
it was found [30] that the reaction produces
Zr and Hf phthalocyanines with a chlorinated
macrocycle, which was assigned the formula
ClPcMCl2. It was later proved [31–33] that
ClPcMCl2 is not an individual compound, it
is a statistical mixture of chlorinated phtha-
locyanines with different numbers of chlorine
atoms in the molecule, which corresponds
to the general formula ClPcMCl2. This con-
clusion was confirmed by NMR spectra of
bis-(acetylacetonato)phthalocyanines of Zr
and Hf obtained from corresponding dichlo-
ride complexes described in [29, 30] and pure
PcMCl2 [31–33].
V.Y. Chernii, I.M. Tretyakova, L.A. Tomachynska, Y.S. Gerasymchuk, S.V. Chernii, V.I. Pekhnyo
85https://ucj.org.ua
UCJ № 8 / Vol. 87
Fig. 2. Crystal structure of Sn didodecanoato phthalocyaninate, CN = 7 (A) [26]; Sn didecanoato
phthalocyaninate, CN = 8 (B) [27]; Hf dinonanoato phthalocyaninate, CN = 8 (C) and Zr bis(dinonano-
ato phthalocyaninate), CN = 8 (D) [28].
The out-of-plane chlorine atoms in Zr and
Hf phthalocyanines are quite “mobile”, they
undergo hydrolysis to form corresponding di-
hydroxo complexes PcM(OH)2 [30, 32, 34, 35].
This feature was used for the synthesis of PcML
(L = pyrocatechins) and PcML2 (L = β-dicar-
bonyl compounds, hydroxybenzoic, sulfo- and
aliphatic carboxylic acids, etc) [28, 36–38].
The general scheme for the synthesis of
out-of-plane coordinated Zr and Hf phthalo-
cyanines is presented in Fig. 3. In the case of
polyphenols, which are bidentate ligands, one
ligand is coordinated to the CA of the macro-
cycle with CN = 6. If β-dicarbonyl compounds
or carboxylic acids are introduced into the re-
action, two ligands are coordinated [36–38]
and the CN of the CA is 8 (Fig. 3). In this case,
the carboxylic acid is a bidentate or bridging
bidentate ligand [28].
According to the scheme shown in Fig. 3,
out-of-plane coordinated Zr and Hf phtha-
locyanines with more complex ligands were
also obtained [37, 39–44] (Fig. 4). The reac-
tivity of out-of-plane coordinated ligands of
Zr and Hf phthalocyanines was also inves-
tigated. It was found [37] that the “mobility”
of the chlorine atom in the 3-chloro-2,4-pen-
tanedionate ligand is very low (in contrast to
free 3-chloro-2,4-pentanedione), so it does
not interact with thiol-containing compounds
OUT-OF-PLANE COORDINATED ZIRCONIUM(IV) AND HAFNIUM(IV) PHTHALOCYANINATES
86 ISSN 2708-129X. Укр. хім. журн., 2021
INORGANIC CHEMISTRY
(Fig. 5, reaction A). As a result of complex-
ing, the phthalocyanine macroring stabilizes
the formed cyclic system of the β-diketonate
ligand, and the mobility of the chlorine atom
sharply decreases [28, 37]. During the reaction
of the ester group, the formation of amides
(Fig. 5, reaction B) was proved [28]. However,
when a reaction with ammonia or hydrazine
takes place, a mixture of indeterminate pro
ducts is formed, or destruction of the macro
cyclic system is observed. The synthesis reac-
tion of Zr and Hf dibromide bis-(N-(5-pen-
tanoato)-4-methyl-pyridiniumcarboxylato)
phthalocyaninates proved to be quite indi
cative. When dichloride complexes of Zr and
Hf phthalocyaninates react with N-(5-pen-
tanoato)-4-methyl-pyridiniumcarboxylic acid
bromide, a corresponding cationic complex is
formed, but the anion is a mixture of chlorides
and bromides (Fig. 5, reaction B).
Fig. 3. Scheme of synthesis of some out-of-plane coordinated Zr and Hf phthalocyanines
According to the scheme shown in Fig. 3, out-of-plane coordinated Zr and Hf phthalocyanines
with more complex ligands were also obtained [37, 39–44] (Fig. 4). The reactivity of out-of-plane
coordinated ligands of Zr and Hf phthalocyanines was also investigated. It was found [37] that the
“mobility” of the chlorine atom in the 3-chloro-2,4-pentanedionate ligand is very low (in contrast to
free 3-chloro-2,4-pentanedione), so it does not interact with thiol-containing compounds (Fig. 5,
reaction A). As a result of complexing, the phthalocyanine macroring stabilizes the formed cyclic
system of the β-diketonate ligand, and the mobility of the chlorine atom sharply decreases [28, 37].
During the reaction of the ester group, the formation of amides (Fig. 5, reaction B) was proved [28].
However, when a reaction with ammonia or hydrazine takes place, a mixture of indeterminate products
is formed, or destruction of the macrocyclic system is observed. The synthesis reaction of Zr and Hf
dibromide bis-(N-(5-pentanoato)-4-methyl-pyridiniumcarboxylato) phthalocyaninates proved to be
quite indicative. When dichloride complexes of Zr and Hf phthalocyaninates react with N-(5-
pentanoato)-4-methyl-pyridiniumcarboxylic acid bromide, a corresponding cationic complex is formed,
but the anion is a mixture of chlorides and bromides (Fig. 5, reaction B).
Fig. 3. Scheme of synthesis of some out-of-plane coordinated Zr and Hf phthalocyanines.
V.Y. Chernii, I.M. Tretyakova, L.A. Tomachynska, Y.S. Gerasymchuk, S.V. Chernii, V.I. Pekhnyo
87https://ucj.org.ua
UCJ № 8 / Vol. 87
Fig. 4. Out-of-plane coordinated derivatives of Zr and Hf phthalocyanines with: 4-benzoyl-3-methyl-
1-phenyl-2-pyrazolin-5-onate (A) [39]; 2-(2,4-dioxopentan-3-ylthio)-N-(4-methoxyphenyl)acetamide
(B) [40]; 2Z)-4-[(4-methylphenyl)-amino]-2-ovate (C) [37]; (4-[4-({2-[(2-methylphenyl)amino]-2-oxo
ethyl}thio)-3-dimethyl-1pyrazol-1-yl]benzoic (D) [37]; oxyquinolinate (E) [ 41], curcuminate (F) [42],
dehydroacetate and its condensed derivatives (G) [43, 44] as ligands, and clathrochelate (H) [45].
If the bis-ω-bromopentanoates of Zr and
Hf phthalocyanines react with 4-methylpyri-
dine individual cationic complexes are formed
(Fig. 5, reaction D) [28, 37]. In [35], it was reco
mmended to carry out similar reactions based
on Zr and Hf dihydroxo phthalocyanines.
Structure of out-of-plane coordinated zir-
conium and hafnium phthalocyanines. In all
out-of-plane coordinated Zr and Hf phthalo-
cyanines, the ligands are located in the cis posi-
tion relative to the plane of the phthalocyanine
macrocycle. This arrangement of ligands has
been proven by X-ray diffraction, NMR, and
UV-Vis spectroscopy [36–38, 46].
According to the X-ray diffraction data of
Zr and Hf dibenzoylmethanato phthalocya-
nines, the CA of the metal is out of the plane of
the phthalocyanine macrocycle, which itself is
not planar [46]. The central atoms are located
almost in the middle between the N4 planes of
the phthalocyanine macrocycle and the O4 of
the extraplanar ligands (Table 1).
OUT-OF-PLANE COORDINATED ZIRCONIUM(IV) AND HAFNIUM(IV) PHTHALOCYANINATES
88 ISSN 2708-129X. Укр. хім. журн., 2021
INORGANIC CHEMISTRY
Fig. 5. Reactivity of extraplanar ligands in Zr and Hf phthalocyanines.
The similarity of the structural parameters
of Zr and Hf bis-(dibenzoylmethanato)phtha-
locyanines is observed (see Table 1). This simi
larity exists for the very close atomic radii of
Zr and Hf ions due to lanthanide compression
[47]. This leads to the similarity of both struc-
tural parameters and other spectral characte
ristics, such as the position of signals in NMR
spectra and absorption maxima in UV-Vis
spectra [46].
Table 1
Selected parameters of bond lengths and distances to the planes N4 and O4
of Zr and Hf bis-(dibenzoylmethanato)phthalocyanines.
Bond Length, Å Angle ω, degree Distance to the plane, Å
Zr ‑ О 2.1610(16) ‑ 2.1807(16) О ‑ Zr ‑ О 71.41 – 74.52 1.184
Hf ‑ О 2.1577(14) ‑ 2.1719(14) О ‑ Hf ‑ О 70.99 – 74.91 1.181
Zr ‑ N 2.282(2) ‑ 2.303(2) N ‑ Zr ‑ N 73.35 – 74.26 1.211
Hf ‑ N 2.2641(17) ‑ 2.2919(16) N ‑ Hf ‑ N 73.58 – 74.58 1.194
V.Y. Chernii, I.M. Tretyakova, L.A. Tomachynska, Y.S. Gerasymchuk, S.V. Chernii, V.I. Pekhnyo
89https://ucj.org.ua
UCJ № 8 / Vol. 87
Most of the described out-of-plane coordi-
nated Zr and Hf phthalocyanines were investi-
gated by NMR spectroscopy. As concerns the
complexes with pyrocatechinate and sulfosali
cylate ligands, their solubility is too low for ac-
curate NMR studies [36]. However, complexes
of Zr and Hf phthalocyanines with β-diketones,
β-ketoethers, and carboxylic acids as extrapla-
nar ligands have been studied extensively [39,
48–50]. In the case of β-dicarbonyl complexes,
the coordination of two ligands to the CA of
the macrocycle was established. Proton signals
in the NMR spectra can be divided into two
groups [48]. The first group is the signals of
phenyl protons of the phthalocyanine macro
cycle located in the region of 9.5–8.0 ppm.
Their position and morphology of multiplets
are similar to the data given in the literature
for β-dicarbonyl phthalocyanine complexes of
thorium and uranium [51]. The second group
is proton signals of extraplanar ligands. They
are always upfield shifted compared to unco-
ordinated ligands. Analysis of NMR spectre
data for pairs of complexes (Zr-Hf) with the
identical ligands shows that the CA has almost
no effect on the position of the signals in the
spectra because they have very similar values
[36, 37, 46]. In the case of complexes with
asymmetric β-dicarbonyl ligands, the forma-
tion of a mixture of cis- and trans-isomers has
been proved [36, 48] (Fig. 6).
Fig. 6. Coordination of asymmetric β-diketones
to the CA of the phthalocyanine macrocycle with
the formation of a mixture of isomers.
Spectral characteristics. The UV-Vis spec-
tra of out-of-plane coordinated Zr and Hf
phthalocyanines in organic solvents have a
typical appearance for most metal phthalocy-
anines, characterized by a B-band of absorp-
tion in the region of 335–350 nm, a Q-band of
680–690 nm, and its satellite in the region of
615–620 nm (Table 2) [36–38]. If the extrapla-
nar ligand is a chromophore (e.g., curcumin or
condensed derivatives of dehydroacetic acid),
there are additional absorption bands in the
UV-Vis spectra located between the B- and
Q-bands [38, 42, 44].
Table 2
UV-Vis data of out-of-plane coordinated Zr and Hf phthalocyanines in toluene.
М Ligand λ, nm (log ε)
B-band Q-satellite Q-band
Zr
OH
OH
O
HO3S 342 (4.72) 618 (4.44) 686 (5.18)
Hf 349 (4.70) 618 (4.38) 688 (5.19)
OUT-OF-PLANE COORDINATED ZIRCONIUM(IV) AND HAFNIUM(IV) PHTHALOCYANINATES
90 ISSN 2708-129X. Укр. хім. журн., 2021
INORGANIC CHEMISTRY
М Ligand λ, nm (log ε)
B-band Q-satellite Q-band
Zr
OH OH
HO3S SO3H 343 (4.88) 617 (4.54) 688 (5.28)
Hf 349 (4.89) 620 (4.56) 690 (5.28)
Zr
O O
CH3H3C 344.6 (4.78) 617.2 (4.58) 684.9 (5.29), 688.1 (5.29) d
Hf 340.9 (4.82) 616.7 (4.61) 684.2 (5.37), 686.8 (5.38) d
Zr
O O
Ph Ph 340.0 (5.05) 617.0 (4.56) 656.0 (4.48), 683.0 (5.31) w
Hf 340.0 (5.05) 617.0 (4.54) 655.0 (4.48), 683.0 (5.30) w
Zr
O O
CF3F3C 336.1 (4.63) 618.8(4.29) 685.2 (5.00), 689.4(5.00) d
Hf 345.0 (4.74) 619.4 (4.40) 682.1 (5.08), 693.3 (5.09) d
Zr
O O
H3C Ph 342.8 (4.58) 618.2 (4.30) 686.4 (5.13) w
Hf 342.8 (4.53) 616.9 (4.27) 684.9 (5.17) w
Zr
O O
CH3
CH3
OCH3
(H3C)3C
341.7 (4.80) 617.1 (4.52) 654.7 (5.28), 685.0 (5.31) w
Hf 337.1 (4.87) 616.3 (4.61) 683.7 (5.57), 685.6 (5.57) w
Zr
O O
H3C O CH3
CH3
341.7 (4.85) 618.1 (4.52) 686.9 (5.27) w
Hf 339.5 (4.78) 616.2 (4.42) 684.1 (5.22) w
Zr
C7H15CO2Н
341 620 sh 684
Hf 340 616 sh 684
Table 2
In the case of water-soluble Zr and Hf
phthalocyanines, such as sulfosalicylate, gal-
late, chromotropic and amino acids, absorp-
tion bands characteristic of phthalocyanine
aggregates are observed in water [52].
The authors showed [46, 48, 49] that in some
cases broadening or splitting of the Q-band in
the UV-Vis spectra of β-diketonate and β-ke-
toester complexes is observed. Such spectral
characteristics are untypical of phthalocyanine
complexes and associated with a significant
decrease in molecule symmetry, proving the
cis-coordination of the ligands relative to the
plane of the phthalocyanine macrocycle.
In [50], the luminescent properties of Zr and
Hf phthalocyanines with extraplanar ligands in
various solvents were investigated. Analyzing
the experimental data, the authors concluded
that the heavy central metal atom reduces the
fluorescence intensity of the complexes. For
example, in the series Zn, Zr, Hf, the highest
fluorescence is shown by zinc phthalocyanine
V.Y. Chernii, I.M. Tretyakova, L.A. Tomachynska, Y.S. Gerasymchuk, S.V. Chernii, V.I. Pekhnyo
91https://ucj.org.ua
UCJ № 8 / Vol. 87
(0.200 in DMSO), the quantum yield of fluo-
rescence of Zr phthalocyanine is about an or-
der of magnitude lower (Table 3), and Hf com-
plexes do not fluoresce, or their fluorescence
is very low. The highest Stokes shift is 20 nm
which is typical of phthalocyanine complexes.
The influence of the nature of the ligands
and solvents on the quantum yield of fluores-
cence and the lifetime of excited states in out-
of-plane coordinated Zr phthalocyanines was
also established. The lowest fluorescence quan-
tum yield was observed for Zr phthalocyanine
dichloride (in DMSO it is 0.006), and for the
complex of Zr phthalocyanine with 4-benzoyl-
3-methyl-1-phenyl-1H-pyrazole-5(4H)-one
it is 0.073 (Table 3). Slightly lower quantum
yields were also observed for carboxylate com-
plexes of Zr phthalocyanine in comparison
with β-diketonate [39, 46, 49, 50]. Regarding
the nature of the solvent, in toluene, the largest
values of the molar extinction coefficient and
the smallest values of the lifetime of the excit-
ed state were observed. At the same time, the
highest values of the quantum yield of fluores-
cence and the lifetime of the excited state were
obtained in DMSO (Table 3).
Table 3
Fluorescence data of out-of-plane coordinated PcZrL2.
L Solvent λF, nm ΦF Δλ τ, ns
O O
CH3H3C toluene 708 0.054 20 1.66
DMSO 702 0.073 18 6.33
O O
CF3F3C toluene 702 0.063 16 2.58
DMSO 700 0.075 18 8.87
O O
H3C Ph toluene 701 0.042 13 1.66
DMSO 703 0.072 17 5.42
O O
CH3
CH3
OCH3
(H3C)3C
toluene 695 0.004 13 1.27
DMSO 697 0.069 12 5.72
O O
Ph Ph toluene 693 0.010 10
DMSO 695 0.020 8
N
N
OO
toluene 708 0.073 17 1.99
DMSO 709 0.063 15 5.79
C7H15CO2Н
toluene 697 0.009 13 9.08
DMSO 703 0.013 15 8.46
OUT-OF-PLANE COORDINATED ZIRCONIUM(IV) AND HAFNIUM(IV) PHTHALOCYANINATES
92 ISSN 2708-129X. Укр. хім. журн., 2021
INORGANIC CHEMISTRY
Prospects for application. Phthalocyanine
complexes are widely used in many fields of
science and technology [53]. The areas of their
application can be divided into two groups.
The first group is based on the use in a ho-
mogeneous phase, such as in photodynamic
therapy, catalysis, etc. The second one is based
on transformations at the phase boundary,
as in sensors, photovoltaic cells, and others.
Depending on the chemical nature of the ex-
traplanar ligand, the prospects of its applica-
tion are studied in different fields. Zr and Hf
bis-(β-diketonato)phthalocyanines due to high
electrochemical stability, fluorescence proper-
ties [46, 49, 50], and prominent electrochro-
mism are promising for use as sensors and the
creation of photovoltaic [40, 54, 55] and OLED
elements [56–58]. Watersoluble complexes
with citrate, lysinate, sulfosalicylate and other
ligands show high cytostatic and cytotoxic
activity and can be proposed as agents for the
photodynamic and dark therapy of malignant
neoplasms [59, 60]. The complexes containing
a free amino or carboxy group in extraplanar
ligands show high antimicrobial activity in the
composite cement with graphite oxide used in
dentistry [61, 62]. Zr and Hf phthalocyanines
with extraplanar ligands can inhibit or redirect
the fibril formation of proteins associated with
neurodegenerative diseases [63–67].
CONCLUSIONS. Thus, it is shown that the
coordination of out-of-plane ligands to the
central metal atom in Zr and Hf phthalocya-
nines makes it possible to change their physi
cochemical properties in a targeted manner.
This approach is much simpler than the in-
troduction of substituents on the periphery of
the phthalocyanine macrocycle. It opens up
prospects for using out-of-plane coordinated
Zr and Hf phthalocyanines as photosensitive,
electrochromic, photoelectrocatalytic materi-
als. Hydrophilic groups in the out-of-plane li-
gands provide their biological activity and the
possibility of use as antitumor, antimicrobial
agents.
ACKNOWLEDGEMENT. This article is
dedicated to our teachers, friends, and
colleagues: Professor Stanislaw Radzki
(1950–2008) from the Maria Curie-Skło
dowska University of Lublin, Academician Ser-
hiy Volkov (1935–2016) and Doctor of Chemi-
cal Sciences Oleg Varzatskii (1970–2017) from
the V.I. Vernadsky Institute of General and
Inorganic Chemistry of the National Acade-
my of Sciences of Ukraine, Doctor of Biologi-
cal Sciences Vladyslava Kovalska (1972–2020)
from the Institute of Molecular Biology and
Genetics of the National Academy of Sciences
of Ukraine.
The work was performed within the state
budget theme «Molecular design, directed
synthesis, physical, biochemical study of coor-
dination and supramolecular systems of bio
genic, pharmaceutically important metals for
medicine and technology», state registration
number: 0121U108899 and with financial sup-
port of the NAS of Ukraine research project
0120U101275 of joint competition of projects
of the NAS of Ukraine – NAS of Belarus. Also
V.C. and S.C. thank Igor Siedov and his team
for their help and support.
V.Y. Chernii, I.M. Tretyakova, L.A. Tomachynska, Y.S. Gerasymchuk, S.V. Chernii, V.I. Pekhnyo
93https://ucj.org.ua
UCJ № 8 / Vol. 87
ПОЗАПЛОЩИННО КООРДИНОВАНІ ФТАЛО
ЦІАНІНАТИ ЦИРКОНІЮ(IV) І ГАФНІЮ(IV)
В. Я Черній*, І. М. Третякова1,
Л. А Томачинська1, Ю. С. Герасимчук2,
С. В. Черній1, В. І. Пехньо1
1Інститут загальної та неорганічної хімії
ім. В. І. Вернадського НАН України, просп.
Академіка Палладіна, 32/34, Київ 03142,
Україна
2Інститут низьких температур та струк-
турних досліджень Польської Академії наук,
вул. Околна 2, 50–422, Вроцлав, Польща
*e-mail: v.chernii@gmail.com
Статтю присвячено методам синтезу,
будові та спектральним характеристикам
фталоціанінатів цирконію та гафнію з по-
заплощинно координованими лігандами.
Наведено загальну схему синтезу позапло-
щинно координованих фталоціанінів Zr
та Hf. Методами РСА, ЯМР та ЕСП пока-
зано, що в усіх отриманих позаплощинно
координованих фталоціанінах Zr і Hf лі-
ганди розташовані в цис-положенні щодо
площини макроциклу. Атом металу вихо-
дить із площини макроциклу фталоціані-
ну і розташований майже посередині між
площинами N4 макроциклу фталоціаніну
та О4 позаплощинних лігандів. ЕСП по-
заплощинно кординованих фталоціанінів
Zr та Hf в органічних розчинниках мають
типовий вигляд для фталоціанінів мета-
лів, що характеризується В-смугою погли-
нання в області 335–350 нм, Q-смугою –
680–690 нм, та коливальним супутником
при 615–620 нм. Якщо позаплощинний лі-
ганд є хромофором (наприклад, куркумін
або конденсовані похідні дегідрацетової
кислоти), у ЕСП спостерігаються додатко-
ві смуги поглинання, що знаходяться між
В- та Q-смугами. Також обговорено вплив
центрального атома металу, лігандів та роз-
чинників на флуоресцентні властивості по-
заплощинно координованих фталоціанінів
Zr та Hf.
Ключові слова: фталоціаніни, цирконій,
гафній, синтез, спектроскопія.
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Стаття надійшла 13.09.2021.
|
| id | oai:ojs2.1444248.nisspano.web.hosting-test.net:article-342 |
| institution | Ukrainian Chemistry Journal |
| keywords_txt_mv | keywords |
| language | English |
| last_indexed | 2026-07-23T01:06:45Z |
| publishDate | 2021 |
| publisher | V.I.Vernadsky Institute of General and Inorganic Chemistry |
| record_format | ojs |
| resource_txt_mv | ucjorgua/18/89f9c57079ad1e039338944282c51218.pdf |
| spelling | oai:ojs2.1444248.nisspano.web.hosting-test.net:article-3422026-07-22T08:23:47Z OUT-OF-PLANE COORDINATED ZIRCONIUM(IV) AND HAFNIUM(IV) PHTHALOCYANINATES ПОЗАПЛОЩИННО КООРДИНОВАНІ ФТАЛОЦІАНІНАТИ ЦИРКОНІЮ(IV) І ГАФНІЮ(IV) Chernii, Viktor Tretyakova, Iryna Tomachynska, Larysa Gerasymchuk, Yuriy Chernii, Svitlana Pekhnyo, Vasyl phthalocyanines, zirconium, hafnium, synthesis, spectroscopy. The article is devoted to methods of synthesis, the structure, and spectral characteristics of zirconium and hafnium phthalocyaninates with out-of-plane coordinated ligands. The general scheme for the synthesis of out-of-plane coordinated Zr and Hf phthalocyanines includes obtaining initial dichloride or dihydroxo complexes, which then undergo substitution reactions with -dicarbonyl compounds, hydroxybenzoic, sulfo- and aliphatic carboxylic acids, etc. In the case of polyphenols, which are bidentate ligands, one ligand is coordinated to the central atom of the macrocycle. If -dicarbonyl compounds or carboxylic acids are introduced into the reaction, two ligands are coordinated. The reactivity of the out-of-plane coordinated ligands of Zr and Hf phthalocyanines was also investigated. In all obtained out-of-plane coordinated Zr and Hf phthalocyanines, the ligands are located in the cis position relative to the plane of the phthalocyanine macrocycle. X-ray diffraction, NMR, and UV-Vis spectroscopy have proved this arrangement of ligands. According to the X-ray diffraction data of Zr and Hf dibenzoylmethanato phthalocyanines, the metal atom is out of the plane of the phthalocyanine macrocycle, which itself is not planar. The central atoms are located almost in the middle between the N4 planes of the phthalocyanine macrocycle and the O4 of the extraplanar ligands. The UV-Vis spectra of out-of-plane coordinated Zr and Hf phthalocyanines in organic solvents have a typical appearance for most metal phthalocyanines, characterized by a B-band of absorption in the region of 335–350 nm, a Q-band at 680-690 nm, and its satellite in the region of 615–620 nm. If the extraplanar ligand is a chromophore (e.g., curcumin or condensed derivatives of dehydroacetic acid), there are additional absorption bands in  UV-Vis spectra located between the B- and Q-bands. The influence of the nature of the central metal atoms, ligands and solvents on the fluorescent properties of the out-of-plane coordinated Zr and Hf phthalocyanines was also discussed. V.I.Vernadsky Institute of General and Inorganic Chemistry 2021-09-24 Article Article Inorganic Chemistry Неорганическая химия Неорганічна хімія application/pdf https://ucj.org.ua/index.php/journal/article/view/342 10.33609/2708-129X.87.08.2021.82-98 Ukrainian Chemistry Journal; Vol. 87 No. 8 (2021): Ukrainian Chemistry Journal; 82-98 Украинский химический журнал; ##issue.vol## 87 ##issue.no## 8 (2021): Ukrainian Chemistry Journal; 82-98 Український хімічний журнал; Том 87 № 8 (2021): Український хімічний журнал; 82-98 2708-129X 2708-1281 en https://ucj.org.ua/index.php/journal/article/view/342/181 Copyright (c) 2021 Viktor Chernii, Iryna Tretyakova, Larysa Tomachynska, Yuriy Gerasymchuk, Svitlana Chernii, Vasyl Pekhnyo https://creativecommons.org/licenses/by-nc/4.0 |
| spellingShingle | Chernii, Viktor Tretyakova, Iryna Tomachynska, Larysa Gerasymchuk, Yuriy Chernii, Svitlana Pekhnyo, Vasyl ПОЗАПЛОЩИННО КООРДИНОВАНІ ФТАЛОЦІАНІНАТИ ЦИРКОНІЮ(IV) І ГАФНІЮ(IV) |
| title | ПОЗАПЛОЩИННО КООРДИНОВАНІ ФТАЛОЦІАНІНАТИ ЦИРКОНІЮ(IV) І ГАФНІЮ(IV) |
| title_alt | OUT-OF-PLANE COORDINATED ZIRCONIUM(IV) AND HAFNIUM(IV) PHTHALOCYANINATES |
| title_full | ПОЗАПЛОЩИННО КООРДИНОВАНІ ФТАЛОЦІАНІНАТИ ЦИРКОНІЮ(IV) І ГАФНІЮ(IV) |
| title_fullStr | ПОЗАПЛОЩИННО КООРДИНОВАНІ ФТАЛОЦІАНІНАТИ ЦИРКОНІЮ(IV) І ГАФНІЮ(IV) |
| title_full_unstemmed | ПОЗАПЛОЩИННО КООРДИНОВАНІ ФТАЛОЦІАНІНАТИ ЦИРКОНІЮ(IV) І ГАФНІЮ(IV) |
| title_short | ПОЗАПЛОЩИННО КООРДИНОВАНІ ФТАЛОЦІАНІНАТИ ЦИРКОНІЮ(IV) І ГАФНІЮ(IV) |
| title_sort | позаплощинно координовані фталоціанінати цирконію(iv) і гафнію(iv) |
| topic_facet | phthalocyanines zirconium hafnium synthesis spectroscopy. |
| url | https://ucj.org.ua/index.php/journal/article/view/342 |
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