Synthesis, structural diversity, luminescent properties and antibacterial effects of cadmium(II) and silver(I) coordination compounds with bis(1,2,3-benzotriazol-1-yl)alkanes

Article abstract of DOI:10.1016/j.poly.2019.114330

A series of bis(benzo-1,2,3-triazolyl)alkanes were prepared by the reaction of 1,2,3-benzotriazole with the corresponding dibromoalkanes. Individual isomers of these flexible polydentate ligands were separated by selective copper(II) chloride complex formation. Seven new coordination compounds of 1,3-bis(benzo-1,2,3-triazol-1-yl)propane (L₃), 1,4-bis(benzo-1,2,3-triazol-1-yl)butane (L₄) and 1,6-bis(benzo-1,2,3-triazol-1-yl)hexane (L₆) with cadmium(II) or silver(I) nitrates were prepared, characterized by single crystal X-ray diffraction, IR spectroscopy, thermogravimetric analysis and luminescence studies. It was found that depending on the solvent used, cadmium(II) nitrate forms discrete binuclear complex with the ligand L₃ in acetone and 1D coordination polymer in acetonitrile. Ligands L₄ and L₆ with longer linkers formed 2D coordination polymers with silver nitrate both in acetone and acetonitrile. Silver coordination polymer with L₆ demonstrated bactericidal effect towards Staphylococcus albus, Pseudomonas aeruginosa and Klebsiella pneumonia bacteria.

Full text of DOI:10.1016/j.poly.2019.114330

Journal Pre-proofs
Synthesis, structural diversity, luminescent properties and antibacterial effects
of cadmium(II) and silver(I) coordination compounds with bis(1,2,3-benzotria-
zol-1-yl)alkanes
Roman D. Marchenko, Anna A. Lysova, Denis G. Samsonenko, Danil N.
Dybtsev, Andrei S. Potapov
PII:
S0277-5387(19)30775-2
DOI:
https://doi.org/10.1016/j.poly.2019.114330
POLY 114330
Reference:
To appear in:
Polyhedron
Received Date:
Revised Date:
Accepted Date:
11 September 2019
9 December 2019
19 December 2019
Please cite this article as: R.D. Marchenko, A.A. Lysova, D.G. Samsonenko, D.N. Dybtsev, A.S. Potapov, Synthesis,
structural diversity, luminescent properties and antibacterial effects of cadmium(II) and silver(I) coordination
compounds with bis(1,2,3-benzotriazol-1-yl)alkanes, Polyhedron (2019), doi: https://doi.org/10.1016/j.poly.
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019.114330
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Synthesis, structural diversity, luminescent properties and antibacterial effects of cadmium(II) and
silver(I) coordination compounds with bis(1,2,3-benzotriazol-1-yl)alkanes
a
b,c
b,c
b,c
Roman D. Marchenko, Anna A. Lysova, Denis G. Samsonenko, Danil N. Dybtsev,
Andrei S. Potapov,* a,b
a
Kizhner Research Center Tomsk Polytechnic University, 30 Lenin Ave., 634050, Tomsk, Russia
Nikolaev Institute of Inorganic Chemistry, Siberian Branch of the Russian Academy of Sciences, 3
b
Acad. Lavrentiev Ave., 630090, Novosibirsk, Russia
c
Novosibirsk State University, 2 Pirogov Str., 630090, Novosibirsk, Russia
*
Corresponding author, potapov@niic.nsc.ru
Abstract
A series of bis(benzo-1,2,3-triazolyl)alkanes were prepared by the reaction of 1,2,3-benzotriazole
with the corresponding dibromoalkanes. Individual isomers of these flexible polydentate ligands were
separated by selective copper(II) chloride complex formation. Seven new coordination compounds of 1,3-
bis(benzo-1,2,3-triazol-1-yl)propane (L
3
), 1,4-bis(benzo-1,2,3-triazol-1-yl)butane (L ) and 1,6-bis(benzo-
4
1
,2,3-triazol-1-yl)hexane (L ) with cadmium(II) or silver(I) nitrates were prepared, characterized by
6
single crystal X-Ray diffraction, IR spectroscopy, thermogravimetric analysis and luminescence studies.
It was found that depending on the solvent used, cadmium(II) nitrate forms discrete binuclear complex
with the ligand L
linkers formed 2D coordination polymers with silver nitrate both in acetone and acetonitrile. Silver
coordination polymer with L demonstrated bactericidal effect towards Staphylococcus albus,
3
in acetone and 1D coordination polymer in acetonitrile. Ligands L
4
and L
6
with longer
6
Pseudomonas aeruginosa and Klebsiella pneumonia bacteria.
Keywords: benzotriazole; cadmium; silver; coordination polymers; crystal structure
1

Introduction
Bis(benzotriazolyl)alkanes possess a range of valuable biological and chemical properties.
Presence of four potential donor nitrogen atoms and conformational flexibility allows them to form
coordination compounds demonstrating a wide variety of structures [1]. Most of these compounds are
coordination polymers [2–4], but several examples of discrete complexes of 1,2-bis(benzotriazol-1-
yl)ethane (L
coordination compounds reported in the literature contain ligands with relatively short linkers (1 to 4
methylene groups, L -L ) and only several coordination polymers with penta- (L ) of hexamethylene (L
linkers are known. Thus, 1D copper(I) bromide [10,11], cadmium(II) bromide [7] and 3D copper(I)
chloride [12] coordination polymers with L were prepared and structurally characterized Quan-Guo Zhai
2
) [5–7] and 1,3-bis(benzotriazol-1-yl)propane (L
3
) [8,9] were reported. The majority of
1
4
5
6
)
6
et al. Very recently 1D copper(I) iodide coordination polymers with promising photophysical properties
making them excellent candidates for yellow-emitting phosphors were prepared [13]. Copper(I) [14] and
palladium(II) [15] in situ formed complexes were used as catalysts for C-N and C-C cross-coupling
reactions. A variety of cadmium(II) [7,16], copper(I) [17,18] and silver(I) [6] coordination polymers
demonstrated luminescent properties. Two-dimensional silver coordination polymer with L
3
exhibited
third-order non-linear optical properties [19]. In most of coordination compounds bis(benzotriazol-1-
3
3’
3
2
2’ 3’
yl)alkanes adopt a N ,N -bridging coordination mode, but in some cases they act as N ,N ,N ,N -
tertradentate bridging two metallocenters in a coordination polymer chain. All previously reported and
structurally characterized coordination compounds with L
3
-L
6
ligands are listed in Table 1. The ligands
, L and L were more potent
themselves were tested as antibacterial agents [20,21]. Compounds L
2
4
6
corrosion inhibitors compared to 1,2,3-benzotriazole and anticorrosion activity increased with
hydrocarbon linker elongation [22].
Table 1. Coordination compounds of bis(1,2,3-benzotriazolyl)alkanes reported in the literature
Compound (dimensionality) Benzotriazole ligand
coordination mode
Properties studied
Reference
3
3’
[
[
(CdI
(CdBr
2
)
2
2
(L
3
)]
∞
(1D)
(2D)
N ,N -bridging
N ,N -bridging, M
photoluminescence
photoluminescence
[7]
[7]
3
3’
)
2
(L
4
6
4
)]
∞
6
2
4
L
4
Br
2
4
8-membered cycles
3
3’
[
[
(CdBr
2
4
)
2
(L
)
]
2
]
∞
(1D)
N ,N -bridging, M
membered cycles
N ,N -bridging, M
membered cycles
N ,N -bridging
N ,N -bridging, M
L
2
26-
52-
photoluminescence
photoluminescence
–
[7]
[7]
3
3’
(CdI
2
)
(L
6
)
∞
(1D)
L
4
3
3’
[
[
(
[
[
[
[
[
[
[
Cu(N(CN)
Cu (N(CN)
0D)
Co(N(CN)
2
)
2
(L
3
)]
∞
(1D)
](ClO
[8]
[8]
3
3’
2
3
)
2
(L
3
)
4
4
)
2
2
L
4
cycles –
3
3’
2
)
2
(L
3
)]
)]
)]
∞
(3D)
(3D)
(2D)
N ,N -bridging
magnetic susceptibility
[8]
[8]
[8]
[9]
[9]
[10]
[10]
3
3’
Ni(N(CN)
Cu(N(CN)
2
)
2
(L
(L
·CH
(2D)
3
∞
N ,N -bridging
N ,N -bridging
magnetic susceptibility
magnetic susceptibility
cyclic voltammetry
cyclic voltammetry
photoluminescence
photoluminescence
3
3’
2
)
2
4
∞
3
3’
Cu(L
Cu(L
3
)Cl
2
]
2
3
OH (0D)
N ,N -bridging
3
3’
4
)1.5Cl
2
]
∞
N ,N -bridging
3
2
2’ 3’
K(Cu
(CuBr)
6
Br
7
)(L
)]
6
)]
∞
(2D)
N ,N ,N ,N -bridging
3
2
2’ 3’
4
(L
6
∞
(2D)
N ,N ,N ,N -bridging
2

3
2
2’ 3’
[
[
[
[
[
[
[
[
[
[
[
[
[
[
[
(CuBr)
K(Cu Br
(CuCl) (L
2
(L
)(L
)]
6
)]
∞
(3D)
N ,N ,N ,N -bridging
photoluminescence
semiconducting
[10]
[11]
[12]
[13]
[13]
[13]
[17]
[17]
[17]
[17]
[17]
3
2
2’ 3’
6
7
6
)]
∞
(2D)
N ,N ,N ,N -bridging
3
3’
2
6
∞
(3D)
N ,N -bridging
photoluminescence
photoluminescence
photoluminescence
white LED prototype
photoluminescence
photoluminescence
photoluminescence
photoluminescence
photoluminescence
3
3’
Cu
Cu
Cu
2
2
4
I
I
2
I
4
2
(L
(L
(L
4
5
5
)]
)]
)]
∞
∞
∞
(1D)
(1D)
(1D)
N ,N -bridging
3
3’
N ,N -bridging
3
3’
N ,N -bridging
3
2
2’ 3’
(CuCl)
2
(L
3
)]
∞
(1D)
(1D)
(2D)
N ,N ,N ,N -bridging
3
3’
(CuI) (L
2
4
)]
∞
N ,N -bridging
3
3’
(CuBr)
(CuBr)
2
(L
(L
4
)]
∞
N ,N -bridging
1
1’
3
3
’)]
∞
(2D)
(3D)
N ,N -bridging
3
2
2’ 3’
(CuCl)
[Ag (L
2
(L
4
)]
∞
N ,N ,N ,N -bridging
3
3’
2
3
3
) ](NO
3
2
) ]
∞
(2D)
N ,N -bridging
non-linear optical properties [19]
3
3’
Co(L
Cu(L
3
)Cl
)Cl
2
]
]
∞
(1D)
(2D)
N ,N -bridging
–
–
–
[23]
[23]
[23]
3
3’
3
2
∞
N ,N -bridging
1
1’
Cu
2
(L
3
’’)
2
Cl
2
]
∞
(1D)
N ,N -bridging, M
membered cycles
2
L
2
16-
3
3’
[
[
[
[
[
Zn(L
Zn(L
3
4
)(NCS)
)(NCS)
2
]
]
∞
(1D)
(1D)
N ,N -bridging
nonlinear optical properties
nonlinear optical properties
nonlinear optical properties
nonlinear optical properties
nonlinear optical properties
[24]
[24]
[25]
[25]
[26]
3
3’
2
∞
N ,N -bridging
3
3’
Ni(L
Co(L
Co(L
3
)
2
(NCS)
2
]
∞
(1D)
(1D)
(2D)
N ,N -bridging
3
3’
3
)
2
(NCS)
(NCS)
2
]
]
∞
N ,N -bridging
3
3’
4
)
2
2
∞
N ,N -bridging, M
membered cycles
4
4
4
L
4
44-
44-
44-
3
3’
[
[
[
Mn(L
Cd(L
CdI (L
4
)
2
(NCS)
(NCS)
)(CH
2
]
∞
(2D)
(2D)
N ,N -bridging, M
membered cycles
L
4
nonlinear optical properties
[26]
[26]
[27]
3
3’
4
)
2
2
]
∞
N ,N -bridging, M
membered cycles
L
4
nonlinear optical properties
3
3’
2
4
3
OH)]
∞
(1D)
N ,N -bridging
–
Bis(benzotriazolyl)alkanes can be prepared by the reactions between 1,2,3-benzotriazole and
dibromoalkanes in the presence of K CO and PEG under microwave irradiation conditions [21] or phase-
2
3
transfer conditions (tetra-n-butylammonium bromide / base) [28]; lithiated 1-alkylbenzotriazoles and
iodine [29]. Xiaodong Shi et al. reported the reaction of 1,2,3-benzotriazole with diols in Mitsunobu
reaction conditions (diisopropyl azodicarboxylate/ Ph P in THF) which favored the formation of 2-
3
substituted derivatives [30]. Bis(benzotriazol-1-yl)methane was selectively obtained by the reaction of
sodium benzotriazolate and 1-chloromethylbenzotriazole [31], by the condensation of 1-
hydroxymethylbenzotriazole with benzoyl chloride [32], or by the thermal decomposition of 1-
methylenebenzotriazol-1-ium [33]. However, alkylation in the superbasic medium (NaOH or preferably
KOH in DMSO) [13,34,35] seems to be the most general method for the synthesis of
bis(benzotriazolyl)alkanes, since the process does not require any specific, highly-dangerous or expensive
reagents, equipment and proceeds under mild conditions. Herein we report the synthesis of individual
isomers of bis(benzotriazolyl)alkanes L
3
-L , synthesis and crystal structures of their discrete and
8
polymeric cadmium(II) and silver(I) coordination compounds, as well as antibacterial and antifungal
activity of silver(I) coordination polymers and luminescent properties of cadmium complexes.
3

Materials and Methods
General methods
NMR spectra were recorded using Bruker AC300 and Bruker AVANCE III HD instruments operating at
1
13
3
00 and 400 MHz for H and 75 and 100 MHz for C.
Chromato-mass spectrometric analysis was carried out using Agilent 7890A gas chromatograph with
Agilient 5975C mass-selective detector with quadrupole mass-analyzer (electron impact ionization energy
7
4
0
0 eV). The injector temperature was maintained at 300 °C and the injection volume was 1 µL (split
0:1). The instrument was equipped with a HP-5ms capillary column of 30 m length, 0.25 mm i.d. and
.25 µm film thickness. The carrier gas was helium at a constant flow rate of 1 ml/min. The GC oven
program started at 79 °C (1.0 min hold) ramped up to 300 °C (heating rate 13 °C/min) for 10 min, total
chromatogram time was 28 min. Transfer line temperature was 300 °C, MS Source – 230 °C and MS
Quadrouple – 150 °C. The electron energy was 70 eV. From 0 min to 4 min the MS was switched off
(solvent delay). Data analysis and instrument control was carried out with MSD 5975C software.
-1
Infrared spectra of solid samples as KBr pellets were recorded using a VERTEX 80 (4000-400 cm ) and
-1
Nicolet 5700 (4000-400 cm ) instruments.
The elemental analyses were obtained on an analyzer «Vario Micro-Cube».
The powder X-ray diffraction data were obtained on «Shimadzu XRD 7000S» powder diffractometer
(Cu-Kα irradiation).
The thermogravimetric analyses were carried out in O
thermoanalyzer with the heating rate of 10 deg/min.
2
/Ar atmosphere on NETZSCH TG 209 F1
The luminescence spectra were recorded on Horiba Jobin Yvon Fluorolog 3 Photoluminescence
Spectrometer, equipped by 450 W xenon lamp, excitation/emission monochromator, and FL-1073 PMT
detector. The excitation was performed with ex = 330 nm, the emission was recorded at em = 400 nm.
Single-Crystal X-ray Diffraction
Diffraction data for single-crystals 1–7 were obtained on an automated Agilent Xcalibur diffractometer
equipped with an area AtlasS2 detector (graphite monochromator, λ(MoKα) = 0.71073 Å, ω-scans).
Integration, absorption correction, and determination of unit cell parameters were performed using the
CrysAlisPro program package [36]. The structures were solved by dual space algorithm (SHELXT [37])
and refined by the full-matrix least squares technique (SHELXL [38]) in the anisotropic approximation
(except hydrogen atoms). Positions of hydrogen atoms of organic ligands were calculated geometrically
and refined in the riding model. The crystallographic data and details of the structure refinements are
summarized in Table S1.
General procedure and analytical data for α,ω-bis(benzotriazolyl)alkanes
4

Powdered potassium hydroxide (0.84 g, 15 mmol) was dissolved in 5 ml of DMSO (Solution 1).
Benzotriazole (1.19 g, 10 mmol) was added to Solution 1. α,ω-Dibromoalkane (5 mmol) was dissolved in
5
ml of DMSO (Solution 2). Solution 1 was stirred on a magnetic stirrer at 80 °C during 30 minutes.
Solution 2 was added drop wise to a cold (10-20 °C) Solution 1 under cooling. The reaction mixture was
stirred and heated at 80 °C for an hour. The product was precipitated by a ten-fold volume of water,
filtered and washed by water. In case of hexane derivative an oily product was obtained and it was
extracted by ethyl acetate (20 ml x 3), the solvent was removed on a rotary evaporator. The product was
air-dried.
1
,3-Bis(benzo-1,2,3-triazolyl)propane mixture of isomers. Yield 80 %, colorless crystals. Anal. Calc.
(%): C, 64.73; H, 5.07; N, 30.20. Found: C, 64.99; H, 4.94; N, 30.47.
for C15
H
14
N
6
1
,3-Bis(benzo-1,2,3-triazol-1-yl)propane (L
3
). Yield 20 %, colorless crystals, m.p. 138-141 °С. m/z:
+
]+, 221.1 (31.1%) [C15
N
]+, 193.1 (28.2%), 180.1 (8.6%),
(
M) 278.1 (0.7%), 250.1 (4.7%) [C15
67.1 (30.6%), 160.1[C
]+, 78.1 (13.5%) [C
, J=6.6 Hz), 4.68 t (4Н, Bta-CH
H
14
N
4
H
13
2
1
9
H
10
N
]+, 132.1 (33.5%), 131.1 (33.6%) , 130.1 (45.2%), 104.1 (17.4%)
]+, 77.1 (100%) [C
3
+
1
[
C
6
H
4
N
2
6
H
6
6
H
5
] . Н NMR (CDCl
3
) δ 2.87 quint (2Н, CH
2
-CH -
2
CH
2
2
-CH
2
-CH
2
-Bta, J=6.5 Hz), 7.34-7.47 m (6Н, Bta), 8.05-8.07 d (2Н,
1
3
−1
Bta, J=6 Hz). С NMR (CDCl
3
) δ 29.4, 44.9, 109.3, 120.3, 124.3, 127.8, 133.2, 146.1. IR (cm ): 3070,
2
947, 2923, 2866, 1616, 1566, 1496, 1460, 1451, 1336, 1278, 1201, 1095, 1087, 746.
1
-(Benzo-1,2,3-triazol-1-yl)-3-(benzo-1,2,3-triazol-2-yl)propane (L
3
’). Yield 40 %, colorless crystals,
]+, 221.1 (9.2%) [C15 ]+, 193.1
]+, 132.1 (38.2%), 131.1 (72.8%), 130.1
+
m.p. 79-80 °С. m/z: (M) 278.1 (0.8%), 249.1 (5.6%) [C15
H
13
N
4
H
13
N
2
(15.6%), 181.1 (3.2%), 166.1 (9.3%), 159.1 (17.3%) [C
9
H
9
N
3
]+, 78.1 (20.0%) [C
H
6
]+, 77.1 (70.6%) [C
H
6 5
] . Н NMR (CDCl ) δ 2.86
+ 1
(100%), 104.1 (20.1%) [C
6
H
4
N
2
6
3
2
1
quint (2Н, Bta-CH
2
-CH
2
-CH
2
-Bta, J=6 Hz), 4.73 t (2Н, Bta -CH
2
-CH
2
-CH
2
-Bta , J=8 Hz), 4.80 t (2Н,
2
1
Bta -CH
2
-CH
2
-CH
2
-Bta , J=6 Hz), 7.33-7.50 m (5Н, Bta), 7.84-7.86 m (2Н, Bta), 8.03-8.05 d (1Н, Bta,
J=8 Hz). 13С NMR (CDCl
) δ 29.77, 45.13, 53.43, 109.34, 118.06, 120.12, 124.11, 126.66, 127.57,
3
−
1
1
1
1
33.15, 144.49, 145.99. IR (cm ): 3433, 3057, 2961, 2943, 1608, 1569, 1496, 1458, 1450, 1323, 1286,
268, 1204, 1160, 1116, 1044, 748.
,3-Bis(benzo-1,2,3-triazol-2-yl)propane (L
3
’’). Yield 20 %, colorless crystals, m.p. 120-122 °С. m/z:
]+, 146.1 (20.3%) [C ]+, 132.1 (7.7%), 131.1 (15.7%),
]+, 78.1 (22.5%) [C ]+, 77.1 (29.7%) [C
-Bta, J=7 Hz), 4.87 t (4Н, Bta-CH
.83-7.85 m (4Н, Bta). С NMR (CDCl
+
(
M) 278.1 (2.7%), 159.1 (100%) [C
9
H
9
N
3
8
H
8
N
3
+
1
1
30.1 (58.0%), 104.1 (32.7%) [C
6
H
4
N
2
6
H
5
6
H
5
] . Н NMR (CDCl )
3
δ 2.93 quint (2Н, Bta-CH
2
-CH -CH
2
2
2
, J=6 Hz), 7.35-7.38 m (4Н, Bta),
1
3
−1
7
3
1
3
) δ 30.03, 53.64, 118.09, 126.55, 144.53. IR (cm ): 3441, 3091,
069, 3001, 2960, 2927, 2856, 1564, 1496, 1458, 1445, 1439, 1327, 1284, 1191, 1142, 1069, 1061.
,4-Bis(benzo-1,2,3-triazolyl)butane mixture of isomers. Yield 80 %, colorless crystals. Anal. Calc. for
C
16
H
16
N
6
(%): C, 65.74; H, 5.52; N, 28.75. Found: C, 65.60; H, 5.78; N, 28.30.
5

1
2
1
,4-Bis(benzo-1,2,3-triazol-1-yl)butane (L
63.1 (8.8%) [C16
]+, 235.1 (17.8%) [C16
73.1 (46.0%) [C10
4
). Yield 20 %, colorless crystals, m.p. 146-147 °С. m/z:
H
15
N
4
H
15
N
2
]+, 207.1 (20.2%), 193.1 (13.7%), 180.1 (11.9%),
+
H
11
N
3
]+, 145.1 (26.7%), 132.1 (71.2%), 104.1 (24.2%) [C
7
H
6
N] , 77.1 (100%)
+
1
[
C
6
H
5
] . Н NMR (CDCl
3
) δ 2.04 quint (4Н, Bta-CH -CH
2
2
, J=3 Hz), 4.66 t (4Н, Bta-CH
2
-CH
2
, J=6 Hz),
1
3
7
1
1
1
.34-7.45 m (6Н, Bta), 8.02-8.08 d (2Н, Bta, J=8 Hz). С NMR (CDCl
3
) δ 26.45, 47.11, 109.14, 120.08,
−
1
24.06, 127.54, 132.78, 145.96. IR (cm ): 3431, 3068, 2949, 2879, 1495, 1467, 1455, 1326, 1273, 1213,
166, 1074, 737.
-(Benzo-1,2,3-triazol-1-yl)-4-(benzo-1,2,3-triazol-2-yl)butane (L
4
’). Yield 40 %, colorless crystals,
]+, 263.1 (51.5%) [C16
H N
15 4
]+, 235.1 (3%) [C16
H
15
N
2
] ,
+
m.p. 84-86 °С. m/z: 264.1 (17.1%) [C16
H
16
N
4
2
1
07.1 (9.5%), 173.1 (100%) [C10
H
11
N
]+, 145.1 (60.1%), 144.1 (31.6%), 132.1 (67%), 120.1 (23.0%),
3
+
+
+ 1
04.1 (24.3%) [C
7
H
6
N] , 91.1 (29.1%) [C
6
H
5
N] , 77.1 (91.4%) [C
6
H
5
] . Н NMR (CDCl
3
) δ 1.90 quint
1
2
1
2
(
2Н, Bta -CH
2
-CH
2
2
-CH -CH
2
-Bta , J=7 Hz), 2.04 quint (2Н, Bta -CH
2
-CH
2
-CH
2
-CH
2
-Bta , J=7 Hz),
1
2
1
2
4
7
2
3
1
1
.54 t (2Н, Bta -CH
2
-CH
2
-CH
2
-CH
2
-Bta , J=8 Hz), 4.65 t (2Н, Bta -CH
2
-CH
2
-CH
2
-CH
2
-Bta , J=6 Hz),
1
3
.20-7.36 m (5Н, Bta), 7.70-7.74 m (2Н, Bta), 7.91-7.93 d (1Н, Bta, J=8 Hz). С NMR (CDCl ) δ 26.39,
3
−
1
6.86, 47.10, 55.36, 109.14, 117.87, 119.93, 123.86, 126.33, 127.26, 132.73, 144.24, 145.86. IR (cm ):
064, 2934, 2858, 1566, 1455, 1460, 1323, 1274, 1194, 1052, 738.
,4-Bis(benzo-1,2,3-triazol-2-yl)butane (L
4
’’). Yield 20 %, colorless crystals, m.p. 110-111 °С. m/z:
]+, 172.1 (17.1%) [C10 ]+, 145.1 (49.3%), 132.1 (5.6%), 120.1 (7.7%), 105.1
]+, 77.1 (25.9%) [C
-Bta, J=7 Hz), 4.77 t (4Н, Bta-CH -CH
73.1 (100%) [C10
H
11
N
3
H N
10 3
+
+ 1
(8.3%) [C
7
H
7
N] , 78.1 (12.4%) [C
6
H
6
6
H
5
] . Н NMR (CDCl ) δ 2.15 quint (4Н, Bta-
3
CH
2
-CH
2
-CH
2
-CH
2
2
2
-CH
2
-CH
2
-Bta, J=4 Hz), 7.33-7.37 m (4Н,
1
3
−1
Bta), 7.81-7.85 m (4Н, Bta). С NMR (CDCl ) δ 26.96, 55.60, 118.02, 126.39, 144.38. IR (cm ): 2964,
3
2
929, 1567, 1466, 1326, 1279, 1242, 1140, 1094, 848, 746.
,5-Bis(benzo-1,2,3-triazolyl)pentane mixture of isomers. Yield 83 %, colorless crystals. Anal. Calc.
(%): C, 66.65; H, 5.92; N, 27.43. Found: C, 66.42; H, 5.68; N, 27.65.
1
for C17
H
18
N
6
1
2
1
,5-Bis(benzo-1,2,3-triazol-1-yl)pentane (L
5
). Yield 20%, colorless crystals, m.p. 103-105 °С. m/z:
77.1 (6.4%) [C17
H
17
N
4
]+, 249.1 (33.4%) [C17
H
17
N
]+, 221.1 (16.7%), 167.1 (21.7%), 158.1 (32.9%),
2
+
+
46.1 (13.8%), 132.1 (27.6%), 119.1 (22.0%), 104.1 (25.9%) [C
7
H
6
N] , 91.1 (44.1%) [C
-CH -CH -CH , J=8 Hz), 2.03 m (4Н,
-CH , J=8 Hz), 7.29-7.42 m (6Н, Bta),
) δ 20.99, 23.85, 28.96, 47.70, 109.23, 119.85, 123.98, 127.37,
45.73. IR (cm ): 3064, 2941, 2864, 1614, 1591, 1496, 1456, 1325, 1261, 1228, 1174, 1049, 742.
6
H
5
N] , 77.1
+
1
(100%) [C
6
H
5
] . Н NMR (CDCl
3
) δ 1.32-1.34 d (2H, CH
2
-CH
2
2
2
2
CH
2
-CH
2
-CH
2
-CH -CH ), 4.51-4.57 q (4Н, CH
2
2
2
-CH -CH -CH
2
2
2
2
1
3
7
1
1
.99 t (2Н, Bta, J=8 Hz). С NMR (CDCl
3
−
1
-(Benzo-1,2,3-triazol-1-yl)-5-(benzo-1,2,3-triazol-2-yl)pentane (L
]+, 277.2 (76.0%) [C17
21.1 (6.6%), 193.1 (21.5%), 187.1 (67.6%) [C11
5
’). Yield 42 %, colorless crystals,
]+, 249.1 (6.1%) [C17
H
17
N
2
] ,
+
mp 75-76 °С. m/z: 278.2 (45.0%) [C17
H
18
N
4
H
17
N
4
2
1
H
13
N
3
]+, 167.1 (12.3%), 159.1 (26.8%), 146.1 (14.7%),
+
+
32.1 (45.5%), 130.1 (24.0%), 120.1 (55.1%), 104.1 (36.9%) [C
7
H
6
N] , 93.1 (46.1%) [C
6
H N] , 91.1
7
6

+
]+, 77.1 (100%) [C
-CH -CH -CH -CH
+ 1
(
45.4%) [C
6
H
7
N] , 78.1 (27.2%) [C
-CH ), 1.74-1.87 m (4Н, CH
), 7.07-7.26 m (5Н, Bta), 7.58-7.78 m (3Н, Bta). 13С NMR (CDCl
6
H
6
6
H
5
] . Н NMR (CDCl
3
) δ 1.12 s (2Н, СH
2
-
-
CH
2
-CH
2
-CH
2
2
2
2
2
2
2
), 4.29-4.43 m (4Н, CH
2
-CH -CH -CH
2
2
2
CH
2
3
) δ 23.09, 28.38, 28.68, 47.15,
−
1
5
2
1
1
1
7
5.41, 108.85, 117.37, 119.18, 123.29, 125.67, 126.65, 132.28, 143.66, 145.27. IR (cm ): 3444, 3051,
954, 2871, 1496, 1464, 1454, 1323, 1286, 1224, 1186, 1160, 1111, 1053, 850, 752, 743.
,5-Bis(benzo-1,2,3-triazol-2-yl)pentane (L
87.1 (100%) [C11
]+, 174.1 (6.1%) [C10
32.1 (14.1%), 120.1 (27.4%), 104.1 (22.9%) [C
5
’’). Yield 21 %, colorless crystals, m.p. 42-44 °С. m/z:
H
13
N
3
H
12
N
3
]+, 159.1 (13.3%), 146.1 (19.2%), 133.1 (16.2%),
+
+
+
7
H
6
N] , 91.1 (19.2%) [C
) δ 1.38 quint (2Н, СH -CH -CH -CH
, J=7 Hz), 4.69 t (4Н, CH -CH -CH -CH -CH , J=6 Hz), 7.33-7.35 m (4Н,
=3 Hz). С NMR (CDCl ) δ 23.58, 29.39, 56.11, 117.98, 126.27,
6
H
7
N] , 78.1 (18.3%) [C
6
H ] ,
6
+
1
7.1 (30.5%) [C
4Н, CH -CH -CH
Bta), 7.80-7.82 dd (4Н, Bta, J
6
H
5
] . Н NMR (CDCl
3
2
2
2
2
-CH , J=7 Hz), 2.16 quint
2
(
2
2
2
-CH -CH
2
2
2
2
2
2
2
13
1
=6 Hz, J
2
3
−
1
1
7
1
44.31. IR (cm ): 2947, 2923, 2866, 1566, 1466, 1450, 1326, 1278, 1201, 1096, 1087, 979, 850, 830,
46.
,6-Bis(benzo-1,2,3-triazolyl)hexane mixture of isomers. Yield 81%, yellow oil. Anal. Calc. for
C
18
H
20
N
6
(%): C, 67.48; H, 6.29; N, 26.23. Found: C, 67.53; H, 6.13; N, 25.94.
,6-Bis(benzo-1,2,3-triazol-1-yl)hexane (L ). Yield 20 %, colorless crystals, m.p. 97-99 °С. m/z: 291.1
3.4%) [C18
]+, 263.1 (13.1%) [C18 ]+, 249.1 (24.2%), 235.1 (10.0%), 221.1 (12.2%), 208.1
10.4%), 193.1 (9.1%), 174.1 (15.6%), 172.1 (15.8%), 167.1 (10.7%), 158.1 (6.2%), 145.1 (20.3%), 132.1
1
6
(
(
(
H
19
N
4
H
19
N
2
+
+
+
1
33.3%), 119.1 (57.1%), 104.1 (28.6%) [C
, 400 MHz) δ 1.38 quint (4H, CH
-CH -CH , J=6.7 Hz), 4.61 t (4Н, CH
m (2Н, Bta), 7.46-7.47 dd (4H, Bta, J =3.5 Hz, J =0.9 Hz), 8.04-8.06 dd (2Н, Bta, J
7
H
6
N] , 91.1 (49.7%) [C
-CH -CH -CH -CH
-CH -CH -CH -CH
6
H
5
N] , 77.1 (100%) [C
-CH , J=3.6 Hz), 1.9 t (4Н, CH
-CH
6
H ] . Н
5
NMR (CDCl
3
2
2
2
2
2
2
2
-
CH -CH -CH
2
2
2
2
2
2
2
2
2
2
2
-CH
2
, J=7 Hz), 7.33-7.39
=8.4 Hz, J =0.8 Hz).
1
2
1
2
13С NMR (CDCl
) δ 26.25, 29.49, 48.01, 109.33, 120.21, 123.97, 127.38, 133.02, 146.14. IR (cm−1):
3
3
7
1
3
069, 2936, 2864, 1616, 1585, 1495, 1468, 1456, 1319, 1312, 1265, 1260, 1200, 1167, 1070, 777, 761,
33, 761, 733, 428.
-(Benzo-1,2,3-triazol-1-yl)-6-(benzo-1,2,3-triazol-2-yl)hexane (L
20.2 (11.2%), 292.2 (27.3%) [C18
]+, 291.2 (52.3%) [C18
]+, 235.1 (5.4%), 221.1 (9.7%), 208.1 (13.4%), 207.1 (13.0%), 195.1 (7.8%), 188.1 (21.6%)
]+, 173.1 (16.8%), 146.1 (16.8%), 133.1 (28.9%), 132.1 (48.6%), 120.1 (80.2%), 119.1
’). Yield 41 %, yellow oil. m/z: (M)+
]+, 263.1 (6%), 249.1 (24.2%)
6
H
20
N
4
H
19
N
4
[
[
(
[
C
17
H
18
14
N
2
3
C
11
H
N
+
+
+
28.2%), 105.1 (21.3%) [C
7
H
7
N] , 104.1 (38.6%) [C
7
H
6
N] , 91.1 (56.2%) [C
, 400 MHz) δ 1.39 quint (4Н, СH
-CH -CH -CH
-CH -CH -CH
6
H N] , 78.1 (27.1%)
5
C
6
H
6
]+, 77.1 (100%) [C
, J=3.5 Hz), 2.0 quint (2Н, CH
6
H
5
] . Н NMR (CDCl
+ 1
3
2
-CH
2
-CH
2
-CH
2
-CH
2
-
2
-
2
-
1
2
CH
CH
CH
2
2
2
2
-CH
2
-CH
2
2
2
2
, J=7.2 Hz), 2.09 quint (2Н, CH
2
-CH
1
2
-CH
2
-CH
2
-CH
2
, J=7.1 Hz), 4.61 t (2Н, CH
2
2
2
2
-CH
2
-CH
2
, J=7 Hz), 4.7 t (2Н, CH
-CH
2
- CH
2
-CH
2
-CH
2
, J=6.9 Hz), 7.36-7.49 m (5Н, Bta), 7.83-7.86 dd (2Н, Bta, J
1
=6.5 Hz, J
2
=3.1
Hz), 8.05-8.07 d (1Н, Bta, J=8.3 Hz). 13С NMR (CDCl
) δ 26.10, 26.25, 29.51, 29.83, 48.16, 56.42,
3
7

−
1
1
1
1
3
09.39, 118.05, 120.04, 124.18, 126.37, 127.47, 144.39. IR (cm ): 2935, 2858, 1614, 1566, 1495, 1452,
323, 1268, 1224, 1158, 1111, 1053, 999, 849, 740, 668.
,6-Bis(benzo-1,2,3-triazol-2-yl)hexane (L
6
’’). Yield 20 %, colorless crystals, m.p. 93-95 °С. m/z: (M)+
]+, 188.1 (22.6%) [C11 ]+, 173.1
20.2 (23.0%), 263.1 (7.4%) [C18
H
19
N
2
]+, 201.1 (45.2%) [C12
H
15
N
3
H
14
N
3
(54.1%), 159.1 (13.1%), 146.1 (37.0%), 145.1 (31.1%), 132.1 (33.3%), 120.1 (100%), 104.1 (47.9%)
+
+
+ 1
[
C
7
H
6
N] , 91.1 (56.7%) [C
-CH -CH -CH -CH -CH
4Н, CH -CH -CH -CH -CH
4Н, Bta, J =6.5 Hz, J
=3 Hz). 13С NMR (CDCl
cm ): 3067, 2947, 2918, 2857, 1566, 1467, 1438, 1369, 1322, 1281, 1239, 1119, 980, 913, 853, 735,
6
H
5
N] , 77.1 (57.9%) [C
, J=3.5 Hz), 2.11 quint (4Н, CH
-CH , J=7 Hz), 7.35-7.38 dd (4Н, Bta, J
) δ 26.14, 29.91, 56.47, 118.07, 126.34, 144.39. IR
6
H
5
] . Н NMR (CDCl
-CH -CH -CH
=6.5 Hz, J
3
, 400 MHz) δ 1.41 quint (4Н,
-CH -CH , J=7 Hz), 4.7 t
=3 Hz), 7.83-7.85 dd
СH
2
2
2
2
2
2
2
2
2
2
2
2
(
(
(
2
2
2
2
2
2
1
2
1
2
3
−
1
6
1
1
68.
,7-Bis(benzo-1,2,3-triazolyl)heptane mixture of isomers. Yield 92 %, yellow oil. Н NMR (CDCl
.28-1.29 m (6H, (СH -(CH -(CH ), 1.91-2.02 m (4H, СH -CH -(CH -CH -CH
), 4.54 t (2H, Bta1-
-(CH , J=7 Hz), 4.64 t (2H, Bta -CH , J=7 Hz), 7.28-7.43 m (5H, Bta), 7.77-7.80 dd (2H,
Bta, J =6.6 Hz, J =3 Hz), 7.96-7.99 dd (1H, Bta, J =0.75 Hz, J =4.12 Hz). Anal. Calc. for C19 (%):
1
3
): δ
2
)
2
2
)
3
2
)
2
2
2
2
)
3
2
2
2
CH
2
2
)
6
2
-(CH
2 6
)
1
2
1
2
H
22
N
6
C, 68.24; H, 6.63; N, 25.13. Found: C, 68.33; H, 6.37; N, 25.19.
+
N
]+, 277.1
1
,7-Bis(benzo-1,2,3-triazol-1-yl)heptane (L
7
). m/z: (M) 334.2 (2.7%), 305.1 (2.8%) [C19
H
21
4
(3.9%) [C19
H
23
N
2
]+, 249.1 (11.7%) [C19
H
21]+, 223.1 (8.2%), 207.1 (7.0%), 193.1 (11.7%), 188.1 (23.6%),
+
1
67.1 (15.1%), 146.1 (17.2%), 132.1 (39.2%), 119.1 (84.6%), 104.0 (31.0%) [C
7
H
6
N] , 91.0 (47.4%)
+
+
[
C
6
H
5
N] , 77.0 (100%) [C
-(Benzo-1,2,3-triazol-1-yl)-7-(benzo-1,2,3-triazol-2-yl)heptane (L
]+, 249.1 (9.9%) [C19 21]+, 202.1 (20.4%) [C12
67.1 (8.2%), 158.1 (8.9%), 146.1 (25.4%), 133.1 (57.9%), 132.1 (45.1%), 120.1 (100%), 104.1 (38.4%)
6
H
5
] .
+
1
7
’). m/z: (M) 334.2 (26.8%), 305.2
]+, 193.1 (21.1%), 174.1 (10.2%),
(
8.7%) [C19
H
21
N
4
H
H
16
N
3
1
+
+
+
[
C
7
H
6
N] , 91.1 (54.0%) [C
,7-Bis(benzo-1,2,3-triazol-2-yl)heptane (L
15.1 (13.0%) [C13
]+, 202.1 (15.7%) [C12
6
H
5
N] , 77.1 (90.0%) [C
’’). m/z: (M) 334.2 (16.1%), 277.2 (12.8%) [C19
]+, 187.1 (15.1%), 173.1 (22.7%), 159.1 (14.2%),
6
H
5
] .
+
+
1
2
1
7
H
21
N ] ,
2
H
18
N
3
H
16
N
3
+
+
46.1 (32.8%), 133.1 (32.1%), 120.1 (100%), 104.1 (34.7%) [C
7
H
6
N] , 91.1 (48.0%) [C
6
H
5
N] , 78.1
]+, 77.1 (41.7%) [C
H
5
] .
+
(26.8%) [C
6
H
6
6
1
1
,8-Bis(benzo-1,2,3-triazolyl)octane mixture of isomers. Yield 81 %, colorless crystals. Н NMR
(
CDCl
3
): 1.27-1.29 m (8H, (CH
2
)
2
-(CH
2
)
4
-(CH
2
)
2
), 1.95-2.08 m (4H, CH
2
-CH
, J=7 Hz), 7.30-7.49 m (4H, Bta), 7.81-7.84
=3 Hz), 8.01-8.04 d (2H, Bta, J=8.4 Hz). Anal. Calc. for C20 (%): C,
2
-(CH
2
)
4
-CH
2
-CH
2
), 4.57 t
1
2
(2H, Bta -CH
2
-(CH
2
)
7
, J=7 Hz), 4.67 t (2H, Bta -CH
2
2 7
-(CH )
dd (2H, Bta, J
1
=6.3 Hz, J
2
H
24
N
6
6
8.94; H, 6.94; N, 24.12. Found: C, 68.70; H, 7.20; N, 23.90.
+
N
]+, 291.2
1
,8-Bis(benzo-1,2,3-triazol-1-yl)octane (L
8
). m/z: (M) 348.2 (0.5%), 319.2 (4.7%) [C20
H
23
4
(5.7%) [C20
H
23
N
2
]+, 277.2 (5.1%), 263.1 (6.0%), 249.1 (19.4%), 202.1 (31.8%), 200.1 (14.3%), 193.1
8

(9.0%), 167.1 (12.0%), 158.1 (6.8%), 146.1 (21.2%), 132.1 (43.7%), 120.1 (42.5%), 119.1 (88.1%), 104.1
+
+
]+, 77.1 (100%) [C
+
(
33.7%) [C
-(Benzo-1,2,3-triazol-1-yl)-8-(benzo-1,2,3-triazol-2-yl)octane (L
12.1%) [C20
]+, 291.2 (5.1%) [C20 ]+, 277.2 (4.2%), 263.1 (6.0%), 249.1 (15.5%), 229.2
9.4%) [C14
]+, 216.2 (29.7%) [C13 ]+, 208.1 (11.5%), 202.1 (9.4%), 193.1 (15.0%), 188.1
22.7%), 180.1 (9.5%), 172.1 (11.6%), 160.1 (13.1%), 147.1 (21.5%), 146.1 (34.3%), 133.1 (53.6%),
7
H
6
N] , 91.1 (64.7%) [C
6
H
5
N] , 78.1 (15.2%) [C
6
H
6
6
5
H ] .
+
1
8
’). m/z: (M) 348.2 (48.7%), 319.2
(
H
23
N
4
H
23
N
2
(
H
19
N
3
H
18
N
3
(
+
+
1
32.1 (54.3%), 120.1 (100%), 119.1 (37.5%), 104.1 (47.2%) [C
7
H
6
N] , 91.1 (69.3%) [C
6
H
5
N] , 78.1
]+, 77.1 (97.6%) [C
H
5
] .
+
(24.5%) [C
6
H
6
6
+
+
1
2
,8-Bis(benzo-1,2,3-triazol-2-yl)octane (L
8
’’). m/z: (M) 348.2 (30.1%), 319.2 (5.1%) [C20
H
23
N
4
] ,
91.2 (15.3%) [C20
H
23
N
2
]+, 249.1 (5.1%), 229.2 (11.6%) [C14
H
19
N
3
]+, 216.2 (10.7%) [C13
H
18
N
3
]+, 201.1
(13.6%), 188.1 (11.8%), 172.1 (24.2%), 161.1 (14.1%), 146.1 (34.3%), 133.1 (34.6%), 132.1 (28.2%),
+
+
H
N]+,
1
7
20.1 (100%), 119.1 (23.8%), 105.1 (19.2%) [C
H
7 7
N] , 104.1 (37.4%) [C
7
H
6
N] , 91.1 (45.8%) [C
6
5
8.1 (25.9%) [C
6
H
6
]+, 77.1 (41.3%) [C
6
H
5
] .
+
Preparation of 1,3-Bis(benzotriazolyl)propane under solvent-free conditions
Powdered potassium hydroxide (0.168 g, 3 mmol), 1,2,3-benzotriazole (0.238 g, 2 mmol) and 1,3-
dibromopropane (0.102 ml, 1 mmol) were loaded into a sealed flask and heated at 110 °C. After 1 hour,
the reaction mixture was suspended in water, the product was extracted by dichloromethane (5 ml x 5);
the extract was washed by water; the solvent was removed by distillation; the product was air-dried. The
yield was 67 %, which contained 33 % of L
3
, 28% of L
3
’, 6% of L ’’.
3
Preparation of copper chloride (II) complexes for the separation of isomers
Portions of isomer mixtures and copper chloride (II) dihydrate were dissolved in acetone separately; the
solutions were mixed and allowed to stand for an hour. The precipitate of the complex was filtered and
washed by acetone. Yield 66-88 %.The complexes were degraded by a small amount of DMSO. The
resulting solutions were diluted by ten-fold excess of water and left to coagulate overnight. Precipitates of
the ligands were filtered using a glass filter, washed by NH
4
OH solution and water, then dried. When
compounds L , L and L were isolated after precipitation by water, oily products were obtained, they
5
6
7
were extracted by dichloromethane (20 ml x 5); the extracts were washed by NH
the solvent was removed by distillation and the products were dried.
Synthesis of coordination compounds
4
OH solution and water;
Synthesis of [Cd(L
3
)
2
(NO
3
2
) ]
∞
(1)
Cadmium(II) nitrate tetrahydrate Cd(NO
3
)
2
∙4H O (0.015 g, 0.05 mmol) was dissolved in 1 ml of acetone.
2
LI (0.042 g, 0.15 mmol) was dissolved in 4.5 ml of acetone. The ligand solution was added dropwise to
the cadmium nitrate solution under stirring. The resulting solution was opaque, so, 2 ml of acetone was
added to the reaction system. The vial with the reaction solution was left at room temperature for slow
evaporation. In two days plate crystals were formed, they were washed with acetone (36.5 ml) and dried
9

in air. Yield 0.0124 g (78 %). Anal. Calc. for C30
H28CdN14
O
6
(%): C 45.44, H 3.56, N 24.73 %. Found: C
–
1
4
5.3, H 3.55, N 24.5. IR data (cm ): 3561 (m), 3100 (w), 3070 (w), 3036 (w), 2951 (m), 1615 (w), 1594
(
w), 1496 (w), 1461 (m), 1436 (m), 1385 (s), 1330 (w), 1310 (w), 1293 (w), 1273 (m), 1225 (m), 1183
m), 1169 (w), 1145 (w), 1116 (w), 1037 (m), 1026 (w), 1004 (w), 988 (w), 942 (w), 743 (s), 432 (w).
(
Synthesis of [Cd
Cadmium(II) nitrate tetrahydrate Cd(NO
acetonitrile. L (0.042 g, 0.15 mmol) was dissolved in 4.5 ml of acetonitrile. The ligand solution was
2
(L
3
)
2
(NO
3
)
4
(H
2
4
O) ] (2)
3
)
2
∙4H O (0.015 g, 0.05 mmol) was dissolved in 1 ml of
2
3
added dropwise to the cadmium nitrate solution under stirring. The vial with the reaction solution was left
at room temperature for slow evaporation. In six days plate crystals were formed, they were washed with
acetonitrile (35.5 ml) and dried in air. Yield 0.0276 g (85 %). Anal. Calc. for
C
30
H36Cd
2
N
16
O
16·3.5CH
3
CN2.5H O (%): C 34.4, H 4.0, N 21.17. Found: C 34.6, H 3.9, N 20.75. IR data
2
–
1
(
cm ): 3461 (s), 3097 (w), 3071 (w), 2950 (w), 1637 (m), 1592 (w), 1494 (w), 1452 (w), 1400 (w), 1385
s), 1331 (s), 1330 (w), 1310 (w), 1279 (w), 1244 (w), 1228 (w), 1203 (m), 1183 (w), 1139 (w), 1117 (m),
(
1
081 (w), 1037 (m), 998 (w), 943 (w), 858 (w), 820 (m), 780 (m), 753 (s), 743 (s), 664 (w), 575 (w), 539
w) 503 (w), 432 (m), 409 (w).
Synthesis of [Cd (L (NO (H
ratio was less than 3, hexagonal plates were formed as an impurity to 1 (when the synthesis
(
2
3
)
2
3
)
4
2
O) ] (3)
2
2
+
When Cd :L
3
was carried out in acetone) or to 2 (when acetonitrile was used as a solution). Their crystal structure and
chemical composition were established by a single-crystal X-ray diffraction method.
Synthesis of [Ag(L
4
)(NO
3
)]
∞
(4)
Silver nitrate AgNO
3
(0.0085 g, 0.05 mmol) was dissolved in 1 ml of acetonitrile. L (0.015 g, 0.05
4
mmol) was dissolved in 2 ml of acetonitrile. The ligand solution was added dropwise to the silver nitrate
solution under stirring. The vial with the reaction solution was closed with a screw cap and left at room
temperature in the dark. In two weeks plate crystals were formed, they were washed with acetonitrile
(
33 ml) and dried in air. Yield 0.0034 g (15 %).
Synthesis of [Ag(L )(NO )] (5)
Silver nitrate AgNO (0.0085 g, 0.05 mmol) was dissolved in 6 ml of acetone. L (0.029 g, 0.10 mmol)
4
3
∞
3
4
was dissolved in 4 ml of acetone. The ligand solution was added dropwise to the silver nitrate solution
under stirring. Then 5 ml of N,N-dimethylformamide was added dropwise to the vial with the solution
under stirring. The vial was closed with a screw cap and left at room temperature in the dark. In two
weeks plate rhombohedral crystals were formed, they were filtered, washed with acetone (314 ml) and
dried in air. Yield 0.0095 (40 %). Anal. calc. for C16
H
16AgN
7
O
3
(%): C 41.58, H 3.49, N 21.21. Found: C
1.6, H 3.2, N 21.3 %. IR data (cm ): 3468 (w), 3091 (w), 3068 (w), 3034 (w), 2953 (w), 1614 (w), 1593
w), 1496 (w), 1457 (m), 1448 (w), 1411 (w), 1385 (s), 1286 (s), 1215 (s), 1185 (m), 1164 (w), 1061 (s),
032 (m), 935 (m), 820 (m), 759 (w), 743 (s), 671 (w), 543 (w), 489 (w) 429 (s).
–
1
4
(
1
1
0

Synthesis of [Ag(L
6
)(NO
3
)]
∞
(6)
Silver nitrate AgNO
3
(0.0336 g, 0.20 mmol) was dissolved in 4 ml of acetonitrile. L (0.064 g, 0.20
6
mmol) was dissolved in 12 ml of acetonitrile. The ligand solution was added dropwise to the silver nitrate
solution under stirring. The vial with the reaction solution was closed with a screw cap and left at room
temperature in the dark. In two weeks square prismatic crystals were formed, they were filtered, washed
with acetonitrile (316 ml) and dried in air. Yield 0.0245 g (25 %). Anal. calc. for C18
H20AgN
7
3
O (%): C
–
1
4
2
1
4.10, H 4.11, N 20.00. Found: C 44.0, H 4.0, N 19.7 %. IR data (cm ): 3063 (w), 2945 (w), 2928 (m),
920 (w), 2853 (m), 2434 (w), 2336 (w), 1612 (w), 1593 (w), 1496 (w), 1456 (m), 1406 (s), 1360 (w),
311 (s), 1276 (w), 1221 (s), 1162 (s), 1148 (w), 1130 (w), 1066 (s), 1041 (m), 1000 (m), 941 (m), 903
(
w), 823 (m), 779 (w), 771 (m), 760 (w), 752 (s), 735 (w), 703 (w), 667 (w), 574 (w), 515 (w), 435 (m).
Synthesis of [Ag(L )(NO )] (7)
Silver nitrate AgNO (0.0085 g, 0.05 mmol) was dissolved in 1 ml of acetonitrile. L (0.0326 g, 0.10
6
3
∞
3
6
mmol) was dissolved in 4 ml of acetonitrile. The ligand solution was added dropwise to the silver nitrate
solution under stirring. The vial with the reaction solution was closed with a screw cap and left at room
temperature in the dark. In two weeks plate crystals were formed, they were filtered, washed with
acetonitrile (35 ml) and dried in air. Yield 0.0086 g (35 %). Anal. calc. for C18
H20AgN
7
O
3
(%): C 44.10,
–
1
H 4.11, N 20.00. Found: C 44.4, H 3.8, N 20.1 %. IR data (cm ): 3454 (w), 3092 (w), 3063 (w), 3035
(w), 2944 (w), 2929 (w), 2915 (w), 2855 (w), 1740 (w), 1611 (w), 1590 (w), 1494 (m), 1462 (m), 1385
(s), 1362 (w), 1318 (s), 1217 (s), 1162 (s), 1139 (w), 1070 (m), 1038 (s), 1004 (w), 942 (w), 902 (w), 822
(m), 778 (s), 762 (m), 736 (m), 704 (w), 669 (w), 528 (w), 441 (m).
Antibacterial and antifungal activity determination
All measurements were conducted in accordance with the Guidelines for Antimicrobial Susceptibility
Testing [39]. The inhibitory, bactericide and fungicide efficiency of compounds L
4
and L were assayed
6
in vitro in the nutrient broth. Staphylococcus albus, Escherichia coli, Pseudomonas aeruginosa,
Klebsiella pneumonia bacteria and Candida albicans yeast strains were used as test cultures. The
bactericidal activity is defined as a reduction of 99% of the total count of colony-forming units (CFU) in
1
ml the original inoculum, whereas the bacteriostatic activity is defined as maintenance of a reduction of
less than 99% of the total count of CFU/ml in the original inoculum.
The meat infusion broth was poured into five test tubes (0.5 ml) for each microorganism. L
4
and L were
6
dissolved in DMSO and added to the broth (0.5 ml). The range of concentrations was from 1024 μg/ml to
6
4 μg/ml. Analyses were conducted with a sequential dilution assay. Inoculums were prepared from the
8
daily culture; microorganism suspensions were compared to 0.5 McFarland standards (1.5x10 CFU/ml).
The culture medium was inoculated with the test microbes (0.5 ml) and cultivated 24 h at 35-37 ºC under
aerobic conditions. Candida albicans was cultivated by the same method in the Sabouraud dextrose broth.
1
1

MIC was determined visually by comparison with control. Microorganisms from the test tubes were
inoculated in the meat-peptone agar and fish peptone agar for bacterium and yeast respectively. After 24 h
at 35-37 ºC under aerobic conditions the cultivation CFU was calculated. Purity control of the cultures
was carried out with Gram’s staining of microorganisms and microscopy at each stage.
The biological activity of coordination compound 6 was studied in a heterogenious system due to
extremely low solubility of the compound. 2 mg of powdered complex was added to 10 ml of broth with
inoculum of microorganisms. It was cultivated at 35-37 ºC during 72 h with stirring. Sampling and broth
renewal (9 ml of medium removed and 9 ml new broth with inoculum added) were carried out each 24 h.
Results and discussion
Synthesis of bis(benzo-1,2,3-triazolyl)alkanes
Benzotriazole was alkylated in a superbasic medium by terminal dibromoalkanes containing
from two to eight methylene groups in hydrocarbon linker (Scheme 1). The proposed method of synthesis
does not require highly toxic reagents, catalysts or solvents and special equipment and affords the
products in high yields and can be carried out on a multigram scale.
Scheme 1. Benzotriazole alkylation scheme
As a result of benzotriazole tautomerism [40], mixtures of isomers (1,x-bis(1,2,3-benzotriazol-1-
yl)alkanes (L
benzotriazol-2-yl)alkanes (L
obtained. The yields were 80-92%.
Qualitative analysis of mixtures was carried out using GC-MS technique, while the ratios of
3
-L
8
), 1-(1,2,3-benzotriazol-1-yl)-x-(1,2,3-benzotriazol-2-yl)alkanes (L ’
3
-L ’
8
), 1,x-bis(1,2,3-
’’-L ’’), further referred to as 1,1-, 1,2- and 2,2-isomers respectively) were
3
8
1
13
isomers were determined from H and C NMR. The isomer ratio was determined for L
3
using the
1
– 4.68 t; L ’
’’
characteristic signals of Bta-CH
2
- in the H NMR spectrum (L
3
3
– 4.73 t and 4.80 t; L
3
–
4
.87 t). In spectra of products with longer hydrocarbon linkers, corresponding signals for different
isomers overlap, this is probably because the induction effect of nitrogen atoms does not extend over a
distance exceeding three methylene groups.
In case of the reaction with 1,2-dibromoethane, the desired product was detected only in trace
amounts, since the elimination process proceeds predominantly with the formation of more stable N-
1
2

vinylbenzotriazoles (Scheme 2). Decreasing the reaction temperature to 40 °C did not lead to a noticeable
change in the composition of the products.
Scheme 2. Elimination to form N-vinylbenzo1,2,3-triazole
To optimize the synthesis of L , the temperature and the excess of base were varied (Table S2). It
3
was found that the length of hydrocarbon linker and KOH excess did not have significant effect on the
amount and composition of the products. Reaction temperature of 80 °C was found to be optimal for the
synthesis of L
We investigated the possibility of synthesizing bis(1,2,3-benzotriazol-1-yl)alkanes without a
solvent on the example of L . Although the yield was lower compared to the reaction in DMSO solution
67 %), formation of 1,1-isomer was more favorable and the ratio of 1,1-, 1,2- and 2,2-isomers was found
3
. In all cases, the ratio of 1,1-, 1,2- and 2,2-isomers is close to statistically expected 1:2:1.
3
(
to be 49:42:9. Presence of the base in this reaction was found to be necessary, since in the absence of
KOH after 24 hours of reaction only trace amounts of the product were formed.
Separation of bis(benzo-1,2,3-triazolyl)alkane isomers by selective complex formation
The conventional method of column chromatography requires significant amounts of eluent and
thus is poorly suited for separation of large quantities of products. We explored the possibility of the
separation of isomers by complex formation with copper(II) chloride. Previously, we have studied the
complex formation of bis(benzotriazol-1-yl)methane with copper(II) ions and found that that the complex
formation is a competitive process and the formation of the complexes by benzotriazol-1-yl fragments is
much more favorable [2]. 1,1-Isomer forms the most stable complex with copper(II) ions, the asymmetric
1
,2-isomer is capable of forming a complex, and the 2,2-isomer does not form a complex at all. These
complexes are probably coordination polymers, but their structures could not be determined, since it was
not possible to obtain the single crystals. Selective complex formation and subsequent complex digestion
by an excess of a strong ligand (e.g. DMSO) can be used to enrich the mixture with a certain isomer
before further separation or to isolate individual isomers by two sequential separations. Separations of the
isomers of ligands with a linker length from three to seven methylene groups at various ligand-metal
ratios were carried out. By selecting the optimal ratio, we were able to obtain the 1,1-isomer with a purity
of 95-100 % for various ligands (Table S3).
Synthesis and crystal structures of coordination polymers
Coordination compounds of bis(benzotriazolyl)alkanes were prepared by their reactions with
cadmium(II) or silver(I) nitrates in acetone or acetonitrile. It should be noted that we were able to isolate
1
3

crystalline products only for 1,1-isomers of the ligands in all tested conditions. Depending on the solvent
and metal-to-ligand ratio discrete complexes and coordination polymers were obtained. The crystal
structures and chemical composition of the prepared coordination compounds were established by the
single crystal X-ray crystallography. The powder X-ray diffraction was used to confirm the phase purity
of the compounds (see Supplementary materials), and elemental analysis was carried to confirm their
chemical purity. In addition, the complexes were characterized by IR spectroscopy (see Supplementary
materials) and thermogravimetric analysis (see Supplementary materials). General synthesis routes for all
of the prepared coordination compounds are shown in Scheme 3.
Scheme 3. Synthesis of the complexes with bis(benzotriazol-1-yl)alkanes.
The colorless plate crystals of [Cd(L
and L in acetonitrile upon solvent evaporation. The asymmetric unit of 1 contains a
cadmium(II) cation, the coordination environment of which consists of three N atoms of three L ligands
3
)
2
(NO
3
)
2
∞
] (1) were formed in the reaction mixture of
Cd(NO
3
)
2
3
3
and four O atoms of two nitrate anions coordinated in a bidentate fashion (Fig. S1, a). The Cd–O
distances are in range 2.3716(15)–2.5282(17) Å and the Cd–N distances are in the range 2.2880(17)–
2
.3133(18) Å, typical for cadmium(II) nitrate and cadmium-benzotriazole complexes correspondingly.
One L molecule connects two Cd(II) cations forming a polymeric chain. Another L molecule acts as a
3
3
terminal ligand and connects to Cd(II) cation only by one triazole ring (Fig. 1). The second heterocycle of
the ligand remains uncoordinated and disordered in two positions (Fig. S1, b). The TG curve
demonstrates no weight loss till 280 C, which testifies to the absence of guest molecules (see
Supplementary materials).
1
4

Fig. 1. Fragment of a polymeric chain in the structure 1. Hydrogen atoms are omitted. Only one of the
possible orientations of terminal L ligand is shown.
The colorless plate crystals of [Cd (L (H
mixture of Cd(NO and L in acetone upon solvent evaporation. The compound 2 is a discrete binuclear
complex consisting of two equivalent cadmium(II) cations, each of which coordinates two L molecules,
two nitrate anions and two aqua ligands (Fig. 2). One of NO −
anions is disordered over two orientations
Fig. S2). The Cd–O distances are in range 2.271(2)–2.3569(19) Å, the Cd–N distances are 2.2869(19)
and 2.290(2) Å. The TG curve demonstrates 6% weight loss till 100 C, corresponding to four H
3
2
3
)
2
2
O)
4
(NO
3
)
4
]·2H O (2) were formed in the reaction
2
3
)
2
3
3
3
(
2
O
molecules, and 3% weight loss till 170 C corresponding to the remaining two H O molecules (see
2
Supplementary materials).
Fig. 2. Structure of the complex 2. Hydrogen atoms are omitted. Only one of the possible orientations of
−
NO
3
anion is shown.
When Cd(II):L
3
ratio was less than 3, some amount of hexagonal plates of
O (3) were formed as an impurity to the compound 1 (when the synthesis
[
Cd
2
(L
3
)
2
(H
2
O)
2
(NO
3
4
) ]·2H
2
was carried out in acetone) or to the compound 2 (when acetonitrile was used as a solvent). Compound 3
is a binuclear complex similar to 2 (Fig. 3). The difference is that two of four nitrate anions adopt
1
5

bridging positions between two equivalent cadmium(II) cations, and each cadmium(II) cation coordinates
only one H O molecule. The Cd–O distances are in range 2.243(9)–2.558(3) Å, the Cd–N distances are
.281(3) and 2.305(3) Å. It should be noted that the bridging bidentate coordination mode of nitrate ions
in binuclear cadmium(II) complexes is quite rare and is observed only in four other structures [41–44],
only one of which is a discrete complex [41]. Terminal NO −
anion and aliphatic fragment of L ligand
2
2
3
3
are disordered over two orientations (Fig. S3). Despite of numerical attempts, no pure phase of 3 could be
obtained.
Fig. 3. Structure of the complex 3. Hydrogen atoms are omitted. Only one of the possible orientations of
−
NO
3
anion and aliphatic fragment of L
The colorless plate crystals of [Ag(L
in acetonitrile. The asymmetric unit of 4 contains two silver(I) cations. The coordination
environment of Ag1 is a highly distorted tetrahedron consisting of two N atoms of two L ligands and two
O atoms of two NO −
anions (Fig. S4). Ag1–N distances are 2.2109(18) and 2.2510(18) Å and Ag1–O
distances are 2.4433(18) and 2.5199(17) Å. The coordination number of Ag2 is 4 + 1 and its coordination
environment consists of two N atoms of two L ligands and three O atoms of two nitrate anions, one of
which is coordinated in a bidentate fashion (Fig. S4). The Ag–O distances are 2.5203(19), 2.5743(16) and
.7137(19) Å, the Ag2–N distances are 2.1992(17) and 2.2240(17) Å. Two Ag1 and Ag2 cations are
bridged via two nitrate anions to form binuclear {Ag (L } units. The binuclear units are
interconnected via bridging L ligands with the formation of a metal-organic layer (Fig. 4). The layers
pack along (21−3) plane family.
3
ligand is shown.
4
)(NO )] (4) were formed in the reaction mixture of AgNO
3
∞
3
and L
4
4
3
4
2
2
4
3 2
)4/2(NO )
4
1
6

Fig. 4. Fragment of the polymeric layer in the structure 4 (projection on bc plane). Hydrogen atoms are
omitted.
The colorless plate rhombohedral crystals of [Ag(L
mixture of AgNO and L in acetone. The asymmetric unit of 5 contains of a silver(I) cation in a highly
distorted tetrahedral environment consisting of two N atoms of two L ligands and two O atoms of two
nitrate anions (Fig. S5). The Ag–O distances are 2.3948(14) and 2.5084(13) Å, the Ag–N distances are
.1989(15) and 2.2704(16) Å. Two silver(I) cations are interconnected via two bridging nitrate anions to
form binuclear {Ag (L } building unit (Fig. 5). The binuclear units are connected to each other
via bridging L ligands forming a metal-organic layer (Fig. 6, a). Two layers interweave to form
4
)(NO
3
)]
∞
(5) were formed in the reaction
3
4
4
2
2
4
)4/2(NO
)
3 2
4
supramolecular layers (Fig. 6, b), which alternate along [1−10] direction to form two-layered crystal
packing. The TG curve demonstrates no weight loss up to 230 C (see Supplementary materials), which
testifies to the absence of guest molecules.
Fig. 5. Structure of the binuclear unit in the structure 5. Hydrogen atoms are omitted.
1
7

Fig. 6. Fragment of the metal-organic layer in the structure 5 (projection on ab plane) (a). Interweaving of
metal-organic layers in the structure 5 (b). Hydrogen atoms are omitted.
The colorless square prismatic crystals of [Ag(L
of AgNO and L in acetonitrile. The asymmetric unit of 6 consists of a silver(I) cation in a distorted
triangular environment of two N atoms of two L ligands and one O atom of the nitrate anion (Fig. S6).
6
)(NO
3
∞
)] (6) were formed in the reaction mixture
3
6
6
The Ag–O distance is 2.333(2) Å, the Ag–N distances are 2.266(2) and 2.330(2) Å. The angles between
the atoms in the Ag coordination environment are 100.0, 105.1 and 154.9 emphasizing notable
distortions. There are also two additional weak AgN interactions from each plane of the coordination
triangle between the Ag(I) cation and nitrogen atoms in position 2 of benzotriazole rings. We consider
such interactions to be predominantly ionic since the corresponding interatomic distances (AgN12
=
2
.614 Å and AgN15 = 2.800 Å) are far longer than the normal coordination interaction. In addition, the
deviations of angles between the actual NAg vectors and the directions of imaginary lone electron pairs
on the corresponding nitrogen atoms are too significant (ca. 29 for AgN12 and 38 for AgN15) for the
conventional coordination bonds. Nevertheless, taking into account both coordination and ionic
interactions the coordination environment around the Ag(I) cations could also be described as distorted
triangular bipyramidal with coordination number CN = 3+2. In the crystal structure of 6 the silver cations
are connected with each other via the Ag–N bonds built with the nitrogen atoms in neighboring positions
of the first benzotriazole fragment of the L
6
ligand to form a polymeric chain. The chains are
interconnected via the Ag–N bonds built with the nitrogen atom of the second benzotriazole ring to form
1
8

a metal-organic layer parallel to bc plane (Fig. 7). The layers alternate along [100] direction to form two-
layered crystal packing. The TG curve demonstrates no weight loss till 250 C (see Supplementary
materials), which testifies to the absence of guest molecules.
Fig. 7. Fragment of the polymeric layer in the structure 6 (projection on bc plane). Hydrogen atoms are
omitted. Ag(I) cations are shown with green balls.
When the AgNO
3
:L ratio in acetonitrile solution was more than 2, colorless plate crystals of
6
compound 7 were formed. Compound 7 has a layered structure similar to compound 6 (Fig. 8), and it has
the same chemical composition. The difference is in the coordination mode of a nitrate anion and
orientation of monodentate coordinated benzotriazole fragments of the L ligand. The nitrate anion acts as
6
a bridging ligand connecting two silver cations with one oxygen atom. The Ag–O distances are 2.485(2)
and 2.776(2) Å. Thus, silver(I) cation has distorted trigonal bipyramidal coordination environment, in
which two axial positions are occupied by O atoms of two nitrate anions, and three equatorial positions
are occupied by N atoms of three L
6
ligands (Fig. S7). The Ag–N distances are 2.252(3), 2.344(2), and
2
.596(3) Å. In the structure of 7, metal-organic layers are parallel to ac plane, and they alternate along b
axis. The TG curve demonstrates no weight loss till 230 C (see Supplementary materials), which
testifies to the absence of guest molecules.
1
9

Fig. 8. Fragment of the polymeric layer in the structure 7, projection on the ac plane. Hydrogen atoms are
omitted.
IR spectra of the ligands and coordination compounds
The IR spectra for ligand isomers show the aromatic C-H stretching vibrations in the region of
-
1
-1
3
1
055-3070 cm , the aliphatic C-H stretching vibrations are found in 2961-2866 cm region. Bands of
,2,3-benzotriazole ring stretching vibrations characteristic for 1-substituted derivatives [45] can be found
-
1
near 1616 and 1590 cm in the spectra of compounds L
3
-L
6
and L
substituted triazole rings were detected near 1564 cm in the spectra of compounds L
in-plane ring stretching vibrations of 1-substituted benzotriazole rings were detected near 1496 cm-1 in
the spectra of compounds L -L and L ’-L ’, while these bands are absent in the spectra of 2-substituted
benzotriazole derivatives L ’’-L
3
’-L
6
’. The corresponding bands for 2-
-1
3
’’-L ’’. Bands of
6
3
6
3
6
3
6
’’. Bands of out-of plane ring vibrations and CH deformations [45] were
-
1
-1
detected at about 796 cm for 1-substituted derivatives and near 844 cm for 2-substituted compounds.
The IR spectra of the complexes 1-7 some of the bands associated with benzotriazole vibrations
are shifted towards higher frequencies as a result of the coordination. The IR spectra of the complexes
-1
also feature characteristic bands of nitrate ion vibrations near 1385 and 1285 cm [46].
Luminescent properties of the coordination polymers
The solid-state photoluminescence properties of the phase-pure compounds 1, 2 and 6 were
investigated and compared with those of the ligands L
3
and L (Figs. 9, 10). Typically, aromatic
6
heterocyclic systems with lone electron pairs on the nitrogen atoms feature two emission peaks in the
luminescence spectra, corresponding to the relaxation from * or n* excited states [47,48]. The
excitation spectra of the ligand L
3
(λem = 380 nm) contains one peak at λ = 330 nm obviously related to
the transitions within the  electron system of the benzotriazole moiety. The emission spectra (λex = 330
2
0

nm) reveals a peak at λ = 384 nm as well as weak shoulder at ca. λ = 550 nm, supporting two pathways of
the photoexcited electron relaxation on the * orbital. The main emission peak at shorter wavelengths
should be attributed to the *→ electron transition as a dominating pathway. Simultaneously, the non-
irradiative n→ transfer takes place enabling the alternative photoemission pathway through *→n
electron transition, apparently observed as the weak shoulder at longer wavelengths. The excitation
spectra (λem = 400 nm) of Cd(II) coordination compounds 1 and 2 feature one peak at 329–332 nm, very
similar to that of the ligand L
two components. The blue line (λ = 392 nm for 1 and λ = 398 nm for 2) should be assigned to the
relaxation of the * excited state. The bathochromic shift, compared to the spectra of the ligand L
3
. The emission spectra (λex = 330 nm) of the complexes 1 and 2 also contain
3
,
results from the coordination interaction with cadmium cations. Indeed, the strongest shift is observed for
the compound 2, having only coordinated benzotriazole moieties, while for 1, having both coordinated
and non-coordinated benzotriazolyl groups this shift is less pronounced.
Fig. 9. Solid-state luminescence spectra of compounds 1, 2 and L
A very similar benzotriazole-centered luminescence behavior and relations between the spectra
were observed for the silver coordination polymer 6 and the corresponding ligand L (Fig. 10). The
excitation spectra of the ligand L and compound 6 recorded with em = 400 nm look very similar and
demonstrate one band with the peak maximum at λ = 343 nm (for L ) or λ = 352 nm (for 6). The
excitation of the samples at ex = 350 nm reveals two bands in the emission spectra, corresponding to the
* and the *n electron transitions. The positions of the maxima are 392 and ca. 540 (shoulder) nm
in case of L , 402 and 548 nm in case of 6 for the blue and red components of the spectra, respectively.
Slight bathochromic shift (Δλ = +10 nm) of the blue emission line of 6, compared with the ligand L is
3
.
6
6
6

6
6
explained by the coordination interaction of the benzotriazole groups with silver(I) cations. The existence
of rather strong *→n luminescence in the coordination compound 6 support the absence of the
2
1

coordination interaction between position 2 nitrogen atoms of the benzotriazole ring and Ag(I) cations.
Otherwise, the involvement of the corresponding non-bonding lone electron pair in the donor-acceptor
interactions would eliminate such transition. The excitation spectra of the ligand L
6
and compound 6
as well
recorded with em = 550 nm contain two maxima for each compound:  = 364 and 438 nm for L
6
as  = 355 and 431 nm for 6. The peak at  ≈ 360 nm must be attributed to the higher energy →*
transition while the peak at  ≈ 435 nm should correspond to the excitation of lower energy n→*
electron transition. Consequently, the luminescence spectra of both L
440 nm) reveal only one peak positioned at  = 529 nm for L and  = 525 nm for 6, corresponding to
the *n relaxation. The measured quantum yield for this transition is ca. 3% for both L and 6.
6
and 6, excited at lower energy (ex
=
6
6
Fig. 10. Solid-state luminescence spectra of 6 and L .
6
Antibacterial and antifungal activity
Silver coordination polymers are known to demonstrate bactericidal effects even in heterogeneous
conditions, associated with the migration of silver ions or its molecular complexes into the medium [49–
5
4] The antimicrobial efficiency of L
4
, L
6
and [Ag(L
6
)(NO
3
∞
)] (6) was evaluated in vitro by their
minimal inhibitory concentrations (MIC, μg/ml). The compounds were tested against such opportunistic
microorganisms as Staphylococcus albus, Escherichia coli, Pseudomonas aeruginosa, Klebsiella
pneumonia bacteria and Candida albicans yeast. Individual tested ligands demonstrate weak
bacteriostatic effect, although it is higher than for the unsubstituted benzotriazole (BtaH) (Table 2).
The benzotriazole complex with silver nitrate [Ag(BtaH)NO ] [55] does not inhibit any test
3
culture used probably due to the strong coordination between the ligand and the metal ion. It should be
noted that the coordination polymer 6 demonstrates a species-specific antibacterial effect during at least 3
days, which is probably due to a slow release of silver ions from the polymer layer, indicating its potential
applicability as an additive to polymeric antibacterial films.
2
2

Table 2. Antibacterial activity of compounds tested.
MIC, μg/ml Bactericidal effect, 200 μg/ml
Test culture
L
4
L
6
BtaH
[Ag(BtaH)NO
3
]
Compound 6
1
day
+
–
2 days
3 days
St. albus
E. coli
1024
1024
1024
1024
1024+
1024
1024+
1024+
1024+
–
–
–
+
–
+
+
–
+
Ps.
+
aeruginosa
Kl.
pneumoniae
C. albicans
1024
512
512
n.d.
1024+
1024+
–
–
+
+
+
–
–
–
«1024+» - MIC could not be reached, «+» - bacteria are inhibited totally.
Conclusion
In summary, a convenient method for the preparation and isomer separation of bis(benzotriazolyl)alkanes
was proposed. Three new coordination compounds with cadmium nitrate and four coordination polymers
with silver nitrate were prepared and structurally characterized. In case of cadmium(II) ions solvent-
dependent effect of dimensionality of the coordination compound was observed. In all cases,
bis(benzotriazole-1-yl)alkanes acted as bridging ligands and nitrogen atoms in position 3 of the
heterocycle acted as donor atoms. Both cadmium(II) and silver(I) coordination polymers demonstrated
two-band emission spectra, associated with *→ and *→n transitions. Coordination polymer of silver
nitrate with 1,6-bis(benzo-1,2,3-tirazol-1-yl)hexane demonstrated a stable bactericidal effect even after 72
hours of exposure to culture medium.
Acknowledgements
The research was supported by the Ministry of Science and Higher Education of the Russian Federation.
The authors thank Alena Laricheva for her assistance with biological experiments.
Appendix A. Supplementary data
CCDC 1952607-1952613 contain the supplementary crystallographic data for compounds 1-7. These data
can be obtained free of charge via http://www.ccdc.cam.ac.uk/conts/retrieving.html, or from the
Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: (+44) 1223-
3
36-033; or e-mail: deposit@ccdc.cam.ac.uk.
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Synopsis
New coordination compounds of cadmium(II) and silver(I) with bis(1,2,3-benzotriazol-1-yl)alkanes were prepared
and structurally characterized. 1,3-Bis(benzo-1,2,3-triazol-1-yl)propane formed both discrete complexes and 1D
coordination polymers with cadmium(II) ions. Longer ligands 1,4-bis(benzo-1,2,3-triazol-1-yl)butane and 1,6-
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Author Contributions Section
Roman D. Marchenko: Methodology, Investigation, Writing- Original draft preparation Anna A.
Lysova: Investigation, Writing- Original draft preparation Denis G. Samsonenko: Investigation,
Visualization Danil N. Dybtsev: Methodology, Writing- Reviewing and Editing Andrei S. Potapov:
Conceptualization, Writing- Reviewing and Editing
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