Synthesis and Spectral-Luminescent Properties of 2,5-Diaryl-1,3,4-oxadiazoles and Their Chelate Complexes with Cadmium(II)

Article abstract of DOI:10.1134/S107036321910030X

Cyclization of N′-(arylcarbonyl)benzohydrazides in SOCl₂ has afforded 2-aryl-5-(4-octyloxyphenyl)-1H-1,3,4-oxadiazoles; the spectral-luminescent properties of the properties have been studied. The obtained cadmium complex based on 2-[5-(4-octyl

Full text of DOI:10.1134/S107036321910030X

ISSN 1070-3632, Russian Journal of General Chemistry, 2019, Vol. 89, No. 10, pp. 2165–2169. © Pleiades Publishing, Ltd., 2019.
Russian Text © The Author(s), 2019, published in Zhurnal Obshchei Khimii, 2019, Vol. 89, No. 10, pp. 1634–1640.
LETTERS
TO THE EDITOR
Synthesis and Spectral-Luminescent Properties
of 2,5-Diaryl-1,3,4-oxadiazoles and Their Chelate Complexes
with Cadmium(II)
I. E. Mikhailova, b, Yu. M. Artyushkinaa, G. A. Dushenkoa, and V. I. Minkina
a Institute of Physical and Organic Chemistry of Southern Federal University,
pr. Stachki 194/2, Rostov-on-Don, 344090 Russia
*e-mail: mikhail@ipoc.sfedu.ru
b Federal Research Center “Southern Scientific Center of the Russian Academy of Science”, Rostov-on-Don, Russia
Received June 27, 2019; revised June 27, 2019; accepted July 2, 2019
Abstract—Cyclization of N′-(arylcarbonyl)benzohydrazides in SOCl2 has afforded 2-aryl-5-(4-octyloxyphenyl)-1H-
1,3,4-oxadiazoles; the spectral-luminescent properties of the properties have been studied. The obtained cadmium
complex based on 2-[5-(4-octyloxyphenyl)-1,3,4-oxadiazol-2-yl]phenol (L2Cd) have exhibited strong violet
luminescence.
Keywords: 2,5-diaryl-1,3,4-oxadiazoles, metal complexes, luminescence, organic and metal complex phosphors
DOI: 10.1134/S107036321910030X
The interest to 2,5-diaryl-1,3,4-oxadiazoles and their
derivatives is owing to their diverse biological activity
[1] as well as their unique spectral-luminescent and
photophysical properties [2–4] allowing the preparation of
demanded organic phosphors exhibiting strong emission
in the short-wave part of the visible range and low self-
absorption [5, 6]. The presence of ortho-hydroxyphenyl
substituents in positions 2 or 5 of the 1,3,4-oxadiazole
cycle leads to the formation of the structures with strong
six-membered bidentate N,O-chelating coordination
node. These compounds have been recently used as
fluorescent chemosensors for heavy metals cations [7]
and in the synthesis of luminescent metal complexes
[8–10] applied as highly efficient emission [11–13]
and electron transport [14] materials in organic light-
emitting diodes (OLEDs) and other modern photo- and
electroluminescent devices.
thionyl chloride afforded 2-aryl-5-(4-octyloxyphenyl)-
1Н-1,3,4-oxadiazoles 3a–3c (Scheme 1). The metal
complex 4 soluble in organic media was synthesized
using compound 3b. The chelate complex of cadmium(II)
(L2Cd) 4 was obtained via refluxing of a mixture of
compound 3b (L) and Cd(OCOCH3)2∙2H2O (molar ratio
2 : 1) in methanol (Scheme 1).
Structure of compounds 2–4 was elucidated using the
data of elemental analysis as well as IR, 1Н NMR, and 13С
NMR spectroscopy; spectral-luminescent properties of
oxadiazoles 3a–3c and cadmium complex 4 were studied.
IR spectra of oxadiazoles 3a–3c and the metal
complex 4 contained a group of medium-intensity bands
at 1607‒1628 and 1532–1595 cm–1 assigned to the
stretching of the double bonds of the oxadiazole moiety
(C=N) and the aromatic rings (C=C). The spectrum
of complex 4 revealed the shift of the stretching band
of the C=N bond involved in the complex formation
(1612 cm–1) by 14 cm–1 to lower frequency as compared
to the respective band in the spectrum of compound 3b
(1626 cm–1). Furthermore, the latter spectrum contained
a broad band assigned to the stretching of the phenol
OH group at 3161 cm–1. That band was absent in the IR
To extend the rand of organic and metal complex
phosphors containing the 2,5-diaryl-1,3,4-oxadiazole
moiety and study their spectral-luminescent properties,
we used aroylation of hydrazides 1a–1c with n-octyl-
oxybenzoyl chloride for the preparation of N'-(arylcar-
bonyl)benzohydrazides 2a–2c, cyclization of which in
2165

2166
MIKHAILOV et al.
Scheme 1.
R
O
NHNH2
1a 1c
ꢀ
NEt3
H
H
C8 17OC6 4COCl
R
O
O
R
N
O
N
H
OC8
17
NHNH
SOCl2
H
OC8
17
3a 3c
ꢀ
2a 2c
ꢀ
R = OH
Cd/2
N
O
N
Cd(OCOCH
O
)
3 2
H
OC8
17
4
R = H (a), OH (b), OMe (c).
spectra of compounds 3a, 3c, and 4 since oxadiazoles
3a, 3c did not contain the hydroxyl group, and its proton
was substituted with the metal ion in complex 4. The
structure of complex 4 was confirmed by the 1Н and 13С
NMR spectra which contained the complete sets of the
expected signals at their usual positions. Let us note the
absence of the phenol OH signal in the proton spectrum
of compound 4 (that signal was observed at 10.17 ppm in
the spectrum of compound 3b). Furthermore, the complex
formation induced the downfield shift of the signals of
the oxyphenyl fragment in the 1Н and 13С NMR spectra
of complex 4 in comparison with those of oxadiazole 3b.
short-living phototautomer formed via intramolecular
proton transfer in the excited state from the phenolic OH
group to the nearest nitrogen atom of oxadiazole [6, 15].
Low overall quantum yield of luminescence of oxadiazole
3b in those solvents (φ = 0.003‒0.007) was due to the
radiationless deactivation of the excited state via the
ESIPT mechanism (Excited-State Intramolecular Proton
Transfer). However, the spectrum of oxadiazole 3b in a
polar solvent (DMSO) contained a single strong short-
wave band (λflmax = 366 nm, φ = 0.32) with normal Stokes
shift (2618 cm–1) assigned to the initial benzoid structure
3b according to the excitation spectra. The formation
of a strong intermolecular hydrogen bond between the
phenolic OH group of oxadiazole 3b and a polar aprotic
molecule (DMSO) inhibited the intramolecular proton
transfer. Oxadiazoles 3a, 3c which did not contain the
mobile phenolic OH proton exhibited high quantum yield
of fluorescence (λflmax = 352–377 nm, φ = 0.73‒0.92) with
normal Stokes shift (2694‒5347 cm–1).Asimilar spectral
behavior has been observed earlier for structurally
analogous 1,3,4-oxadiazoles [3, 4, 16, 17].
The electronic absorption spectra of oxadiazoles
3a–3c showed the maximums of the long-wave band
(assigned to the π→π*-transitions) at 318‒335 nm,
evidencing the benzoid structure of the compounds. The
emission spectra of oxadiazole 3b in isooctane, dioxane,
and acetonitrile contained two weak bands: the short-
wave one (λflmax = 358–378 nm, φ = 0.001‒0.004) with
normal Stokes shift (2098‒3665 cm–1) and a long-wave
(λflmax = 469–483 nm, φ = 0.001‒0.005) with unusually
high Stokes shift (8529‒9416 cm–1). The short-wave band
in the excitation spectra was assigned to the initial benzoid
structure 3b, and the long-wave one corresponded to the
Even though cadmium complex 4 in acetonitrile
and DMSO revealed absorption at longer wavelengths
(λmax = 372, 373 nm) in comparison with oxadiazoles
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SYNTHESIS AND SPECTRAL-LUMINESCENT PROPERTIES
2167
3a–3c, the presence of a band due to the charge transfer
between the ligand and the metal led to the appearance
of its single emission band between those of the benzoid
structure and the phototautomer (CH3CN, λflmax = 432 nm;
spectrum (DMSO-d6), δ, ppm: 0.89 t (3H, CH3, Oct, J =
7.2 Hz), 1.24‒1.55 m (10H, CH2, Oct), 1.66‒1.85 m (2H,
CH2, Oct), 4.07 t (2H, OCH2, Oct, J = 6.6 Hz), 6.93‒7.19
m (4HAr), 7.49 d. d (1HAr, J1 = 7.0, J2 = 7.1 Hz), 7.89‒8.0
m (3HAr), 10.53 s (1H, OH), 10.66 s (1H, NH), 12.01
s (1Н, NH). 13C NMR spectrum (DMSO-d6), δC, ppm:
14.41 (CH3, Oct), 22.54 (CH2, Oct), 25.94 (CH2, Oct),
29.03 (CH2, Oct), 29.12 (CH2, Oct), 29.18 (CH2, Oct),
31.69 (CH2, Oct), 68.22 (OCH2, Oct), 114.65 (2СAr),
115.04 (CiAr), 117.86 (СAr), 119.49 (СAr), 124.72 (CiAr),
128.72 (СAr), 129.89 (2СAr), 134.60 (СAr), 159.81 (CiAr),
162.06 (CiAr), 165.55 (C=O), 168.30 (C=O). Found, %:
С 68.77; Н 7.31; N 7.34. С22H28N2O4. Calculated, %: С
68.73; Н 7.34; N 7.29.
DMSO, λfl
= 443 nm). Rigid configuration of the
max
cadmium complex 4 prevented radiationless deactivation
of its excited state, and therefore it exhibited strong (φ =
0.28, 0.35) violet luminescence. Hence, complex 4 could
be regarded as efficient metal complex phosphor, and the
oxadiazole ligand 3b could act as a chemosensor with
respect to toxic cadmium cations.
4-Octyloxy-N'-(phenylcarbonyl)benzohydrazide
(2a). 2 mL of triethylamine and then a solution of 1.34 g
(0.005 mol) of 4-octyloxybenzoyl chloride in 20 mL of
anhydrous benzene were added at stirring to a solution
of 0.68 g (0.005 mol) of benzohydrazide 1a in 50 mL
of anhydrous benzene. The reaction mixture was stirred
during 2 h at room temperature and then refluxed during
6 h. The solvent was removed in vacuum, and 50 g of
crushed ice was added to the oily residue. The formed
precipitate was filtered off, washed with water (2×
10 mL), dried in air, and recrystallized from isopropanol
(2×20 mL). Yield 1.53 g (83%), colorless crystals, mp
125‒127°С. IR spectrum, ν, cm–1: 3201 (N‒H), 1663,
1622 (C=O, amide), 1602, 1599 (C=C); 1572 (N‒H),
1509, 1445, 1368; 1314, 1272 [νs(Ar‒O‒C)]; 1119,
1103 (С‒O‒C); 1043, 975; 844, 809 [δ(CArH)]; 745, 736
2-Methoxy-N'-[(4-octyloxyphenyl)carbonyl]
benzohydrazide (2c) was prepared similarly from
o-methoxybenzoic acid hydrazide 1c. Yield 1.67 g
(84%), colorless crystals, mp 103‒104°С. IR spectrum,
ν, cm–1: 3258, 3196 (N‒H); 1668, 1633 ν(C=O, amide);
1608, 1577 (C=C); 1555 [δ(NH)]; 1505, 1480, 1470,
1326; 1307, 1294, 1248 [νs(Ar‒O‒C)]; 1178, 1116
[νas(Ar‒O‒C)]; 1106, 1070, 1045, 1026, 969, 910; 878,
842 [δ(CArH)]; 800, 788;751 [δ(CH)]. 1Н NMR spectrum
(DMSO-d6), δ, ppm: 0.90 t (3H, CH3, Oct, J = 7.2 Hz),
1.27‒1.58 m (10H, CH2, Oct), 1.67‒1.85 m (2H, CH2,
Oct), 3.88 s (3H, OCH3), 4.06 t (2H, OCH2, Oct, J = 6.7
Hz), 6.94‒7.20 m (4HAr), 7.50 d. d (1HAr, J1 = 6.9, J2 =
7.0 Hz), 7.75 d. d (1HAr, J1 = 0.9, J2 = 6.7 Hz), 7.94 d
(2HAr, J = 8.4 Hz), 10.81 s (1H, NH), 11.93 s (1Н, NH).
13C NMR spectrum (DMSO-d6), δC, ppm: 14.42 (CH3,
Oct), 22.53 (CH2, Oct), 25.95 (CH2, Oct), 29.01 (CH2,
Oct), 29.14 (CH2, Oct), 29.17 (CH2, Oct), 31.68 (CH2,
Oct), 56.37 (OCH3), 68.23 (OCH2, Oct), 112.58 (CAr),
114.67 (2СAr), 121.01 (СAr), 122.19 (CiAr), 129.85 (2CAr),
130.96 (CAr), 133.19 (CAr), 134.62 (CiAr.), 157.59 (CiAr),
162.07 (CiAr), 165.23 (C=O), 168.28 (C=O). Found, %:
С 69.37; Н 7.62; N 7.02. С23H30N2O4. Calculated, %: С
69.32; Н 7.59; N 7.03.
1
[δ(CH)]. Н NMR spectrum (DMSO-d6), δ, ppm: 0.87
t (3H, CH3, Oct, J = 7.2 Hz), 1.26–1.58 m (10H, CH2,
Oct), 1.64–1.83 m (2H, CH2, Oct), 4.11 t (2H, OCH2,
Oct, J = 6.6 Hz), 7.07 d (2HAr, J = 8.4 Hz), 7.40‒7.56 m
(3HAr), 7.79‒7.86 m (2HAr), 7.93 d (2HAr, J = 8.4 Hz),
9.45 s (1H, NH), 10.78 s (1Н, NH). 13C NMR spectrum
(DMSO-d6), δC, ppm: 14.43 (CH3, Oct), 22.57 (CH2,
Oct), 25.93 (CH2, Oct), 29.06 (CH2, Oct), 29.17 (CH2,
Oct), 29.19 (CH2, Oct), 31.70 (CH2, Oct), 68.25 (OCH2,
Oct), 114.37 (2СAr), 125.74 (CiAr), 126.85 (2СAr), 129.12
(2СAr), 129.19 (2СAr), 131.54 (СAr), 158.45 (CiAr), 161.36
(CiAr), 166.13 (C=O), 168.37 (C=O). Found, %: С 71.74;
Н 7.69; N 7.56. С22H28N2O3. Calculated, %: С 71.71; Н
7.66; N 7.60.
2-(4-octyloxyphenyl)-5-phenyl-1,3,4-oxadiazole
(3a). Asolution of 1.47 g (0.004 mol) of benzohydrazide
2a in 20 mL of thionyl chloride was refluxed during 5 h.
Thionyl chloride was distilled off, the reaction mass was
cooled down to ambient, and 50 g of crushed ice was
added. The precipitate was filtered off and purified by
column chromatography on silica gel (0.063‒0.200 mm,
eluent: ethyl acetate‒petroleum ether, 1 : 10) collecting
the fraction with Rf 0.70‒0.75. The solvent was distilled
off, and the residue was recrystallized from isopropanol.
Yield 0.99 g (71%), colorless crystals, mp 79‒81°С.
2-Hydroxy-N'-[(4-octyloxyphenyl)carbonyl]
benzohydrazide (2b) was prepared similarly from
salicylic acid hydrazide 1b. Yield 1.56 g (81%), colorless
crystals, mp 125‒127°С. IR spectrum, ν, cm–1: 3315
(O‒H), 3224 (N‒H), 1665, 1626 (C=O, amide); 1609,
1595(C=C); 1544 [δ(NH)]; 1502, 1488, 1456; 1303, 1258
[νs(Ar‒O‒C)]; 1181, 1155, 1132 [νas(Ar‒O‒C)]; 1065,
1
1025, 997, 972; 838 [δ(CArH)]; 748 [δ(CH)]. Н NMR
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MIKHAILOV et al.
IR spectrum, ν, cm–1: 1615, 1607 (C=N); 1583, 1549
(C=C); 1530, 1507; 1443 (N‒N); 1424, 1371, 1305;
1261, 1245 [νs(Ar‒O‒C)]; 1118, 1071 [νas(Ar‒O‒C)];
988, 882; 851 [δ(CArH)]; 792, 773; 743 [δ(CH)]. UV
spectrum, λmax, nm (ε×10–4, Lmol–1 cm–1, λex = 315 nm):
isooctane, 242 (0.28), 284 sh (1.50), 295 (1.71), 306 sh
(1.41), 320 sh (0.57), λflmax(φ) 352 (0.81); acetonitrile,
244 (0.80), 282 sh (2.44), 294 (2.73), 306 sh (2.17), 318
sh (0.94), λflmax(φ) 369 (0.92); DMSO, 299 (1.61), 311
(CiAr), 117.11 (СAr), 119.75 (СAr), 126.31 (СAr), 128.64
(2СAr), 133.27 (СAr), 157.41 (CiAr), 162.23 (CiAr), 163.12
(CHt), 163.55 (CHt). Found, %: С 72.16; Н 7.14; N 7.68.
С22H26N2O3. Calculated, %: С 72.11; Н 7.15; N 7.64.
2-(2-Methoxyphenyl)-5-(4-octyloxyphenyl)-1,3,4-
oxadiazole (3c). Yield 1.20 g (78%), colorless crystals,
mp 59‒60°С. IR spectrum, ν, cm–1: 1628, 1612 (C=N);
1595, 1557 (C=C); 1501, 1489; 1447 (N‒N); 1422,
1327, 1298, 1273; 1248, 1231 [νs(Ar‒O‒C)]; 1173, 1168
[νas(Ar‒O‒C)]; 1075, 1016, 923; 860, 831 [δ(CArH)]; 758
[δ(CH)]. UV spectrum, λmax, nm (ε×10–4, L mol–1 cm–1,
λex = 325 nm): dioxane, 291 (3.11), 306 (2.74), 316 sh
(2.33), 330 sh (1.03), λflmax(φ) 366 (0.88); acetonitrile,
239 (0.88), 244 (0.98), 278 sh (2.47), 289 (2.57), 308
(2.22), 329 (0.87), λflmax(φ) 361 (0.85); DMSO, 284 sh
(3.42), 292 (3.48), 320 sh (2.55), 333 (1.21), λflmax(φ) 367
(0.92). 1Н NMR spectrum (CDCl3), δ, ppm: 0.96 t (3H,
CH3, Oct, J = 7.2 Hz), 1.12‒1.63 m (10H, CH2, Oct),
1.76‒1.98 m (2H, CH2, Oct), 3.90‒4.25 m (5H, OCH3,
OCH2, Oct), 6.90‒7.25 m (3HAr), 7.33 d. d (1HAr, J1 =
1.1, J2 = 7.0 Hz), 7.58 d. d (1HAr, J1 = 7.0, J2 = 7.1 Hz),
7.98‒8.26 (3HAr). 13C NMR spectrum (CDCl3), δC,
ppm: 14.11 (CH3, Oct), 22.67 (CH2, Oct), 25.94 (CH2,
Oct), 29.14 (CH2, Oct), 29.25 (CH2, Oct), 29.36 (CH2,
Oct), 31.83 (CH2, Oct), 56.37 (OCH3), 68.28 (OCH2,
Oct), 108.22 (CiAr), 114.97 (2СAr), 115.27 (CiAr), 117.11
(СAr), 119.75 (СAr), 126.31 (СAr), 128.64 (2СAr), 133.27
(СAr), 157.41 (CiAr), 162.23 (CiAr), 163.12 (CHt), 163.55
(CHt). Found, %: С 72.63; Н 7.40; N 7.39. С23H28N2O3.
Calculated, %: С 72.60; Н 7.42; N 7.36.
1
sh (1.38), 324 sh (0.63), λflmax(φ) 377 (0.73). Н NMR
spectrum (CDCl3), δ, ppm: 0.93 t (3H, CH3, Oct, J = 7.2
Hz), 1.20‒1.58 m (10H, CH2, Oct), 1.73‒1.91 m (2H,
CH2, Oct), 4.04 t (2H, OCH2, Oct, J = 6.6 Hz), 7.03 d
(2HAr, J = 8.4 Hz), 7.50‒7.58 m (3HAr), 8.07 d (2HAr, J =
8.4 Hz), 8.10‒8.19 m (2HAr). 13C NMR spectrum (CDCl3),
δC, ppm: 14.11 (CH3, Oct), 22.66 (CH2, Oct), 26.01 (CH2,
Oct), 29.14 (CH2, Oct), 29.24 (CH2, Oct), 29.35 (CH2,
Oct), 31.81 (CH2, Oct), 68.27 (OCH2, Oct), 114.96 (2СAr),
116.12 (CiAr), 124.11 (CiAr), 126.79 (2СAr), 128.64 (2СAr),
129.01 (2СAr),131.48 (СAr), 161.98 (CiAr), 164.05 (CHt),
164.58 (CHt). Found, %: С 75.42; Н 7.45; N 8.03.
С22H26N2O2. Calculated, %: С 75.40; H 7.48; N 7.99.
2-[5-(4-Octyloxyphenyl)-1,3,4-oxadiazol-2-yl]-
phenol (3b). Yield 1.24 g (85%), colorless crystals, mp
77‒79°С. IR spectrum, ν, cm–1: 3161 (O‒H); 1626, 1614
(C=N); 1593, 1544 (C=C); 1498, 1486; 1455 (N‒N);
1426, 1397, 1377; 1302 [νs(C‒Ophenol)]; 1257, 1238
[νs(Ar‒O‒C)]; 1181, 1172, 1130 [νas(Ar‒O‒C)]; 1090,
1066 [νas(C‒Ophenol)]; 1034, 999, 972; 836 [δ(CArH)]; 751
[δ(CH)]. UV spectrum, λmax, nm (ε×10–4, L mol–1 cm–1,
λex = 325 nm): isooctane, 239 (1.09), 246 (1.19), 279
(3.38), 292 (3.96), 308 sh (3.23), 319 (4.23), 333 (3.35),
λflmax(φ) 358 (0.001), 482 (0.002); dioxane, 292 (3.29),
308 (3.10), 319 (3.82), 332 sh (2.82), λflmax(φ) 378
(0.002), 483 (0.005); acetonitrile, 247 (1.04), 282 sh
(2.56), 291 (2.88), 317 (3.29), 335 sh (2.94), λflmax(φ)
361 (0.004), 469 (0.001); DMSO, 293 (2.83), 312 (2.60),
Bis{2-[5-(4-octyloxyphenyl)-1,3,4-oxadiazol-2-yl]-
phenolato}cadmium(II) (4). 0.27 g (0.001 mol) of
cadmium acetate dihydrate in 5 mL of methanol was
added at stirring and room temperature to a solution of
0.73 g (0.002 mol) of oxadiazole 3b in 15 mLof methanol.
The mixture was refluxed during 5 h and then cooled
down to ambient. The precipitate was filtered off, washed
with methanol (2×30 mL), dried in air, and recrystallized
from methanol (300 mL). Yield 0.53 g (63%), colorless
crystals, mp 285‒287°C. IR spectrum, ν, cm–1: 1612
(C=N); 1553, 1532 (C=C); 1504, 1480; 1435 (N‒N);
1342; 1303 [νs(C‒Ophenol)]; 1258 [νs(Ar‒O‒C)]; 1102,
1126, 1176 [νas(Ar‒O‒C)]; 1065, 1025, 998, 970, 906;
837 [δ(CArH)]; 750 [δ(CH)]. UV spectrum, λmax, nm
(ε×10–4, L mol–1 cm–1, λex = 370 nm): acetonitrile, 280
sh (2.75), 292 (3.02), 304 (2.51), 319 (2.29), 331 (1.81),
372 (0.88), λflmax(φ) 432 (0.28); DMSO, 293 (2.46), 305
(2.19), 322 (1.45), 335 (1.15), 373 (1.34), λflmax(φ) 443
1
334 sh (1.63), λflmax(φ) 366 (0.32). Н NMR spectrum
(CDCl3), δ, ppm: 0.87 t (3H, CH3, Oct, J = 7.2 Hz),
1.23‒1.50 m (10H, CH2, Oct), 1.70‒1.83 m (2H, CH2,
Oct), 3.95 t (2H, OCH2, Oct, J = 6.6 Hz), 6.92‒7.00 m
(3HAr), 7.06 d. d (1HAr, J1 = 1.1, J2 = 6.7 Hz), 7.37 d. d
(1HAr, J1 = 6.7, J2 = 6.9 Hz), 7.74 d. d (1HAr, J1 = 1.0, J2 =
7.1 Hz), 7.96 d (2HAr, J = 8.4 Hz), 10.17 s (1H, OH).
13C NMR spectrum (CDCl3), δC, ppm: 14.11 (CH3, Oct),
22.67 (CH2, Oct), 25.94 (CH2, Oct), 29.14 (CH2, Oct),
29.25 (CH2, Oct), 29.36 (CH2, Oct), 31.83 (CH2, Oct),
68.28 (OCH2, Oct), 108.22 (CiAr), 114.97 (2СAr), 115.27
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SYNTHESIS AND SPECTRAL-LUMINESCENT PROPERTIES
2169
(0.35). 1Н NMR spectrum (DMSO-d6, 90°C) δ, ppm: 0.88
t (3H, CH3, Oct, J = 7.2 Hz), 1.25‒1.37 m (8H, CH2, Oct),
1.41‒1.47 m (2H, CH2, Oct), 1.72‒1.79 m (2H, CH2, Oct),
4.09 t (2H, OCH2, Oct, J = 6.6 Hz), 6.47 d. d (1HAr, J1 =
7.4, J2 = 7.5 Hz), 6.71 d. d (1HAr, J1 = 1.2, J2 = 7.6 Hz),
7.11 d (2HAr, J = 8.4 Hz), 7.19 d. d (1HAr, J1 = 7.4, J2 =
7.6 Hz), 7.73 d. d (1HAr, J1 = 1.1, J2 = 7.5 Hz), 7.96 d
(2HAr, J = 8.4 Hz). 13C NMR spectrum (DMSO-d6), δC,
ppm: 13.18 (CH3, Oct), 21.41 (CH2, Oct), 24.90 (CH2,
Oct), 27.98 (CH2, Oct), 28.08 (CH2, Oct), 28.11 (CH2,
Oct), 30.62 (CH2, Oct), 67.72 (OCH2, Oct), 107.36
(CiAr), 115.03 (2СAr), 115.50 (CiAr), 127.73 (СAr), 127.91
(2СAr), 132.76 (СAr), 160.49 (CiAr), 161.15 (CAr), 161.25
(CAr), 163.12 (CiAr), 165.48 (CHt), 176.96 (CHt). Found,
%: С 62.38; Н 6.11, N 6.70; Cd 13.07. С44H50CdN4O6.
Calculated, %: С 62.67; Н 5.98; N 6.64; Cd 13.33.
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IR spectra (Vaseline oil, thin film) were recorded
using a Varian Excalibur 3100 FT-IR spectrometer. Н
1
[250 (2, 3), 600 MHz (4)] and 13С [63 (2, 3), 151 MHz
(4)] NMR spectra were recorded using Bruker DPX-250
and Bruker Avance-600 instruments. Absorption and
fluorescence spectra were recorded using a Cary Scan 100
spectrophotometer and Cary Eclipse spectrofluorimeter,
respectively. Quantum yields of fluorescence were
determined using a solution of anthracene in acetonitrile
as reference [12].
FUNDING
This study was financially supported by the Ministry of
Education and Science of Russian Federation in the scope of
the State Task (project no. 4.979.2017/4.6).
CONFLICT OF INTEREST
No conflict of interest was declared by the authors.
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