H
C. Bonnier, D. S. Josey, and T. P. Bender
Experimental
Phenyl-BsubPc (3a): 35 % yield. Spectroscopic characterisa-
dH (CDCl , 400 MHz) 8.86
3
[18]
tion agrees with the literature.
(
General Considerations
3
4
6H, m), 7.89 (6H, m), 6.72 (1H, tt, J 7.4, J 1.3), 6.59
HH HH
CH Cl and THF solvents were purchased from Caledon Lab-
2
3
2H, m), 5.45 (2H, d, J 7.7).
2
(
HH
oratory Ltd (Caledon, Ontario, Canada); THF was dried and
purified by passing through activated alumina. Phenylmagne-
sium bromide (1.0 M in THF), 4-bromobiphenyl, Mg turnings,
I2, and BCP (99.6 %) were purchased from Sigma-Aldrich and
used as received. PEDOT:PSS (Heraeus, Clevois P VP AI
4
6H, m), 7.87 (6H, m), 6.42 (2H, d, J 7.8), 5.36 (2H, d), 1.90
-Tolyl-BsubPc (3b): 37 % yield. d (CDCl , 400 MHz) 8.84
H 3
3
(
(
1
(
HH
3H, s). d (CDCl , 100 MHz) 151.0, 137.4, 131.0, 129.7, 128.6,
C
3
27.9, 122.15, 21.0; C-BsubPc signal was not observed. dB
CDCl , 128 MHz) ꢀ15.8 (s). m/z (high-resolution mass spec-
3
4
083), Ag (R.D. Mathis, 99.999 %), and silver paint (PELCO,
trometry direct analysis in real time (HRMS DART))
4
Conductive Silver 187) were purchased and used as received.
a-6T (Sigma-Aldrich) and C60 (SES Research, 99.5 %) were
purchased and purified once by train sublimation before use.
Column chromatography was carried out on Silicycle Silica 60
silica gel (particle size 40–63 mm) and thin layer chromato-
graphy was performed on silica gel 60 coated with F254 nm. All
12
1
11 14
þ
87.18315; [ C H B N ] requires 487.18425.
31 20
6
4
00 MHz) 8.85 (6H, m), 7.88 (6H, m), 6.14 (2H, d, J 8.6),
-Methoxyphenyl-BsubPc (3c): 38 % yield. dH (CDCl3,
3
4
5
1
HH
.39 (2H, d), 3.43 (3H, s). d (CDCl , 100 MHz) 159.2, 150.9,
3
C
31.0, 129.9, 129.7, 122.1, 112.8, 54.9; C-BsubPc signal was not
observed. d (CDCl , 128 MHz) ꢀ15.9 (s). m/z (HRMS DART)
B
3
NMR spectra were recorded in CDCl (purchased from Cam-
3
12
1
11 14 16
þ
03.17780; [ C H B N O] requires 503.17916.
31 20 6
5
bridge Isotope Laboratories Inc. and used as is) on a Bruker
1
Advance III 400 MHz spectrometer operating at 400 MHz ( H),
4
.87 (6H, m), 7.90 (6H, m), 7.19 (5H, m), 6.82 (2H, d, J 8.1),
-Biphenyl-BsubPc (3d): 17 % yield. d (CDCl , 400 MHz)
H 3
3
8
5
1
1
28 MHz ( B), 100 MHz ( C), and 376 MHz ( F) at 258C.
1
13
19
HH
1
Chemical shifts are reported in ppm relative to the residual
.54 (3H, d). d (CDCl , 100 MHz) 151.0, 141.0, 140.6, 131.0,
C
3
29.8, 129.1, 128.6, 127.1, 127.0, 126.0, 122.2; C-BsubPc signal
1
13
11
solvent signal ( H and C), BF ꢃOEt ( B, 0 ppm) and C F
3
2
6 6
was not observed. d (CDCl ,128 MHz) ꢀ15.8 (s). m/z (HRMS
1
9
B
3
11 14
22
(
F, 0 ppm) standards.
UV-Visible spectra were obtained using a PerkinElmer
12
DART) 549.19858; [ C H B N ] requires 549.19990.
1
3
þ
6
6
4
MHz) 8.85 (6H, m), 7.89 (6H, m), 6.27 (2H, dd, J 8.9,
-Fluorophenyl-BsubPc (3e): 24 % yield. dH (CDCl 400
3
Lambda 25 spectrophotometer operating in double-beam mode
with a slit width of 1 nm. Fluorescence spectra were obtained
using a PerkinElmer LS55 spectrophotometer. Electrochemi-
3
HF
3
4
J
d, J 245), 151.0, 131.0, 130.4 (d, J 7.5), 129.8, 122.2,
8.3), 5.40 (2H, dd, J 5.9). d (CDCl , 100 MHz) 162.5
HF C 3
HH
1
3
CF CF
(
1
ꢀ
1
cal studies were performed at 100 mV s using a Bioanalytical
Systems C3 workstation with a three-electrode cell, consisting
of a Pt wire auxiliary electrode, an Ag/AgCl reference elec-
trode, and a glassy carbon disc (1 mm) working electrode.
Solutions comprised 1 mM test compound and 0.1 M
2
14.1 (d, J 20); C-BsubPc signal was not observed. d (CDCl ,
CF B 3
1
m/z (HRMS DART) 491.15917; [ C H B F N ] requires
28 MHz) ꢀ16.0 (s). d (CDCl , 376 MHz) ꢀ114.03 (s).
F
3
12
1
3
11 19 14
17
þ
6
0
4
91.15918.
þ ꢀ
nBu N] [PF ] as the supporting electrolyte in deoxygenated
4 6
[
OPV Fabrication
OPV device fabrication and characterisation was performed
CH Cl . All E values were referenced internally to Cp* Fe
2
2
2
1/2
[
27]
(
E1/2 ¼ ꢀ0.012 V in CH Cl versus Ag/AgCl).
X-ray crys-
2
2
[35]
tallographic analyses were performed on suitable crystals
mounted on a Kappa CCD system.
according to a previously described method.
OPV devices
were fabricated on 25 mm by 25 mm glass substrates coated with
ITO, with a sheet resistance of 15 O per square (Thin Film
Devices, Inc.). The ITO was pre-patterned, leaving 8 mm from
one side as uncoated glass. Substrates were cleaned by succes-
sive sonication processes in detergent and solvents, followed by
[13]
[40]
Br-BsubPc (1),
-methoxyphenylmagnesium bromide (2c),
4-tolylmagnesium bromide (2b),
[
40]
4
phenylmagnesium bromide (2e) were synthesised according
and 4-fluoro-
[
41]
to literature procedures.
5
min of atmospheric plasma treatment. PEDOT:PSS was spin-
Synthesis
coated onto the substrates at 500 rpm for 10 s, followed by
4000 rpm for 30 s. Substrates were baked on a hot plate at 1108C
for 10 min, and then transferred into a nitrogen atmosphere
glove box (O , 10 ppm, H O , 10 ppm).
Preparation of 4-Biphenylmagnesium Bromide (2d)
Under an atmosphere of Ar, Mg turnings (1.2 equiv.) and a
crystal of I were dissolved in anhydrous THF, and the mixture
was warmed at 358C. 4-Bromobiphenyl (1 equiv.), dissolved in a
minimum amount of anhydrous THF, was added dropwise, and
the resulting mixture was stirred at 358C for 5 h.
2
2
2
All subsequent device layers were thermally evaporated at
ꢀ7
ꢀ1
˚
1.0 A s
,
and a working pressure of ,1 ꢄ 10
torr for
ꢀ
6
organic layers and ,1 ꢄ 10 torr for Ag. Silver electrodes
were evaporated to a thickness of 80 nm through a shadow mask,
2
defining 0.2 cm as the active area for each device. A transfer
General Preparation of Aryl-BsubPc (3a–e)
back to the glove box was required between BCP and Ag layers
to change the shadow masks.
In a 500-mL three-neck flask, equipped with a condenser and
an argon inlet, the corresponding aryl magnesium bromide
reagent (2.0 equiv.) was added dropwise to a suspension of Br-
BsubPc (2.44 g, 5.1 mmol, 1.0 equiv.) in anhydrous THF
OPV Characterisation
(
400 mL). The mixture was refluxed under an atmosphere of
The layer thickness and deposition rates of the evaporated films
were monitored using a quartz crystal microbalance calibrated
against films deposited on glass, and also measured with a KLA-
Tencor P16þ surface profilometer. To enhance the electrical
contact during testing, silver paint was applied to the ITO and
metal electrode contact points, and left to dry for 20 min.
Devices were kept in the nitrogen-filled glove box throughout
testing. Voltage sweeps of the devices were performed under
argon for 16 h and after being cooled to room temperature, the
excess aryl magnesium bromide reagent was quenched with
methanol (MeOH). Volatiles were removed via rotary evapora-
tion, and the crude material was purified through column
chromatography using CH Cl as the eluent and further purified
2
2
by recrystallization from a mixture of CH Cl /hexanes and/or
2
train sublimation, affording red–bronze solids.
2