СИНТЕЗ ТА ДОСЛІДЖЕННЯ ВЛАСТИВОСТЕЙ КОМПЛЕКСУ ЦИНКУ З 3-(2-ПІРИДИЛ)-5-(3,4,5-ТРИМЕТОКСИФЕНІЛ)-1,2,4-ТРИАЗОЛОМ
A procedure has been developed for the synthesis of a zinc complex with chelating li-gand 3-(2-pyridyl)-5-(3,4,5-trimethoxyphenyl)-1,2,4-triazole. Within the framework of the density functional method, with the B3LYP functional in the SBKJC basis, the equilibrium geometry of the ground electronic st...
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| Дата: | 2020 |
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| Автори: | , , , , , |
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| Мова: | Англійська |
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V.I.Vernadsky Institute of General and Inorganic Chemistry
2020
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Репозитарії
Ukrainian Chemistry Journal| _version_ | 1871465478495404032 |
|---|---|
| author | Khomenko, Dmytro Doroshchuk, Roman Starova, Victoria Raspertova, Ilona Severinovskaya, Olga Lampeka, Rostyslav |
| author_facet | Khomenko, Dmytro Doroshchuk, Roman Starova, Victoria Raspertova, Ilona Severinovskaya, Olga Lampeka, Rostyslav |
| author_institution_txt_mv | [
{
"author": "Dmytro Khomenko",
"institution": null
},
{
"author": "Roman Doroshchuk",
"institution": null
},
{
"author": "Victoria Starova",
"institution": "Taras Shevchenko National University of Kyiv"
},
{
"author": "Ilona Raspertova",
"institution": null
},
{
"author": "Olga Severinovskaya",
"institution": null
},
{
"author": "Rostyslav Lampeka",
"institution": null
}
] |
| author_sort | Khomenko, Dmytro |
| baseUrl_str | https://ucj.org.ua/index.php/journal/oai |
| collection | OJS |
| datestamp_date | 2026-07-22T08:23:43Z |
| description | A procedure has been developed for the synthesis of a zinc complex with chelating li-gand 3-(2-pyridyl)-5-(3,4,5-trimethoxyphenyl)-1,2,4-triazole. Within the framework of the density functional method, with the B3LYP functional in the SBKJC basis, the equilibrium geometry of the ground electronic state of the ligand molecule and zinc complex was determined. The physicochemical properties of the ligand were also characterized: logP = 4.1±0.1, рКf1 = 3.31±0.05,  рКf2 = 10.2±0.1,  ε275 ≈ 1·105 l·mol–1·cm–1. It was shown that complexation is accompanied by an increase in fluorescence  intensity, for the complex λemmax ≈ 458 nm.  The absorption spectrum of the complex is characterized by two bands with maxima at 278 nm (ε278 ≈ 1.3·104 l·mol–1·cm–1) and 322 nm (ε322 ≈ 1.2·104 l·mol–1·cm–1).
  |
| doi_str_mv | 10.33609/2708-129X.86.6.2020.65-73 |
| first_indexed | 2025-09-24T17:43:27Z |
| format | Article |
| fulltext |
НЕОРГАНІЧНА ХІМІЯ
ISSN 2708-129X. УКР . ХІМ . ЖУРН ., 2020, т . 86, No 6 65
UDC 541.49+546.47+547.792+535. doi: 10.33609/2708-129X.86.6.2020.65-73
D. N. Khomenko
1
*, R. A. Doroshchuk
1
, V. S. Starova
1
, I. V. Raspertova
1
,
O. V. Severinovskaya
2
, R. D. Lampeka
1
SYNTHESIS AND STUDY OF PROPERTIES OF ZINC COMPLEX WITH 3-(2-
PYRIDYL)-5-(3,4,5-TRIMETOXYPHENYL)-1,2,4-TRIAZOLE
1
Taras Shevchenko National University of Kyiv, 60 Volodymyrska Str., Kyiv, 01033, Ukraine
2 Chuiko Institute of Surface Chemistry, National Academy of Sciences of Ukraine, 17 Ge-
neral Naumov Str., Kyiv, 03164, Ukraine
*e-mail: dkhomenko@ukr.net
A procedure has been developed for the synthesis of a zinc complex with chelating li-
gand 3-(2-pyridyl)-5-(3,4,5-trimethoxyphenyl)-1,2,4-triazole. Within the framework of
the density functional method, with the B3LYP functional in the SBKJC basis, the equi-
librium geometry of the ground electronic state of the ligand molecule and zinc complex
was determined. The physicochemical properties of the ligand were also characterized:
logP = 4.1±0.1, рКf
1 = 3.31±0.05, рКf
2 = 10.2±0.1, ε275 ≈ 1·105 l·mol–1·cm–1. It was shown
that complexation is accompanied by an increase in fluorescence intensity, for the
complex λem
max ≈ 458 nm. The absorption spectrum of the complex is characterized by
two bands with maxima at 278 nm (ε278 ≈ 1.3·104 l·mol–1·cm–1) and 322 nm (ε322 ≈
1.2·104 l·mol–1·cm–1).
K e y w o r d s: 1,2,4-triazole, zinc, fluorescence, DFT.
INTRODUCTION. The study of coor-
dination compounds of zinc with chelating
ligands is relevant in the context of the de-
velopment of fluorophores — compounds
for measuring the distribution and con-
centration of metal ions in biological sys-
tems [1]. Of the variety of currently avai-
lable organic reagents that are used for fluo-
rescence determination of microquantities of
Zn
2+
ion, hydrophobic reagents low sensitive
to changes in the acidity of the medium over
a wide pH range with high values of molar
extinction coefficient and quantum yield are
the most interesting [2–4].
In our opinion, the previously obtained
[5] 3-(2-pyridyl)-5-(3,4,5-trimethoxyphenyl)-
1,2,4-triazole (HL) seems to be a promising
fluorophore reagent for the quantitative de-
termination of zinc ions, because it can meet
all of the above requirements. The fluores-
cence properties of this ligand, like most
natural compounds that are derivatives of
pyrogallol, are due to the rigidity of the
structure and the presence of three electron-
© D.N Khomenko, R.A. Doroshchuk, V.S. Starova, I.V. Raspertova, O.V. Severinovskaya,
R.D. Lampeka, 2020
mailto:dkhomenko@ukr.net
D.N. Khomenko, R.A. Doroshchuk, V.S. Starova, I.V. Raspertova, O.V. Severinovskaya, R.D. Lampeka
66 ISSN 2708-129X. УКР . ХІМ . ЖУРН ., 2020, т . 86, No 6
donor groups in the phenyl substituent [6, 7].
Additionally, the use of the 3-(2-pyridyl)-
1,2,4-triazole system as the chelating part of
the ligand molecule makes it possible for its
complexes to be in the deprotonated form,
which increases the stability of the latter [8].
This paper presents the synthesis and
study of the physicochemical properties of a
zinc complex compound based on 3-(2-
pyridyl)-5-(3,4,5-trimethoxyphenyl)-1,2,4-
triazole.
EXPERIMENT AND DISCUSSION OF
THE RESULTS. For the synthesis of com-
plexes, Zn(CH3COO)2 (Merck) was used. 3-
(2-pyridyl)-5-(3,4,5-tri-methoxyphenyl)-
1,2,4-triazole was prepared according to the
previously described procedure [5] from 2-
cyanopyridine and 3,4,5-trimethoxybenzoic
acid hydrazide .
Zn2(L)4
.
6CH3OH. To a solution of
Zn(СН3СОО)2 (0.091 g, 0.5 mmol) in 10 ml
of CH3OH a solution of HL (0.312 g, 1
mmol) in 50 ml of CH3OH was added. With
slow crystallization for two days at room
temperature, colorless crystals precipitated
from this solution. They were filtered off,
washed with methanol and dried in air. The
yield of Zn2(L)4
.
6CH3OH was 76 %. Calcu-
lated for C70H84N16O18Zn2 (%): C 53.6; H
5.4; N 14.3. Found: C 53.8; H 5.8; N 14.2.
NMR spectra were recorded on a Va-
rian Mercury 400 instrument (400 MHz). To
measure the chemical shift in the PMR spe-
ctra, the central signal of the residual protons
DMSO-d6 (δ = 2.503 ppm) was used as a
secondary standard in DMSO-d6.
When studying the properties of HL and
the zinc complex based on it, their working so-
lutions were prepared by dissolving the corres-
ponding exact weights in dimethyl sulfoxide
(DMSO). This organic solvent was of spectro-
scopic purity (Merck).
The study of the acid-base properties of
the ligand was carried out by potentiometric tit-
ration using a pH meter (pH-340) with a glass
electrode ESL-43-07. Titration of the proto-
nated form of 3-(2-pyridyl)-5-(3,4,5-trime-
thoxyphenyl)-1,2,4-triazole was carried out
with a standardized NaOH solution in a mix-
ture of water-DMSO (ωH2O:ωDMSO = 10:90). Ba-
sed on the pH metric titration curves in Hy-
perquad 2000, the values of the formal dissoci-
ation constants of this ligand were calculated.
The ligand distribution coefficient in the
(logD7.4) water-octanol extraction system was
determined at pH 7.4 (phosphate buffer) using
the formula logD7.4=Со/Сw. The ligand con-
centration in the aqueous phase (Сw) was deter-
mined spectrophotometrically by addition tech-
nique, registering the optical density at the ma-
ximum of the absorption band; and the ligand
concentration in the octanol phase was deter-
mined by the difference in the substance con-
tent in the solution before extraction and the
Сw. Distribution constant was calculated by the
formula: logP= logD7.4 + log?10(1+10
(pKa–pH)
).
The complexation of the ligand with
Zn
2+
ions was studied spectrophotometrically.
The ligand and complex spectra were rec-
orded using a 2800 UV/Vis spectrophotome-
ter (Unico, USA). The comparison solution
was DMSO-water (ωH2O:ωDMSO = 10:90), the
thickness of the cuvette was 1 cm.
The fluorescence spectra of HL so-
lutions and its complex were recorded using
LS 55 luminescent spectrophotometer (Per-
kin–Elmer, UK) at optimal wavelengths se-
lected for each compound minus the back-
ground of the solvent. Spectra were recorded
in the wavelength range from 200 to 800 nm.
Synthesis and study of properties of zinc complex…
ISSN 2708-129X. УКР . ХІМ . ЖУРН ., 2020, т . 86, No 6 67
The frequency of data collection was 0.5 nm.
The error in determining the wavelength of
the maximum fluorescence intensity did not
exceed 1 nm. The sizes of the cuvette, exci-
tation and emission gaps were 1 cm, 10 and
20 nm respectively.
MALDI mass spectra were obtained at
the CCDU of Chuiko Institute of Surface
Chemistry of the National Academy of Sci-
ences of Ukraine by the method of mat-
rixless laser desorption/ionization using the
“Autoflex II” device (Bruker Daltonics,
Germany). The experiments were carried out
in the reflex mode of positive and negative
ions registration in the mass range 0–1500
m/z. For mass spectroscopic experiments,
aliquots of 1 μl of methanol solutions of the
studied compounds with a concentration of
1 mg/ml were applied to a standard steel
substrate and left to dry completely, after
which they were placed in the working area
of the device. Data was processed using Flex
Analysis software (Bruker Daltonics, Ger-
many).
The equilibrium geometry of the stu-
died compounds in the singlet electronic
state was optimized by the density functional
method (DFT) using the B3LYP hybrid
functional [9, 10] in the SBKJC basis [11].
All calculations at the DFT theory level we-
re performed within the framework of the
Firefly v.8.1.1 software package [12].
3-(2-Pyridyl)-5-(3,4,5-trimethoxyphe-
nyl)-1,2,4-triazole is characterized by high
hydrophobicity (logP = 4.1±0.1) and is prac-
tically insoluble in water, therefore, further
study of its physicochemical properties were
carried out in water–DMSO medium (ωH2O:
ωDMSO = 10:90). Based on the obtained tit-
ration curves of this ligand in a water–
DMSO solution, it was found that the ex-
ponent of its first formal dissociation con-
stant (рК
f
1) is 3.31±0.05. This value is res-
ponsible for the dissociation of protonated
nitrogen in the pyridine ring. Dissociation of
the N–H in triazole fragment occurs in a
strongly alkaline medium at pH > 10 (the
found value of рК
f
2 = 10.2±0.1).
Fig. 1. Absorption spectrum of 3-(2-pyridyl)-5-
(3,4,5-trimethoxyphenyl)-1,2,4-triazole and its
complex with Zn2+. C = 1·10s5 M, рН 2.5. (top
– experimental, bottom - calculated).
The absorption spectrum of 3-(2-py-
ridyl)-5-(3,4,5-trimethoxyphenyl)-1,2,4-tri-
azole is characterized by one intense band
with a maximum at 275 nm, which corres-
ponds to π-π* transitions inside the ligand
chromophore system (fig. 1). The molar ex-
D.N. Khomenko, R.A. Doroshchuk, V.S. Starova, I.V. Raspertova, O.V. Severinovskaya, R.D. Lampeka
68 ISSN 2708-129X. УКР . ХІМ . ЖУРН ., 2020, т . 86, No 6
tinction coefficient of the ligand is ε
275
≈ 1·10
5
l·mol
–1
·cm
–1
. The complexation of
Fig. 2. Graphical determination of the compo-
sition and stability of the complex 3-(2-pyridyl)-
5-(3,4,5-trimethoxyphenyl)-1,2,4-triazole with
Zn (II) by the equilibrium shift method. СZn2+ =
5·10–6 M, CHL= 0–3·10–4 M, рН 2.5. The linear
regression equation: log(Ax/A0–Ax) = (8.9±0.5) +
(1.9±0.1)·logCL; r2 = 0.987, where Ax is the op-
tical density at a given point of the saturation
curve, A0 is the optical density at which full
binding of the central ion to the complex is
achieved, CL is the total concentration of the lig-
and.
3-(2-pyridyl)-5-(3,4,5-trimethoxyphenyl)-
1, 2,4-triazole with Zn
2+
ions is accompani-
ed by a slight bathochromic shift of this
band (Δλ ≈ 4 nm) and the appearance of an-
other absorption band in the long-wa-
velength region of the spectrum λmax =
322 nm (fig. 1), which appears due to elec-
tron transfer from the ligand to the central
ion. The molar absorption coefficients of
these bands are: ε
278
≈ 1.3·l·mol
–1
·cm
–1
and
ε
322
≈ 1.2·10
4
l·mol
–1
·c
–1
, respectively.
In the absorption spectrum of the li-
gand, calculated in the vacuum approxima-
tion, there is one absorption band with a
maximum at 268 nm. In the calculated ab-
sorption spectrum of the zinc complex, two
bands are observed at 270 and 318 nm. It
should be noted that the calculated curves of
the absorption spectra in the form of inten-
sity agree well with the experimental data.
Using the equilibrium shift method, it
was shown that in the presence of an excess
amount of ligand in a DMSO–water solu-
tion, a coordination compound with M:L ra-
tio of 1:2 is formed (fig. 2). The logarithm of
the stability constant of this complex is ap-
proximately 8.9±0.5.
The fluorescence spectra of the HL so-
lution in DMSO show an intense band with a
maximum at 454 nm, and in the excitation
spectrum — at 294 nm (fig. 3).
Fig. 3. Excitation (1–3) and fluorescence (4–6)
spectra of solutions of ligand (1, 4) and complex
(2, 3, 5, 6) in DMSO–water. Cligand = 3·10–7 M
(1, 4), Ccomplex (M) = 1.5·10–7 (2, 5), 3·10–7 (3, 6).
Synthesis and study of properties of zinc complex…
ISSN 2708-129X. УКР . ХІМ . ЖУРН ., 2020, т . 86, No 6 69
Fig. 4. The mass spectrum registered in MALDI
(a) and the calculated (b) isotopic pattern of the
molecular ion [Zn2(L)3]+
Also, a slight bathochromic shift of the
fluorescence spectrum of the complex with
respect to the ligand fluorescence spectrum
(Δλ = 4 nm) is observed. The maximum flu-
orescence intensity of the complex in the ex-
citation spectra is observed at 287 nm, in the
emission spectra — at 458 nm.
In the mass spectrum of the zinc com-
plex, a small number of low-intensity peaks
with masses of 218, 334, and 396 Da are ob-
served. The peak at 334 Da corresponds to
the formation of a quasimolecular ion for-
med by a ligand molecule and a sodium ca-
tion [НL+Na]
+
. In addition, in the mass spec-
trum there is a more intense peak with a
mass of 1061 Da (fig. 4). The isotopic pat-
tern corresponding to this peak indicates the
presence of two zinc atoms and three ligands
in the molecular ion — [Zn2(L)3]
+
. The pre-
sence of such a molecular ion in the mass
spectrum indicates that the complex con-
tains a binuclear fragment, which with a
most likely has the composition Zn2(L)4.
The
1
H NMR spectrum of the stu-died
coordination compound in the DMSO-d6 so-
lution has a number of features that distin-
guish it from the ligand spectrum (fig. 5).
First, in the spectrum of the complex there is
no signal of the triazole proton, as well as
signals of the methyl group protons from the
acetate ion.
Fig. 5. 1H NMR spectrum of HL (1) and
Zn2(L)4
.6CH3OH (2) (spectra measured in
DMSO-d6). The arrow indicates the signal of
the α-pyridine proton
This indicates that the ligand is includ-
ed in the complex in deprotonated form, re-
sulting in the formation of a molecular com-
plex. The second difference is a noticeable
D.N. Khomenko, R.A. Doroshchuk, V.S. Starova, I.V. Raspertova, O.V. Severinovskaya, R.D. Lampeka
70 ISSN 2708-129X. УКР . ХІМ . ЖУРН ., 2020, т . 86, No 6
broadening of proton signals in the
1
H NMR
spectrum of the complex, compared with the
spectrum of an uncoordinated ligand, which
is typical for zinc complexes with deriva-
tives of 3-(2-pyridyl)-1,2,4-triazole and,
most likely, is due to complex lability [13].
Thirdly, the signal of the α-pyridine proton
in Zn2(L)4
.
6CH3OH is at 8.4 ppm, while in
HL the signal of this proton is at 8.7 ppm.
The difference in 0.3 ppm means the coordi-
nation of the ligand through the nitrogen of
the pyridine ring. Based on the foregoing, we
can make an unambiguous conclusion about
the bidentate-chelate coordination of the
ligand by zinc ion.
Fig. 6. Equilibrium geometry of 3-(2-pyridyl)-5-
(3,4,5-trimethoxyphenyl)-1,2,4-triazole (1) mo-
lecule and anion (2) calculated using the DFT
method with B3LYP functional in SBKJC basis
It should be noted that methanol proton
signals are also present in the
1
H NMR spec-
trum. Based on their integrated intensity, the
results of CHN analysis and the results of
mass-spectrometric studies for the resulting
complex, we can propose the following com-
position — Zn2(L)4
.
6CH3OH.
The calculation of the ligand ground
state structure by the DFT method showed
that the calculated geometry agrees well
with the experimental data of X-ray diffrac-
tion analysis [14]. Fig. 6 shows the cal-
culated equilibrium configurations of HL
and L
–
. For the ligand and its anion, the to-
tal energies of the molecules were calcu-
lated, which amounted to –187.1293 a.u. and
–186.5783 a.u. Based on these data, the en-
ergy of deprotonation of the ligand is
0.551 a.u (1446.65 kJ/mol).
Based on the assumption of binuclear
structure of the zinc complex, the equilib-
rium configurations and total energies for
particles (Zn(HL)2)
2+
(E = 600.0003 а.u),
ZnL2 (E = –599.2812 а.u) and Zn2L4 (E =
= –1198.5947 а.u) were calculated (fig. 7).
Dimerization energy according to the for-
mula ΔE = Σ Efull(reaction products) – Σ Efull(reagents)
is –0.0323 a.u (–84.79 kJ/mol).
It is known that the HOMO energy de-
scribes electron-donor properties, while the
LUMO characterizes electron-acceptor pro-
perties. The HOMO–LUMO orbital schemes
for the ligand and inc complex are pre-
sented in fig. 8. In the ligand, the electron
density of the HOMO is localized on 3,4,5-
trimethoxybenzene and partially triazole
fragments. At the same time, LUMO is lo-
calized on pyridine and partially triazole
fragments. A similar picture is observed for
the complex. The difference is that the
Synthesis and study of properties of zinc complex…
ISSN 2708-129X. УКР . ХІМ . ЖУРН ., 2020, т . 86, No 6 71
Fig. 7. Equilibrium geometry (Zn(HL)2)2+ (3), ZnL2 (4) and Zn2L4 (5) calculated using the DFT
method with the B3LYP functional in the SBKJC basis. (Hydrogen atoms and methoxy groups for 5
are not shown to simplify the figure)
localization of electron density is observed
in two “separate” ligand molecules. The
widths of the energy gaps for the ligand and
complex are 3.73 and 3.31 eV, respectively.
Fig. 8. Diagram of the boundary molecular or-
bitals for L and Zn2L4
Based on the totality of the obtained da-
ta, we proposed the structure of the Zn2(L)4
.
6CH3OH complex in which the ligands are
in bidentate-chelate coordination and only
two of them are bridged:
CONCLUSION. It was found that 3-(2-
pyridyl-5-(3,4,5-trimethoxyphenyl)-1,2,4-
triazole is a highly hydrophobic ligand,
which in a wide pH range (4–10) is in mo-
lecular form, characterized by high molar
absorption coefficient and intense fluores-
cence. As a result of the complexation of this
ligand with zinc ions, a bidentate chelate com-
plex Zn2(L)4
.
6CH3OH is formed, which also
exhibits intense fluorescence at λ
em
max ≈
≈ 458 nm. Based on the density functional
method, the equilibrium geometry of the
ground electronic state of both the ligand
and the zinc complex is determined. Such
physicochemical properties of the ligand and
D.N. Khomenko, R.A. Doroshchuk, V.S. Starova, I.V. Raspertova, O.V. Severinovskaya, R.D. Lampeka
72 ISSN 2708-129X. УКР . ХІМ . ЖУРН ., 2020, т . 86, No 6
its complex with zinc confirm the prospects
of using 3-(2-pyridyl)-5-(3,4,5-
trimethoxyphenyl)-1,2,4-triazole as an ana-
lytical reagent for determining the trace
amounts of zinc ions.
СИНТЕЗ ТА ДОСЛІДЖЕННЯ ВЛАСТИ-
ВОСТЕЙ КОМПЛЕКСУ ЦИНКУ З 3-(2-
ПІРИДИЛ)-5-(3,4,5-ТРИМЕТОКСИФЕНІЛ)-
1,2,4-ТРИАЗОЛОМ
Д. М. Хоменко1*, Р. О. Дорощук1, В. С. Ста-
рова1, І. В. Распертова1, О. В. Северинов-
ська2, Р. Д. Лампека1
1 Київський національний університет імені
Тараса Шевченка, вул.°Володимирська, 60,
Київ, 01033, Україна
2 Інститут хімії поверхні ім. О. О. Чуйка
НАН України, вул. Генерала Наумова, 17,
Київ, 03164, Україна
*e-mail: dkhomenko@ukr.net
Розроблено методику синтезу комплек-
су цинку з хелатуючим лігандом 3-(2-
піридил)-5-(3,4,5-триметоксифеніл)-1,2,4-
триазолом. Методом функціоналу густини з
фунціоналом B3LYP в базисі SBKJC визна-
чено рівноважну геометрію основного елек-
тронного стану молекули ліганду та ком-
плексу цинку. Також охарактеризовано
фізико-хімічні властивості ліганду: logP =
4.1±0.1, рКf
1= 3.31 ±0.05, рКf
2 = 10.2±0.1, ε275 ≈
1·105 л·моль–1·см–1. Показано, що комплексо-
утворення супроводжується збільшенням
інтенсивності флуоресценції, для комплексу
λem
max ≈458нм. Спектр поглинання комплексу
характеризується двома смугами з максиму-
мами при 278 нм (ε278≈1.3·104 л·моль–1·см–1)
та 322 нм (ε322≈ 1,2·104 л·моль-1·см-1).
К л ю ч о в і с л о в а: 1,2,4-триазол, цинк,
флуоресценція, теорія функціоналу.
СИНТЕЗ И ИССЛЕДОВАНИЕ СВОЙСТВ
КОМПЛЕКСА ЦИНКА С 3-(2-ПИРИДИЛ)-
5-(3,4,5-ТРИМЕТОКСИФЕНИЛ)-1,2,4-
ТРИАЗОЛОМ
Д.Н. Хоменко1*, Р.А. Дорощук1, В.С. Старо-
ва1, И.В. Распертова1, О.В. Севериновская2,
Р.Д. Лампека1
1 Киевский национальный университет имени
Тараса Шевченка, ул. Владимирская, 60, Ки-
ев, 01033, Украина
2 Институт химии поверхности им. А.А.
Чуйко НАН Украины, ул. Генерала Наумова,
17,Киев, 03164, Украина
*е-mail: dkhomenko@ukr.net
Разработана методика синтеза комплек-
са цинка с хелатирующим лигандом 3-(2-
пиридил)-5-(3,4,5-триметоксифенил)-1,2,4-
триазолом. В рамках метода функционала
плотности, с функционалом B3LYP в базисе
SBKJC, определена равновесная геометрия
основного электронного состояния молекулы
лиганда и комплекса цинка. Также охаракте-
ризованы физико-химические свойства лига-
нда: logP=4.1±0.1, рКf
1= 3.31±0.05, рКf
2=
10.2±0.1, ε275≈ 1·105 л·моль-1·см-1. Показано,
что комплексообразование сопровождается
увеличением интенсивности флуоресценции,
для комплекса λem
max≈ 458 нм. Спектр пог-
лощения комплекса характеризуется двумя
полосами с максимумами при 278 нм (ε278≈
1,3·104 л·моль-1·см-1) и 322 нм (ε322≈ 1,2·104
л·моль-1·см-1).
К л ю ч е в ы е с л о в а: 1,2,4-триазол, цинк,
флуоресценция, теория функционала плотно-
сти.
REFERENCES
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mailto:dkhomenko@ukr.net
Synthesis and study of properties of zinc complex…
ISSN 2708-129X. УКР . ХІМ . ЖУРН ., 2020, т . 86, No 6 73
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Надійшла 08.05.2020
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| id | oai:ojs2.1444248.nisspano.web.hosting-test.net:article-186 |
| institution | Ukrainian Chemistry Journal |
| keywords_txt_mv | keywords |
| language | English |
| last_indexed | 2026-07-23T01:02:40Z |
| publishDate | 2020 |
| publisher | V.I.Vernadsky Institute of General and Inorganic Chemistry |
| record_format | ojs |
| resource_txt_mv | ucjorgua/a1/c5f5360a2b7ca78e30a24e20faafeba1.pdf |
| spelling | oai:ojs2.1444248.nisspano.web.hosting-test.net:article-1862026-07-22T08:23:43Z SYNTHESIS AND STUDY OF PROPERTIES OF ZINC COMPLEX WITH 3-(2-PYRIDYL)-5-(3,4,5-TRIMETOXYPHENYL)-1,2,4-TRIAZOLE СИНТЕЗ И ИССЛЕДОВАНИЕ СВОЙСТВ КОМПЛЕКСА ЦИНКА С 3-(2-ПИРИДИЛ)-5-(3,4,5-ТРИМЕТОКСИФЕНИЛ)-1,2,4-ТРИАЗОЛОМ СИНТЕЗ ТА ДОСЛІДЖЕННЯ ВЛАСТИВОСТЕЙ КОМПЛЕКСУ ЦИНКУ З 3-(2-ПІРИДИЛ)-5-(3,4,5-ТРИМЕТОКСИФЕНІЛ)-1,2,4-ТРИАЗОЛОМ Khomenko, Dmytro Doroshchuk, Roman Starova, Victoria Raspertova, Ilona Severinovskaya, Olga Lampeka, Rostyslav 1,2,4-triazole, zinc, fluorescence, DFT. A procedure has been developed for the synthesis of a zinc complex with chelating li-gand 3-(2-pyridyl)-5-(3,4,5-trimethoxyphenyl)-1,2,4-triazole. Within the framework of the density functional method, with the B3LYP functional in the SBKJC basis, the equilibrium geometry of the ground electronic state of the ligand molecule and zinc complex was determined. The physicochemical properties of the ligand were also characterized: logP = 4.1±0.1, рКf1 = 3.31±0.05,  рКf2 = 10.2±0.1,  ε275 ≈ 1·105 l·mol–1·cm–1. It was shown that complexation is accompanied by an increase in fluorescence  intensity, for the complex λemmax ≈ 458 nm.  The absorption spectrum of the complex is characterized by two bands with maxima at 278 nm (ε278 ≈ 1.3·104 l·mol–1·cm–1) and 322 nm (ε322 ≈ 1.2·104 l·mol–1·cm–1).   V.I.Vernadsky Institute of General and Inorganic Chemistry 2020-07-20 Article Article Inorganic Chemistry Неорганическая химия Неорганічна хімія application/pdf https://ucj.org.ua/index.php/journal/article/view/186 10.33609/2708-129X.86.6.2020.65-73 Ukrainian Chemistry Journal; Vol. 86 No. 6 (2020): Ukrainian Chemistry Journal; 65-73 Украинский химический журнал; ##issue.vol## 86 ##issue.no## 6 (2020): Украинский химический журнал; 65-73 Український хімічний журнал; Том 86 № 6 (2020): Український хімічний журнал; 65-73 2708-129X 2708-1281 en https://ucj.org.ua/index.php/journal/article/view/186/109 Copyright (c) 2020 Dmytro Khomenko, Roman Doroshchuk, Victoria Starova, Ilona Raspertova, Olga Severinovskaya, Rostyslav Lampeka https://creativecommons.org/licenses/by-nc/4.0 |
| spellingShingle | Khomenko, Dmytro Doroshchuk, Roman Starova, Victoria Raspertova, Ilona Severinovskaya, Olga Lampeka, Rostyslav СИНТЕЗ ТА ДОСЛІДЖЕННЯ ВЛАСТИВОСТЕЙ КОМПЛЕКСУ ЦИНКУ З 3-(2-ПІРИДИЛ)-5-(3,4,5-ТРИМЕТОКСИФЕНІЛ)-1,2,4-ТРИАЗОЛОМ |
| title | СИНТЕЗ ТА ДОСЛІДЖЕННЯ ВЛАСТИВОСТЕЙ КОМПЛЕКСУ ЦИНКУ З 3-(2-ПІРИДИЛ)-5-(3,4,5-ТРИМЕТОКСИФЕНІЛ)-1,2,4-ТРИАЗОЛОМ |
| title_alt | SYNTHESIS AND STUDY OF PROPERTIES OF ZINC COMPLEX WITH 3-(2-PYRIDYL)-5-(3,4,5-TRIMETOXYPHENYL)-1,2,4-TRIAZOLE СИНТЕЗ И ИССЛЕДОВАНИЕ СВОЙСТВ КОМПЛЕКСА ЦИНКА С 3-(2-ПИРИДИЛ)-5-(3,4,5-ТРИМЕТОКСИФЕНИЛ)-1,2,4-ТРИАЗОЛОМ |
| title_full | СИНТЕЗ ТА ДОСЛІДЖЕННЯ ВЛАСТИВОСТЕЙ КОМПЛЕКСУ ЦИНКУ З 3-(2-ПІРИДИЛ)-5-(3,4,5-ТРИМЕТОКСИФЕНІЛ)-1,2,4-ТРИАЗОЛОМ |
| title_fullStr | СИНТЕЗ ТА ДОСЛІДЖЕННЯ ВЛАСТИВОСТЕЙ КОМПЛЕКСУ ЦИНКУ З 3-(2-ПІРИДИЛ)-5-(3,4,5-ТРИМЕТОКСИФЕНІЛ)-1,2,4-ТРИАЗОЛОМ |
| title_full_unstemmed | СИНТЕЗ ТА ДОСЛІДЖЕННЯ ВЛАСТИВОСТЕЙ КОМПЛЕКСУ ЦИНКУ З 3-(2-ПІРИДИЛ)-5-(3,4,5-ТРИМЕТОКСИФЕНІЛ)-1,2,4-ТРИАЗОЛОМ |
| title_short | СИНТЕЗ ТА ДОСЛІДЖЕННЯ ВЛАСТИВОСТЕЙ КОМПЛЕКСУ ЦИНКУ З 3-(2-ПІРИДИЛ)-5-(3,4,5-ТРИМЕТОКСИФЕНІЛ)-1,2,4-ТРИАЗОЛОМ |
| title_sort | синтез та дослідження властивостей комплексу цинку з 3-(2-піридил)-5-(3,4,5-триметоксифеніл)-1,2,4-триазолом |
| topic_facet | 1,2,4-triazole zinc fluorescence DFT. |
| url | https://ucj.org.ua/index.php/journal/article/view/186 |
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