ISSN 1070-3632, Russian Journal of General Chemistry, 2019, Vol. 89, No. 1, pp. 87–95. © Pleiades Publishing, Ltd.

, 2019.
Russian Text © T.E. Kokina, Yu.P. Ustimenko, M.I. Rakhmanova, L.A. Sheludyakova, A.M. Agafontsev, P.E. Plyusnin, A.V. Tkachev, S.V. Larionov, 2019,
published in Zhurnal Obshchei Khimii, 2019, Vol. 89, No. 1, pp. 100–109.

Luminescent Complexes of Zn(II) and Cd(II)

with Chiral Ligands Containing 1,10-Phenanthroline
and Natural Monoterpenoids (+)-3-Carene
or (+)-Limonene Fragments
T. E. Kokinaa,b*, Yu. P. Ustimenkoc, M. I. Rakhmanovaa, L. A. Sheludyakovaa,b,
A. M. Agafontsevc, P. E. Plyusnina,b, A. V. Tkachevb,c, and S. V. Larionova,b†
a
A.V. Nikolaev Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia
*е-mail: kokina@niic.nsc.ru
b
Novosibirsk National Research State University, Novosibirsk, Russia
c
N.N. Vorozhtsov Novosibirsk Institute of Organic Chemistry, Siberian Branch,
Russian Academy of Sciences, Novosibirsk, Russia

Received May 31, 2018; revised May 31, 2018; accepted August 16, 2018

Abstract—New chiral 1,10-phenanthroline-derived ligands containing fragments of (+)-3-carene (L1) and

(+)-limonene (L2) natural monoterpenoids and their complexes Zn(L1,2)Cl2·1.5H2O, Cd(L1,2)Cl2·nH2O,
Zn(L1)Br2·2H2O, and Cd(L1)Br2·2H2O were synthesized. According to NMR and IR spectroscopy data, a
conclusion was made about the polynuclear structure of the compounds obtained. Luminescent properties of
the compounds obtained were investigated. Lifetimes of the excited states and luminescence quantum yields
(φf) were determined. For free ligands, blue fluorescence was observed. In the case of Zn(II) and Cd(II)
complexes, luminescence appeared in the green region of the spectrum.
Keywords: terpenes, complexes, zinc, cadmium, luminescence
DOI: 10.1134/S107036321901016X

Synthesis and structure of metal complexes with
сhiral ligands is among topical directions of coordina-
tion chemistry. With a view to the creation of new
functional materials, a variety of physical properties of
synthesized compounds are investigated. Much
attention is given to the synthesis and study of chiral
metal complexes, including those having a circularly
polarized luminescence [1–4]. Researchs on finding
chiral molecular magnets [5, 6] are in progress.
Possibilities of applying biologically active chiral com-
plexes are promising [7].
When synthesizing chiral coordination compounds,
particular attention is paid to use of natural optically
active compounds as ligands. Metal complexes with
chiral natural amino acids [8] and [9] saccharides are
studied. Chiral metal complexes with derivatives of
natural terpenes are of considerable interest. Terpenes,
†
Deceased.
which serve as source compounds for the synthesis of
such chiral ligands, are widespread in the plant world
and have high enantiomeric purity. The largest number
of complexes were obtained with ligands based on
available α-pinene, β-pinene, (+)-3-carene, and limo-
nene [10–14]. A number of synthesized complexes
exhibit promising physical properties. So, Eu(III) and
Dy(III) chiral complexes with 2,2'-bipyridine involv-
ing two fragments of (+)-pinene or (–)-pinene have
ferroelectric properties [15, 16]. Luminescent chiral
complexes of lanthanides with N-heterocyclic ligands
containing pinene [1, 17] and camphor [4, 18] frag-
ments were obtained.
Complexes of Zn(II) with levo- and dextrorotatory
ligands based on 2,2'-bipyridine with (+)-and (–)-
pinene fragments were synthesized [19]. The com-
pound with the levorotatory ligand has a blue-and-
white photoluminescence (λmax = 470 nm), which the
authors attributed to phosphorescence. Spectra of

87
88
circularly polarized luminescence for Zn(II) com-
plexes were obtained for the first time with the
example of these compounds. Further the both mono-
nuclear Zn(II) complex and binuclear Cd(II) complex
with pyrazolinequinoline, which is a derivative of (+)-
3-carene terpenoid, were synthesized. In the solid
phase Zn(II) and Cd(II) compounds exhibit white and
blue photoluminescence (λmax = 418 and 490 nm),
respectively [20, 21]. Mononuclear Zn(II) complex and
binuclear Cd(II) complex with chiral dihydrophenan-
throline, a derivative of natural (–)-α-pinene, were
obtained [22]. The compounds have blue photolumine-
scence (λmax = 405 and 415 nm, respectively).
Quantum yield of photoluminescence for the Cd(II)
complex is 24%. Complexes of Zn(II) and Cd(II) with
bipyridine containing (−)-α-pinene fragments were
synthesized [23]. The central cycle of this ligand is
five-membered, but not six-membered as in chiral
dihydrophenanthroline. It was shown by the X-ray
analysis that the Zn(II) complex is mononuclear and
the Cd(II) complex is a 1D-coordination polymer. For
these Zn(II) and Cd(II) complexes photoluminescence
(λmax = 505 and 460 nm, respectively) is also typical.
The increase in the photoluminescence intensity due to
chelating (CHEF) was found [24]. Mononuclear
17 18
15 16
14
12
N N
13
11 N
N 10
10 3
N 1
2 OH
4
1 5
5
6 4
8 7
9 9
L1
To develop procedures for the synthesis of such
compounds, the reaction of piperazine with 2-chloro-
phenanthroline was studied, and conditions for its
monoarylation and also for isolation and purification
of reaction products were selected (Scheme 1).
Further the reaction of the piperazine derivative
with nitrozochlorides of monoterpenes [(+)-limonene
and (+)-3-carene] was studied (Scheme 2). Conditions
of its realization and for isolation and purification of
the target reaction products were selected. As a result,
KOKINA et al.
complexes of Zn(II) with 2,2'-bipyridyl containing a
(+)-pinene or (–)-pinene fragment were synthesized
[25]. The Zn(II) complex with the levorotatory ligand
in the solid phase luminesces in the blue area (λmax
~455 nm).
The synthesis of new luminescent Zn(II) and Cd(II)
complexes with hybrid N-heterocyclic ligands of the
new structural type, containing fragments of 1,10-
phenanthroline and α-aminooxime terpene bound by a
linker – piperazine is promising. The presence of
voluminous terpene fragments in the composition of
these organic compounds will make it possible to
study the effect of these fragments on the complex-
forming properties of the 1,10-phenanthroline core.
The purpose of this work was the synthesis and
study of the structure and luminescent properties of
Zn(II) and Cd(II) complexes with representatives of
ligands of the new structural type – chiral oximes
(1R,4S,6S,E)-4-[4-(1.10-phenanthroline-2-yl)pipera-
zine-1-yl] 4,7,7-trimethylbicyclo[4.1.0]heptane-3-on
(L1) and (2S,5R,E)-2-[4-(1,10-phenanthroline-2-yl)pi-
perazine-1-yl]-2-methyl-5-(prop-1-en-2-yl)cyclohexa-
none (L2) containing fragments of (+)-3-carene and
(+)-limonene, respectively.
17 18
15 16 19 20
19 20
23 14 21
21 12 24 23
24 N N
13 22
22 11 N
N
2 N
6 OH
3
7 8
L2
we synthesized the first representatives of the series of
hybrid chiral ligands L1 and L2 containing two possible
coordination sites, a fragment of 1,10-phenanthroline
and a fragment of α-aminooxime.
As a result of the reaction of Zn(II) and Cd(II)
chlorides with L1 and L2 in the MeOH medium, the
compounds with the ratio metal : ligand = 1 : 1,
ZnL1,2Cl2·1.5H2O (1, 3) and Cd(L1,2)Cl2·nH2O (2, 4)
were isolated. The yields are 20–40%. Apparently,
rather low yields are connected with the presence of
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 89 No. 1 2019
 LUMINESCENT COMPLEXES OF Zn(II) AND Cd(II) 89

Scheme 1.
7 6
12
8 5

HN NH 11
9
N 14
13
4
10
N N 3
toluene, t 1
2
N
N 15
Cl
16
N
H

Scheme 2.

N N
N Cl N N
MeOH/K2CO3
N + R R
NO N
N
OH

N
H

other more soluble in the solution complex species. In the IR spectra of ligands L1, L2 and complexes
For the synthesis of complexes a small excess of MCl2 1–4, the bands corresponding to the vibrations of main
was taken. The complexes contain water molecules. functional groups were identified (Table 1). The band
The number of water molecules varies from one corresponding to ν(OH) of oxime group is observed at
experiment to another in the range n = 1–2 for 3133 and 3168 cm–1 in the spectra of ligands L1 and
complexes of Zn(II) and n = 4–6 for complexes of L2. In the spectra of complexes 1–4 in the range of
Cd(II). Average elemental analysis data for two of the 3408–3351 cm–1 characteristic of water stretching
experiments are presented in the experimental part. vibration a wide band is seen, which overlaps with the
The study of thermal properties of compounds L1, L2, ν(OH) band of the oxime group shifted in the high-
and 1–4 in an inert atmosphere in the temperature
range of 25–300°C showed that the TG curves contain
no steps clearly corresponding to the loss of only water
molecules (see figure). When heating the free ligands,
a step of weight loss is observed in the temperature
range of 100–175°C, i.e. the decomposition of ligands
L1 and L2 occurs, which is confirmed by the data of
m, %

mass-spectrometric analysis of gaseous products.

When complexes 1–4 are heated, a smooth mass loss
starts from room temperature. Removing water in the
temperature range of 100–175°С is accompanied by
partial decomposition of the complex compounds. In
this connection, it is difficult to detect the exact
content of water in the complexes, because processes T, °C
of dehydration and decomposition of complexes 1–4 Curves of thermal analysis of (1) compound L1 and
proceed simultaneously on heating. complexes (2) 1 and (3) 2.

RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 89 No. 1 2019

90 KOKINA et al.
Table 1. Main parameters (ν, cm–1) of IR spectra of ligands L1, L2 and complexes 1–4
L1 1 2 L2
3133 3396 3380 3168
1617, 1608 1627 1623 1615
1589, 1551, 1594, 1569, 1594, 1569, 1590, 1553,
1511, 1489 1522, 1493 1522, 1493 1513, 1490
969, 948, 922 972, 940, 973, 922 968, 939
919
– 330, 310 278 sh, 262, – 328, 306
214
– 259 242, 229
energy region relative to its position in the spectra of
free ligands. Bands ν(N-O) in the spectra of the
complexes almost do not change their position in
relation to the spectra of ligands L1 and L2, which
implies the absence of the oxime group N atom from
the coordination sphere of the metal ions, and the
change in the band ν(OH) position is connected with a
change in the system of H-bonds upon the complex
formation. In comparison with the spectra of free
ligands, the group of stretching vibration bands of C=C
and C=N bonds of the phenanthroline fragment in the
spectra of the complexes is shifted in the high-
frequency region of the spectrum, which points to the
coordination the phenanthroline fragment N atom by
Zn2+ and Cd2+ ions. In the region of metal–ligand
bonds vibrations in IR spectra of complexes 1–4,
intense split ν(M–Cl) bands were detected (Table 1).
One of the reasons for the band splitting may be
different natures of M–Cl bonds. Apparently, in
complexes 1–4 Cl atoms are both bridging and
terminal, or their participation in intermolecular inter-
actions is possible. With the aim to demonstrate
correctness of assignment of ν(M–Cl) bands, we
recorded the IR spectra of complexes 5 and 6 in the
range of 600-80 cm–1 and found the ν(M–Br) bands
with maxima at 251, 232 and 198, 169 cm–1,
respectively. For complexes 1, 2 and 5, 6 the ratios of
frequencies ν(Zn–Br)/ν(Zn–Cl) = 0.75, 0.76 and
ν(Cd–Br)/ν(Cd–Cl) = 0.79, 0.76 were found, which fall
within the interval 0.74-0.77 and thus confirm the
assignment [26] of the ν(M–Cl) bands. In the spectra
of complexes 1–4 new bands were detected, which are
absent from the spectra of ligands L1 and L2 and relate
to ν(M–N) (Table 2), the ν(Cd–N) band being split.
According to the IR-spectroscopy data for complexes
1–4, the coordination sphere of Zn2+ and Cd2+ ions
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 89 No. 1 2019
3 4 Assignment
3408, 3258 sh 3351, 3259 sh OH, H2O
1627 1622 С=N (NOH)
1594, 1568, 1593, 1561, С=С (ring)
1525, 493 1521, 1492 С=N (ring)
970, 929 971, 939 N–O
301 sh, 278, 210 M–Cl
256 245, 227 M–N
contains N atoms of the phenanthroline fragment and
Cl atoms, which can perform the functions of both
bridging and terminal ligands participating in H-bonds.
Complexes 1–4 are poorly soluble in water and
some organic solvents (EtOH, i-PrOH, CHCl3, and
CH2Cl2), but we were able to dissolve these com-
pounds in a CDCl3–DMSO mixture and to undertake
their NMR study. Comparison of the NMR parameters
of solutions of free ligand L1 and complexes 1, 2
(Table 2) indicates that on transition from the ligand to
the complexes signals of the terpene fragment change
only slightly. It suggests that the ligand is coordinated
to the phenanthroline fragment. This conclusion is
consistent with the IR spectroscopy data. It can be
assumed that the complexes 1–4 have a polynuclear
structure similar to that of the Cd(II) tetranuclear
complex with a pirazinephenanthroline derivative [27].
Luminescence excitation spectra of L1 and L2 solid
samples at 300 K contain a band in the visible (λmax =
410 nm) and UV (λmax = 360 nm) regions, respectively.
In the excitation spectrum of complex 1 a split band
(λmax = 410 nm) is observed, and in the spectrum of
complex 3 – a broad band with λmax ~ 400 nm. In the
excitation spectra of complexes 2 and 4 there are wide
bands with λmax ~ 400 and 450 nm, respectively. It is
interesting that the positions of bands in the excitation
spectra of Zn(II) and Cd(II) complexes with the ligand
L2 are noticeably shifted in the longwave region com-
pared with the L2 spectrum. To obtain photolumine-
scence spectra, we used the wavelength of excitation
light corresponding to the maximum of the most
intense bands in the excitation spectra of the compounds.
Photoluminescence spectra of free ligands L1 and
2
L have bands with λmax = 440 and 450 nm (λexc =
 LUMINESCENT COMPLEXES OF Zn(II) AND Cd(II) 91

Table 2. Parameters of 1Н and 13C NMR spectra of ligand L1 and complexes 1 and 2

Atom L1 (CDCl3) 1 (CDCl3 + DMSO-d6) 2 (CDCl3 + DMSO-d6)

no. δCi, ppm δHi, ppm (JHH, Hz) δHi, ppm (JHH, Hz) δHi, ppm (JHH, Hz)
1 17.16 0.67 d. d. d (JHH = 9.3, 9.3, 6.0) 0.61 d. d. d (JHH = 9.4, 9.4, 5.9) 0.61 m (W1/2 = 21 Hz)
2 32.10 2.37 d. d (JHH = 15.9, 9.3, pro-S) 2.28 d. d (JHH = 15.9, 9.4, pro-S) 2.29 d. d (JHH = 15.8, 9.6, pro-S)
1.23 d. d (JHH = 15.9, 6.0, pro-R) 1.13 d. d (JHH = 15.9, 5.9, pro-R) 1.09 d. d (JHH = 15.8, 5.9, pro-R)
3 59.02
4 158.23
5 18.41 2.30 d. d (JHH = 17.9, 8.8, pro-R) 2.16 d. d (JHH = 17.8, 8.9, pro-R) 2.19 m (W1/2 = 45 Hz)
3.05 d. d (JHH = 17.8, 1.2, pro-S) 2.91 d. d (JHH = 17.8, 1.1, pro-S) 2.54 m (W1/2 = 33 Hz)
6 20.91 0.97 d. d. d (JHH = 9.3, 8.8, 1.2) 0.88 d. d. d (JHH = 9.4, 8.9, 1.1) 0.89 d. d (JHH = 9.6, 9.6)
7 18.39
8 14.74 0.82 s 0.74 s 0.74 s
9 28.05 1.00 s 0.96 s 0.95 s
10 14.38 1.04 s 0.95 br. s (W1/2 = 3 Hz) 0.93 br. s (W1/2 = 7 Hz)
11 46.19 2.58 d. t (JHH = 11.3, 5.0) 2.61 m (W1/2 = 23 Hz) 2.75 m (W1/2 = 36 Hz)
2.82 d. t (JHH = 11.3, 5.0) 2.83 m (W1/2 = 23 Hz) 2.87 m (W1/2 = 40 Hz)
12 46.61 3.87 t (JHH = 5.0) 3.98 m (W1/2 = 20 Hz) 3.87 m (W1/2= 46 Hz)
13 163.80
14 109.85 7.10 d (JHH = 9.1) 7.37 d (JHH = 9.1) 7.24 d (JHH = 9.1)
15 137.28 7.94 d (JHH = 9.1) 8.17 d (JHH = 9.1) 8.02 d (JHH = 9.1)
16 121.91
17 126.28 7.60 d (JHH = 8.6) 7.81 d (JHH = 8.7) 7.69 d (JHH = 8.6)
18 122.03 7.45 d (JHH = 8.6) 7.72 d (JHH = 8.7) 7.57 d (JHH = 8.6)
19 129.19
20 135.97 8.15 d. d (JHH = 8.1, 1.7) 8.55 d. d (JHH = 8.2, 1.1) 8.38 d. d (JHH = 8.1, 1.1)
21 121.20 7.51 d. d (JHH = 8.1, 4.3) 7.86 d. d (JHH = 8.2, 4.8) 7.70 d. d (JHH = 8.1, 4.7)
22 149.29 9.10 d. d (JHH = 4.3, 1.7) 8.95 d. d (JHH = 4.8, 1.1) 9.11 m (W1/2 = 11 Hz)
23 145.01
24 145.31
OH 10.0 br. s (W1/2 = 25 Hz) 10.02 s 9.93 s

410 and 360 nm), respectively. The lifetime of the
excited states is ~ 10–9 s (Table 3). It is known that at
room temperature 1,10-phenanthroline (Phen) dis-
solved in CH2Cl2 has a weak fluorescence, λmax =
358 nm [28, 29]. In the luminescence spectrum of a
solid sample Phen.H2O at 77 K there is a band with
λmax = 420 nm (λexc = 266 nm). To increase the fluore-
scence quantum yield, the introduction of substituents
in positions 2,9 and 4,7 of the Phen molecule is used
[29]. It is noted that the introduction of the substituents
may lead to a bathochromic shift of the band in the
photoluminescence spectrum. Apparently, the batho-
chromic shift of the photoluminescence bands for L1
and L2, compared to the bands in the spectrum of solid
Phen.H2O, results from the introduction of the
substituent with a terpenoid fragment in position 2 of

RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 89 No. 1 2019

92 KOKINA et al.

Table 3. Maxima of bands, quantum yields, and luminescence lifetimes of solid samples of compounds L1, L2 and 1–4

Compound λex, nm λmax, nm φf, % τ1, ns A1τ1, % τ2, ns A2τ2, % τ3, ns A3τ3, %
1
L 410 450 – 9.2 46 43.0 32.0 3.10 22.0
1 400 550 0.15 2.5 26 25.0 14.0 0.42 61.0
2 400 510 0.40 6.5 84 326.0 4.8 7.20 11.0
L2 360 440 0.60 0.3 83 1.8 14.0 8.10 3.2
3 400 530 0.70 6.6 12 1.3 75.0 93.00 12.0
4 450 550 4.40 7.6 62 26.0 15.0 1.30 23.0

the Phen molecule. Complexes of organic ligands with
Zn2+ and Cd2+ ions with the electronic configuration
d10 exhibit a ligand-centered luminescence [30].
Photoluminescence spectra of complexes 1 and 3
contain a broad band with λmax = 550 and 530 nm, and
spectra of 2 and 4 – bands with λmax = 510 and 550 nm,
respectively. These spectra are related to the ligand-
centered fluorescence, because lifetimes of the excited
state of the complexes are in the range of 10–6–10–9 s
(Table 3).
We fail to detect luminescence quantum yield (φf)
for ligand L1. It is likely that the low intensity of the
free ligand L1 luminescence is caused by its structure
providing effective photo-induced transfer of unshared
electron pairs of N atoms in the π-system of the L1
phenanthroline fragment. For ligand L2 the value of φf
is 0.6%. Hence, the example of the (+)-3-carene
fragment replacement by the (+)-limonene fragment in
the terpenoid ligand composition has shown that the
fragment nature affects substantially the luminescent
properties. When moving from free ligands L1 and L2
to their Zn(II) and Cd(II) complexes, φf values increase
(Table 3). Thus, in the case of these complexes the
CHEF effect is observed [24, 31]. Values of quantum
yields for Cd(II) complexes are higher than for Zn(II)
complexes. The φf values found for polynuclear com-
plexes 1–4 are lower, respectively, than the φf values
for previously studied mononuclear and binuclear Zn(II)
and Cd(II) complexes with 2,2-bipiridine derivatives
obtained on the basis of terpenes [19, 22]. A feature of
the compounds synthesized is the significant batho-
hromic shift (~100 nm) of bands in the photolumine-
scence spectra of the complexes compared to the bands
in the spectra of the free ligands. The free ligands are
characterized by blue fluorescence, whereas
fluorescence in the green region of the spectrum is
observed for the Zn(II) and Cd(II) complexes.
Luminescence decay kinetics of solid samples of
compounds L1, L2, and 1–4 was studied. To process
the kinetic curves, we used the three-exponent approxi-
mation, which best describes the experimental curves:
−(t/τ1) −(t/τ3)
I(t) = A1e + A1e −(t/τ2) + A3e .
The percentage of emitted quanta in each exponent
is determined by the product Aiτi. Table 3 presents the
results of processing kinetic curves (lifetimes and
percentage of emitted quanta). Lifetimes of excited
states of free ligands L1 and L2 lie in the range 0.3–
43.5 ns, those for Zn(II) complexes, 0.42–92.8 ns, and
for Cd(II) complexes, 6.52–326 ns (Table 3). Most
likely, a wide range of times is caused by the
heterogeneity of emitting centers. Some of them may
be located on the surface of polycrystals, others are in
the depths of a lattice or near various defects.
As a result of the work we have synthesized and
studied a new group of Zn(II) and Cd(II) complexes
with chiral ligands L1 and L2 containing fragments of
1,10-phenanthroline and terpene α-aminooxime bound
by a linker group – piperazine. It was shown that the
new compounds show luminescence in the visible
region of spectrum. Luminescence quantum yields and
lifetimes of excited states were determined. In all
cases, the luminescence kinetics of the solid
compounds is complicated and well described by a set
of three exponents.
EXPERIMENTAL
For the syntheses we used analytical grade ZnCl2,
CdCl2·2.5H2O, ZnBr2·2H2O, and CdBr2·4H2O
chemically-pure grade, EtOH rectificate, methylene
chloride, chloroform, toluene, ethyl acetate, piperazine,
1,10-phenanthroline monohydrate, potassium carbonate,
anhydrous sodium sulfate, and methanol, special-
purity grade i-PrOH, (+)-3 carene obtained in the

RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 89 No. 1 2019

 LUMINESCENT COMPLEXES OF Zn(II) AND Cd(II)
laboratory of terpene compounds (isolated from
turpentine of Scots pine, ee ≥ 99.5%), and R-(+)-
limonene (Sigma-Aldrich, ee = 98%). Nitrosochlorides
of (+)-3-carene and R-(+)-limonene were obtained by
standard technique, passing nitrosyl chloride gas over a
terpene solution [12]. 2-Chloro-1,10-phenanthroline
was obtained by the procedure [32]. For thin-layer
chromatography ready-made Sorbfil plates were used.
The microanalysis for C, H, N was carried out on
an EuroEA 3000 analyzer. The IR spectra were recorded
in the range of 4000–200 cm–1 on ScimitarFTS 2000
and Vertex 80 IR Fourier spectrometers. Samples were
prepared by pressing with KBr and polyethylene.
Melting points were determined by the differential
scanning calorimetry method using NETZSCH STA
409 thermoanalyzer. The NMR spectra were recorded
on a Bruker DRX-500 spectrometer [500.13 (1H),
125.77 MHz (13C)] at 30°C for solutions of compounds
L1, 1, and 2 in CDCl3 or in CDCl3-DMSO-d6 mixtures
(Isotope, St. Petersburg) with deuterium atomic
fraction of no less than 99.8%. The NMR parameters
are given in Table 2. Analysis of tightly coupled
systems was fulfilled using the SpinWorks 4.2.0
software package (© 2015, KirkMarat, University of
Manitoba, Canada). Thermal analysis in helium
atmosphere was carried out using a TG 209 F1 Iris
NETZSCH microbalance. The experiments were
performed in the temperature range 20–300°C at the
heating rate 10 deg/min, using crucibles of Al2O3, at
the gas flow rate of 60 mL/min. Experimental data
were processed using the standard Proteus analysis
software packages. The luminescence excitation and
luminescence spectra were recorded using a Horiba
Jobin Yvon Fluorolog 3 photoluminescent spectrometer
equipped with a Xenon lamp, 450 W, integrating
sphere, double-grating resonant and emission Czerny-
Turner (Groove/1200 mm) monochromators, and an
FL-1073 PMT detector. The excitation spectra were
recorded in the range of 300–600 nm and corrected for
the spectral distribution of the lamps intensity, using a
photodiode reference detector. The emission spectra
were recorded in the range of 400–750 nm and
corrected for spherical response of the monochromators
and detector, using typical correcting spectra, provided
by the manufacturer. Quantum yields were measured
using a Quanta-φ integrating sphere. Luminescence
decay kinetics was recorded on a TCSPC using Nano-
LED pulsed light sources and a NanoLED-C2 controller.
2-(Piperazine-1-yl)-1,10-phenanthroline. A mixture
of 150 mL of toluene, 4.28 g (20 mmol) of 2-chloro-
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 89 No. 1 2019
93
1,10-phenanthroline and 1.03 g (120 mmol) piperazine
were boiled up to the disappearance of original 2-
chloro-1,10-phenanthroline. Control over the reaction
course was carried out by means of TLC (chloroform :
ethyl acetate = 1 : 1). Toluene was distilled off and the
residue was dissolved in chloroform and
chromatographed on silica gel, eluents—chloroform–
ethyl acetate (1 : 1) and chloroform–ethanol (10 : 1).
Yield 3.33 g (63%). 1Н NMR spectrum (CDCl3), δ,
ppm: 9.04 d.d (1Н, H9, J = 4.3, 1.6 Hz), 8.08 d.d (1Н,
H7, J = 8.1, 1.6 Hz), 7.90 d (1Н, H4, J = 9.1 Hz), 7.55
d (1Н, H5, J = 8.5 Hz), 7.45 d.d (1Н, H8, J = 8.1,
4.3 Hz), 7.41 d (1Н, H6, J = 8.6 Hz), 7.02 d (1Н, H3,
J = 9.1 Hz), 3.90 t (4Н, H15, J =5.0 Hz), 2.98 t (4Н,
H16, J = 5.0 Hz). 13C NMR spectrum (CDCl3), δC,
ppm: 156.60 (C2), 148.52 (C9), 144.33 (C13), 144.26
(C14), 137.25 (C4), 135.25 (C7), 128.57 (C12), 125.52
(C5), 121.64 (C11), 121.53 (C6), 121.36 (C8), 108.76
(C3), 43.59 (C15), 43.05 (C16).
Synthesis of ligands L1 and L2. A mixture of
70 mL of methanol, 2.64 g (10 mmol) of 2-(piperazine-
1-yl)-1,10-phenanthroline, 2.01 g (10 mmol) of a
corresponding terpene nitrozochloride, and 1.38 g
(10 mmol) of potassium carbonate was stirred at room
temperature up to complete nitrozochloride dissolution
(about 48 h). On completion of the reaction, methanol
was distilled off, and 100 mL of water and 100 mL of
chloroform were added to the residue. The aqueous
and organic phases were separated and the aqueous
phase was extracted with chloroform (2×50 mL). The
combined organic extract was dried with anhydrous
sodium sulfate, then the solvent was distilled off. The
residue was chromatographed on silica gel, eluents—
chloroform-ethyl acetate (1 : 1) and chloroform-
ethanol (10 : 1).
(1R,4S,6S,E)-4-[4-(1,10-phenanthroline-2-yl)pipe-
razine-1-yl]-4,7,7-trimеthylbicyclo[4.1.0]-heptane-3-
on oxime (L1). Yield 1.93 g (45%), mp 167–168°C
(decomp.), [α]25489 115 (c = 0.33, CHCl3). Mаss spec-
trum, m/z: 429.2523 [M]+ (calculated for C26H31ON5:
429.2519). Mаss spectrum, m/z (Irel, %): 371 (10), 264
(16), 263 (75), 222 (20), 208 (100), 179 (26).
(2S,5R,E)-2-[4-(1,10-phenanthroline-2-yl)pipera-
zine-1-yl]-2-mеthyl-5-(prop-1-en-2-yl)cyclohexanone
oxime (L2). Yield 2.39 g (56%), mp 204°C (decomp.),
[α]25489 28 (c = 0.56, CHCl3). Mаss spectrum, m/z:
429.2523 [M]+ (calculated for C26H31ON5: 429.2524).
Mаss spectrum, m/z (Irel, %): 412 (12), 264 (16), 263
(56), 222 (9), 208 (100), 179 (14). 1Н NMR spectrum
(CDCl3), δ, ppm: 10.20 br.s (1Н, ОН), 9.15 d.d (1Н,
94 KOKINA et al.
H22, J = 4.3, 1.7 Hz), 8.15 d.d (1Н, H20, J = 8.1,
1.5 Hz), 7.94 d (1Н, H15, J = 9.1 Hz), 7.60 d (1Н, H17,
J = 8.6 Hz, 7.52 d (1Н, H21, J = 7.8, 4.2 Hz), 7.45 d
(1Н, H18, J = 8.4 Hz), 7.10 d (1Н, H14, J = 9.1 Hz, 4.72
m (2Н, H8), 3.86 m (4Н, H12), 3.28 d (1Н, H3pro-S, J =
10.1 Hz), 2.75 m и 2.56 m (4Н, H11), 2.17 m (1Н, H6pro-S,
H5pro-S, H3pro-R), 1.91 d.d.d (1Н, H4, J = 13.2, 12.1, 3.0,
3.0 Hz), 1.73 s (3Н, 3H9), 1.47 d.d.d (1Н, H5pro-S, J =
13.4, 3.4, 3.0 Hz), 1.38 d.d.d (1Н, H6pro-S, J = 13.5, 13.5,
3.6 Hz), 1.11 c (3Н, H10). 13S NMR spectrum (CDCl3),
δS, ppm: 162.80 (C13), 158.20 (C4), 149.30 (C22),
148.86 (C7), 145.27 (C24), 144.93 (C23), 137.29 (C15),
136.12 (C20), 129.24 (C19), 126.34 (C17), 122.11 (C18),
122.03 (C16), 121.24 (C21), 109.96 (C14), 109.22 (C8),
60.63 (C1), 46.23 (C12), 45.52 (C4), 44.99 (C11), 37.15
(C6), 25.33 (C5), 25.04 (C3), 20.12 (C9), 14.29 (C10).
Synthesis of ZnL1Cl2·1.5H2O (1). To a solution of
0.022 g (0.050 mmol) of ligand L1 in 4 mL of MeOH,
a solution of 0.010 g (0075 mmol) of ZnCl2 in 3 mL of
MeOH was added with stirring. Gradually a fine light
yellow precipitate was formed. The solvent was
evaporated to the lowest possible volume (1 mL).
After suction filtration, the precipitate was washed
with i-PrOH and dried in a vacuum desiccator. Yield
0.010 g (34%). Found, %: C 52.3; Н 5.5; N 11.4.
C26H36Cl2N5O2.5Zn. Calculated, %: C 52.5; H 6.1; N 11.8.
CdL1Cl2·4H2O (2) was synthesized similarly from
0.022 g (0.050 mmol) of ligand L1 and 0.017 g
(0.075 mmol) of CdCl2.2.5H2O. Yield 0.003 g (9%).
Found, %: C 45.8; Н 5.3; N 10.0. C26H41Cl2N5O5Cd.
Calculated, %: C 45.5; H 6.0; N 10.2.
ZnL2Cl2·1.5H2О (3) was synthesized similarly from
0.022 g (0.050 mmol) of ligand L2 and 0.010 g
(0.075 mmol) of ZnCl2. Yield 0.013 g (44%). Found,
%: C 52.3; Н 5.5; N 11.4. C26H36Cl2N5O2.5Zn. Cal-
culated, %: C 52.5; H 6.1; N 11.8.
CdL2Cl2·5.5Н2О (4) was synthesized similarly from
0.022 g (0.050 mmol) of ligand L2 and 0.017 g
(0.075 mmol) of CdCl2.2.5H2O. Yield 0.008 g (22%).
Found, %: C 43.7; Н 4.7; N 9.5. C26H44Cl2N5O6.5Cd.
Calculated, %: C 43.7; H 6.2; N 9.8.
ZnL1Br2·2H2О (5) was synthesized similarly from
0.022 g (0.050 mmol) of ligand L1 and 0.013 g
(0.050 mmol) of ZnCl2.2H2O. Yield 0.016 g (46%).
Found, %: C 44.8; Н 4.6; N 9.9. C26H37Br2N5O3Zn.
Calculated, %: C 45.0; H 5.4; N 10.1.
CdL1Br2·2H2О (6) was synthesized similarly from
0.022 g (0.050 mmol) of ligand L1 and 0.017 g
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 89 No. 1 2019
(0.050 mmol) of CdBr2.4H2O. Yield 0.020 g (54%).
Found, %: C 42.8; Н 4.4; N 9.6. C26H37Br2N5O3Cd.
Calculated, %: C42.2; H 5.0; N 9.5.
FUNDING
This work was financially supported by the Federal
Agency for science and education of Russia, Russian
Foundation for basic research (project no. 18-33-
00243), Russian Foundation for basic research, and the
Government of the Novosibirsk region (project no. 17-
43-540857p_a).
CONFLICT OF INTEREST
No conflict of interest was declared by the authors.
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