172
BELDOVSKAYA et al.
mechanism [5]. Unlike oxadiazole II, the beryllium
complex III luminescence was fairly intense (Φ =
0.13–0.28). Emission spectrum of III contained the
only band (toluene, λfl 411 nm; CH3CN, λfl 409 nm) in
between the spectral ranges typical of benzenoid and
quinoid structures. In the case of DMSO solution spec-
trum, bathochromic shift was observed (λfl 454 nm) as
compared with the quinoid form.
(0.001 mol) of KOH in 2 mL of water was added to
boiling suspension of 0.36 g (0.001 mol) of oxadiazole
II in 15 mL of methanol. The mixture was refluxed
during 30 min. Then, solution of 0.17 g (0.0005 mol)
of BeSO4·4H2O in 1.5 mL water was added, and the
mixture was further refluxed during 7 h. The formed
precipitate was filtered off, washed subsequently with
methanol (10 mL) and with water (15 mL), dried in
vacuum, and recrystallized from toluene (50 mL).
Yield 0.41 g (56%), colorless crystals, mp 246–248°С.
IR spectrum, ν, cm–1: 1503, 1536, 1564, 1589, 1614
To conclude, we obtained new oxadiazole ligand
system and converted it into the organosoluble metal
complex luminophor, which can be used to produce
various photo- and electroluminescence devices.
1
(С=С, C=N). Н NMR spectrum (CDCl3), δН, ppm:
3
0.84 t (6Н, CH3, JHH 7.3 Hz), 1.18–1.27 m (24Н,
3
2-Hydroxy-N'-(4'-nonylbenzoyl)benzohydrazide (I).
Solution of 2.7 g (0.01 mol) of 4-nonylbenzoic acid in
20 mL of toluene and 20 mL of saturated Na2CO3
aqueous solution were subsequently added within
10 min to suspension of 1.52 g (0.01 mol) of salicylic
acid hydrazide in 15 mL of water upon stirring; pH
was maintained at about 8. The reaction mixture was
the stirred during 4 h and incubated overnight. The
formed precipitate was filtered off, washed with water
(2×20 mL), dried in vacuum and recrystallized from
ethanol. Yield 3.3 g (85%), colorless crystals, mp 163–
165°С. IR spectrum, ν, cm–1: 1546, 1607, 1628, 1656
(С=С, C=N), 3042 (NН), 3313 (ОН). 1Н NMR
СН2), 1.59 q (4Н, СН2, JHH 7.3 Hz), 2.62 t (4Н, СН2,
3JHH 7.5 Hz), 6.80–7.92 m (16Н, НAr). Found, %: С
75.50; Н 6.80; N 8.00; Be 1.60. С46H54BeN4O4.
Calculated, %: С 75.11; Н 7.34; N 7.61; Be 1.22.
IR spectra of thin films were registered with Varian
1
Excalibur 3100 FT-IR spectrometer. H NMR spectra
(250.13 MHz) were recorded with Bruker DPX-250
spectrometer. Absorption and fluorescence spectra
were registered with Cary Scan 100 spectrophotometer
and Cary Eclipse spectrofluorimeter, respectively.
Fluorescence quantum yields were determined relative
to acetonitrile solution of anthracene [5, 6].
3
spectrum (DMSO-d6), δН, ppm: 0.92 t (3Н, СН3, JHH
ACKNOWLEDGMENTS
7.3 Hz), 1.21–1.44 m (12Н, СН2), 1.69 q (2Н, СН2,
3JHH 7.3 Hz), 2.68 t (2Н, СН2, 3JHH 7.5 Hz), 6.92–8.01
m (8Н, НAr), 10.50 s (1Н, NH), 10.68 s (1Н, NH),
12.02 s (1Н, ОН). Found, %: С 72.60; Н 7.40; N 7.60.
С23H30N2O3. Calculated, %: С 72.27; Н 7.85; N 7.33.
This work was financially supported by Russian
Foundation for Basic Research (grant no. 11-03-
00145a, 12-03-00179a), the Program of Department of
Chemistry and Materials Science, Russian Academy of
Sciences (OKh-1), and by President of Russian
Federation (NSh-927.2012.3).
2-[5-(4'-Nonylphenyl)-1,3,4-oxadiazol-2-yl]phenol
(II). 7.2 mL of thionyl chloride was added to 3.83 g of
hydrazide I (0.01 mol). The mixture was refluxed
during 4 h, cooled to room temperature, poured into
100 g of crushed ice, and incubated overnight. The
formed precipitate was filtered off, washed with water
(3×30 mL), dried in vacuum, and twice recrystallized
from propan-2-ol (10 mL). Yield 2.44 g (67%),
colorless crystals, mp 75–77°С. IR spectrum, ν, cm–1:
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3
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RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 84 No. 1 2014