Chemistry - A European Journal
10.1002/chem.201703324
FULL PAPER
+
[
29] were synthesized according to reported procedures with minor
HRMS (ESI): m/z calcd. for C56H63N4 [MH ] 1031.7803; found 1031.7817
modifications; 2-bromo-4-(2,2-dimethylpropyloxy)pyridine, 2-bromo-4-
decyloxypyridine, 2-bromo-4-pentylpyridine were synthesized in
innovative way. All compounds were characterized by H and C NMR
spectroscopic analysis (see the Supporting Information for details).
P5 (81 mg, 57%) as yellow solid
H NMR (400 MHz, DMSO) δ 8.95 (s, 4H), 8.93 (s, 4H), 8.62 (s, 2H),
1
13
1
7.45 (dd, J = 18.9, 7.3 Hz, 16H), 7.38 (d, J = 6.8 Hz, 4H), 5.78 (s, 8H).
1
3
C NMR (101 MHz, DMSO) δ 146.01, 136.06, 128.94, 128.32, 128.12,
Suzuki-Miyaura Cross-Coupling for the synthesis of 1,3,6,8-
tetrakis(4-substituted-2-pyridyl)pyrenes P1–P3. General Procedure:
In 100 mL round-bottom flask, 1,3,6,8-tetrakis(4,4,5,5-tetramethyl-1,3,2-
dioxaborolan-2-yl)pyrene (1.32 g, 1.87 mmol), 2-bromo-4-substituted-
pyridine (8.30 mmol), potassium phosphate trihydrate (6.33 g, 23.76
mmol), [Pd(PPh3)4] (0.350 g, 0.30 mmol) and 12 mL of DME/water
mixture (3:1 v/v) were placed. The mixture was saturated with argon,
heated to 105 ⁰C and stirred for 48 h. After cooling to room temperature,
the mixture was extracted with chloroform (3 x 50 mL) and water (3 x
127.51, 125.80, 125.73, 125.43, 125.20, 53.26.
HRMS (ESI): m/z calcd. for C52H38N12Na [M+Na] 853.3240; found
853.3235
Measurements: NMR spectra were recorded in CDCl3 with Bruker
1
13
Advance 400 MHz instruments (for H and C NMR). High-resolution
mass spectrometry (HRMS) analysis was performed with a Waters
Synapt G2-S HDMS Q-TOF mass spectrometer (Waters Corporation)
equipped with an ESI source operating in positive-ion modes. Full-scan
MS data were collected from 100 to 1000 Da in positive ion mode with a
scan time of 0.1 s. To ensure accurate mass measurements, data were
collected in centroid mode and mass was corrected during acquisition
using leucine enkephalin solution as an external reference (Lock-
SprayTM), which generated reference ion at m/z 556.2771 Da ([M + H]+)
in positive ESI mode. The accurate mass and composition for the
molecular ion adducts were calculated by using the MassLynx software
(Waters) incorporated with the instrument.
5
0 mL). The combined organic layers were dried and the solvent was
evaporated. The crude product was purified by column chromatography
silica gel; CH2Cl2:ethyl acetate (2:1)).
(
1,3-Dipolar cycloaddition for the synthesis of 1,3,6,8-tetrakis(1-
substituted-1,2,3-triazol-4-yl)pyrenes P4–P5. General Procedure: In
a 50 mL round-bottom flask, 1,3,6,8-tetrakis((trimethylsilyl)ethynyl)pyrene
(0.10 g, 0.17 mmol), substituted azide (0.82 mmol), tert-butyl alcohol (7
mL) and water (7 mL) were placed. The mixture was saturated with argon
and then KF (0.048 g, 0.82 mmol), CuSO4⸱5H2O (0.205 g, 0.82 mmol),
sodium ascorbate (0.162 g, 0.82 mmol) and pyridine (0.5 mL) were
added. The mixture was stirred at room temperature for 48 h. Then,
CH2Cl2 (20 mL) and 5% solution of ammonia (15 mL) were added and
the mixture was stirred for 30 min. The mixture was extracted with water
Spectroscopic Measurements: UV−Vis spectra were recorded using
Evolution 300 ThermoFisherScientific spectrophotometer at room
temperature in denoted solvents with a conventional 1.0 cm quartz cell.
Photoluminescence spectra (PL) in solutions were measured using
Varian Carry Eclipse Spectrometer. Quantum yields (Φf) measurements
were estimated using the integrating sphere Avantes AvaSphere-80 with
FLS-980 Spectrophotometer (Edinburgh Instruments). Quantum yields
were determined by an absolute method using the excitation wavelength
with the most intense luminescence.
(50 mL) and CH2Cl2 (2 x 50 mL). The combined organic layers were dried
with anhydrous MgSO4 and the volatile fractions were evaporated. The
crude product was purified by column chromatography (silica gel; CH2Cl2,
ethyl acetate).
P1 (994 mg, 62%) as yellow solid
H NMR (400 MHz, CDCl3) δ 8.63 (d, J = 5.4 Hz, 4H), 8.43 (s, 4H), 8.32
Film and blend on glass preparation: Films and blends in poly(N-
vinylcarbazole) (PVK) and poly(N-vinylcarbazole):2-(4-biphenylyl)-5-(4-
tert-butylphenyl)-1,3,4-oxadiazole (PVK:PBD) (50:50 in weight %) on
glass substrate were prepared by spin-coating (1000 rpm, 60 s) from
homogenous chloroform solution (10 mg/mL) and dried 24 h in a vacuum
oven at 60 ºC.
1
(
s, 2H), 7.30 (s, 4H), 6.91 (d, J = 3.6 Hz, 4H), 3.73 (s, 8H), 1.06 (s, 36H).
C NMR (101 MHz, CDCl3) δ 165.94, 160.96, 150.78, 136.12, 129.22,
1
3
128.91, 126.02, 125.95, 112.37, 109.23, 77.98, 31.97, 26.65.
+
HRMS (ESI): m/z calcd. for C56H63N4O4 [MH ] 855.4849; found 855.4835
OLED preparation and EL measurements: Devices with following
configuration ITO/PEDOT:PSS/PVK:PBD:compound/Al with 1 and 2 wt.
% complex content in the blend were prepared. Devices were prepared
on OSSILA substrates with pixilated ITO anodes, cleaned with detergent,
deionized water, 10% NaOH solution, water, and isopropanol in an
ultrasonic bath. Substrates were covered with PEDOT:PSS film by spin-
coating at 5000 rpm for 60 s and annealed for 15 min at 120 °C. Active
layer was spin-coated on top of the PEDOT:PSS layer from CHCl3
solution (10 mg/mL) at 1000 rpm for 60 s and annealed for 5 min at 100
°C. Finally, Al was vacuum-deposited. Electroluminescence (EL) spectra
were measured with the voltage applied using a precise voltage supply
(Gw Instek PSP-405) and the sample was fixed to an XYZ stage. Light
from the OLED device was collected through a 30 mm lens, focused on
the entrance slit (50 μm) of a monochromator (Shamrock SR-303i) and
detected using a CCD detector (Andor iDus 12305). Typical acquisition
times were equal to 10 seconds. The pre-alignment of the setup was
done using a 405 nm laser.
P2 (510 mg, 24%) as dark yellow oil
H NMR (400 MHz, CDCl3) δ 8.61 (d, J = 5.7 Hz, 4H), 8.43 (s, 4H), 8.33
1
(s, 2H), 7.28 (d, J = 1.8 Hz, 4H), 6.86 (dd, J = 5.6, 2.1 Hz, 4H), 4.06 (t, J
=
6.3 Hz, 8H), 1.87 – 1.74 (m, 8H), 1.50 – 1.39 (m, 8H), 1.25 (s, 46H),
1
3
0
1
3
.84 (d, J = 7.0 Hz, 14H). C NMR (101 MHz, CDCl3) δ 165.50, 160.85,
50.74, 136.03, 129.22, 128.82, 125.96, 125.85, 112.25, 109.05, 68.22,
1.89, 29.55, 29.54, 29.35, 29.31, 28.99, 25.97, 22.68, 14.11.
+
HRMS (ESI): m/z calcd. for C76H103N4O4 [MH ] 1135.7997; found
1135.7979
P3 (725 mg, 49%) as dark yellow oil
1
H NMR (400 MHz, CDCl3) δ 8.72 (d, J = 5.1 Hz, 4H), 8.41 (s, 4H), 8.36
(s, 2H), 7.63 (s, 4H), 7.19 (d, J = 4.9 Hz, 4H), 2.78 – 2.66 (m, 8H), 1.79 –
1
3
1.64 (m, 12H), 1.46 – 1.29 (m, 12H), 0.98 – 0.82 (m, 12H). C NMR (101
MHz, CDCl3) δ 159.25, 152.34, 149.68, 136.23, 129.63, 128.90, 126.37,
26.19, 125.91, 122.45, 35.55, 31.60, 30.33, 22.60, 14.13.
1
+
HRMS (ESI): m/z calcd. for C56H63N4 [MH ] 791.5053; found 791.5051
Electrochemical Measurements: Electrochemical measurements were
carried out using Eco Chemie Autolab PGSTAT128n potentiostat, glassy
carbon electrode (diam. 2 mm), platinum coil, and silver wire as working,
P4 (151 mg, 86%) as yellow solid
H NMR (400 MHz, CDCl3) δ 8.71 (s, J = 4.0 Hz, 4H), 8.54 (s, 2H), 8.02
1
(
2
s, 4H), 4.52 (t, J = 7.3 Hz, 8H), 2.13 – 1.98 (m, 8H), 1.41 (t, J = 16.7 Hz,
0H), 1.27 (s, 36H), 0.87 (t, J = 6.8 Hz, 12H). C NMR (101 MHz,
auxiliary, and a reference electrode, respectively. Potentials are
1
3
referenced with respect to ferrocene (Fc), which was used as the internal
standard. Cyclic voltammetry experiments were conducted in a standard
one-compartment cell, in CH2Cl2 (Carlo Erba, HPLC grade), under argon.
CDCl3) δ 147.11, 128.71, 128.60, 126.06, 125.83, 125.77, 123.27, 50.76,
2.00, 30.59, 29.65, 29.56, 29.41, 29.21, 26.78, 22.80, 14.23.
3
This article is protected by copyright. All rights reserved.