Benzodipyrrolidones and their polymers

Article abstract of DOI:10.1021/ma2017293

The packing structure, thermal properties, and photophysical and electrochemical properties are presented. Some soluble benzodipyrrolidone-based small molecules were synthesized, and the first two benzodipyrrolidone- based polymers were prepared by means

Full text of DOI:10.1021/ma2017293

Supporting Information of
“Benzodipyrrolidones and Their Polymers” by
F. Wudl et al.
Contents
1. General methods and synthesis.
2. Figure S1. TGA curves of 5a-1 and 5a-2.
3. Figure S2. DSC curve of 5a-2.
4. Figure S3. CV curves of 5a-1, 5a-2.
5. Figure S4. PBDPDP-B mobility dependence on annealing temperature.
6. Figure S5. PBDPDP-T mobility dependence on annealing temperature.

Experimental section
Materials. Toluene and DMF (N, N-dimethylformamide) were purified through a solvent
purification system. Commercially available reagents were used without further purification
unless otherwise stated. Compounds 2a and 3a were prepared following the same procedure as in
literature.
1
General Measurements. H NMR and 13C NMR were recorded on Varian-NMR 600
spectrometers in D6-DMSO, CDCl3 or CD2Cl4 with tetramethylsilane (TMS) as interval
standard. Mass spectrometry was performed by the UC Santa Barbara Mass Spectrometry
Laboratory. GPC measurements were conducted on a Waters 2695 system using polystyrene as
standard. Electronic absorption spectra were obtained on an Agilent Technologies G1103A
UV/vis Spectrometer. Thermogravimetric analysis (TGA) was carried out on a TGA Q50 (TA
Instruments) at a heating rate of 10 oC min-1 at a nitrogen flow. Differential scanning calorimetry
o
(DSC) was run on a DSC Q10 (TA Instrument) at a heating/cooling rate of 10/-10 C min-1 at a
nitrogen flow. Cyclic voltammetry (CV) were performed on a Princeton Applied Research
Model 263A Potentiostat/Galvanostat with a three-electrode cell in a solution 0.1 M
tetrabutylammonium hexafluorophosphate (Bu4NPF6) as supporting electrolyte dissolved in
methylene chloride or o-dichlorobenzene at a scan rate of 50 mV/s. A Pt disk was used as
working electrode, a Pt wire as the counter electrode and an Ag/AgCl electrode as the reference
electrode. The potential was calibrated by the ferrocene/ferrocenium standard. HOMO energy
levels were estimated by the equation: HOMO = -(4.80 + ∆Eoxdonset).

O
HN
OH
HO
NH
2a
O
1,4-Bis(α-hydroxyphenylacetylamino)benzene (2a).16 A mixture of p-phenylenediamine
(1.80 g, 16.7 mmol) and mandelic acid (7.60 g, 50.0 mmol) in chlorobenzene (30 mL) was
o
heated at 130 C for 18 h. On cooling to the room temperature, the precipitate was filtered,
1
washed with ethanol and dried in vacuo to yield 1a (80 %) as a white solid. H NMR (D6-
DMSO, 600 MHz) δ ppm 9.83 (s, 2H), 7.58 (s, 4H), 7.53 (d, J= 8.4 Hz, 4H), 7.48 (d, J= 7.2 Hz,
4H), 7.33 (t, J= 7.8 Hz, 4H), 7.26 (t, J= 7.2 Hz, 2H), 6.37 (d, J= 4.8 Hz, 2H), 5.05 (d, J= 4.8 Hz,
2H).
Br
O
HN
OH
HO
NH
2b
O
Br
1,4-Bis(α-hydroxy(4-bromophenyl)acetylamino)benzene (2b). 2b was prepared
following the same procedure as 2a. Yield 85%. 1H NMR (D6-DMSO, 600 MHz) δ ppm 9.85 (s,
2H), 7.56 (s, 4H), 7.53 (d, J= 8.4 Hz, 4H), 7.43 (d, J= 8.4 Hz, 4H), 6.47 (d, J= 4.8 Hz, 2H), 5.06
13
(d, J= 4.8 Hz, 2H). C NMR (D6-DMSO, 600 MHz) δ ppm 170.88, 140.71, 134.62, 131.43,
129.16, 121.19, 120.46, 73.69.

O
HN
NH
3a
O
3.7-Diphenyl-2,6-dioxo-1,2,3,4,5,6,7-hexahydrobenzo[1,2-b:4,5-b’]dipyrrole (3a). 1,4-
Bis(α-hydroxyphenylacetylamino)benzene (2a) (2.50 g, 6.50 mmol) was added to sulfuric acid
(25 mL). After stirred at room temperature for 20 h, the mixture was poured into ice water. The
1
precipitate was filtered, washed with water and dried to yield 3a (90 %) as a light red solid. H
NMR (D6-DMSO, 600 MHz) δ ppm 10.40 (s, 2/3H), 10.30 (s, 4/3H), 7.26-7.35 (m, 6H), 7.14-
7.16 (m, 8/3H), 6.79 (s, 2/3H), 6.73-6.78 (m, 4/3H), 6.56 (s, 4/3H), 4.72-4.73 (m, 4/3H), 4.51 (s,
2/15H), 3.84 (s, 8/15H). (NMR spectrum is complicate because of the existence of different
isomers)
O
HN
Br
Br
NH
3b
O
3.7-Di(4-bromophenyl)-2,6-dioxo-1,2,3,4,5,6,7-hexahydrobenzo[1,2-b:4,5-b’]dipyrrole
1
(3b). 3b was prepared following the same procedure as 3a. Yield 95%. H NMR (D6-DMSO,
600 MHz) δ ppm 10.43 (s, 0.4H), 10.38 (s, 0.4H), 10.36 (m, 1.2H), 7.46-7.55 (m, 2.4H), 7.45 (d,
J= 8.4 Hz, 0.8H), 7.10-7.14 (m, 2.4H), 7.02 (d, J= 9.0 Hz, 0.8H), 6.79 (s, 0.8H), 6.73 (d, J= 8.4
Hz, 0.8H), 6.57 (s, 1.2H), 6.53 (d, J= 7.8 Hz, 0.8H), 4.78 (s. 0.4H), 4.76 (s, 0.8H), 4.55 (s, 0.4H),
3.99 (s, 0.4H). (NMR spectrum is complicate because of the existence of different isomers) TOF
MS (FD+): m/z (%): 497.94 (100)[M]+.

O
HN
NH
4a
O
3,7-Diphenyl-2,6-dioxo-1,2,5,6-tetrahydrobenzo[1,2-b:4,5-b’]dipyrrole (4a). Sodium
hydroxide solution (0.75 mL, 5 N) was dropwised to a suspension of 3a (0.700 g, 2.06 mmol) in
ethanol. Then potassium persulfate (1.50 g, 5.55 mmol) in water (5 mL) was added. The
resulting mixture was heated at reflux for 2 h. The precipitate in the mixture was filtered, washed
1
with water and ethanol, dried to yield 4a (80 %). H NMR (D6-DMSO, 600 MHz) δ ppm 10.25
(s, 2H), 7.64 (d, J= 7.8 Hz, 4H), 7.49 (t, J= 7.8 Hz, 4H), 7.42 (t, J= 7.5 Hz, 4H), 6.36 (s, 2H).
O
HN
Br
Br
NH
4b
O
3,7-Di(4-bromophenyl)-2,6-dioxo-1,2,5,6-tetrahydrobenzo[1,2-b:4,5-b’]dipyrrole (4b).
1
4b was prepared following the same procedure as 4a. Yield 75 %. H NMR (D6-DMSO, 600
MHz) δ ppm 10.34 (s, 2H), 7.69 (d, J= 7.8 Hz, 4H), 7.60 (d, J= 7.8 Hz, 4H), 6.34 (s, 2H). TOF
MS (FD+): m/z (%): 495.94 (100)[M]+.
O
N
N
5a-1
O
N,N’-Dimethyl-3,7-diphenyl-2,6-dioxo-1,2,5,6-tetrahydrobenzo[1,2-b:4,5-b’]dipyrrole
(5a-1). A mixture of 4a (0.050 g, 0.15 mmol) and t-BuOK (0.132 g, 1.18 mmol) in DMF (1.50

mL) was added MeI (0.168 g, 1.18 mmol). After stirred for 24 h at room temperature, the
mixture was poured into water and extracted with DCM. The organic layer was washed with
brine and dried over anhydrous MgSO4. On removal of the solvent, the residue was purified by
column chromatography on silica gel with DCM:EA=50:1 as eluent to yield 5a-1 (73%) as a
1
dark brown solid. H NMR (CDCl3, 600 MHz) δ ppm 7.72 (d, J= 7.8 Hz, 4H), 7.50-7.53 (m,
4H), 7.44-7.46 (m, 2H), 6.37 (s, 2H).
O
N
N
5a-2
O
N,N’-Di(2-ethylhexyl)-3,7-diphenyl-2,6-dioxo-1,2,5,6-tetrahydrobenzo[1,2-b:4,5-
b’]dipyrrole (5a-2). A mixture of 4a (0.200 g, 0.590 mmol) and t-BuOK (0.265 g, 2.36 mmol)
in DMF (3.0 mL) was added ethylhexyl bromide (0.455 g, 2.36 mmol). After stirred for 24 h at
o
80 C, the mixture was poured into water and extracted with DCM. The organic layer was
washed with brine and dried over anhydrous MgSO4. On removal of the solvent, the residue was
purified by column chromatography on silica gel with Hexane: DCM=1:2 as eluent to yield 5a-2
1
(0.150 g, 45 %) as a dark brown solid. H NMR (CDCl3, 600 MHz) δ ppm 7.70 (d, J= 7.8 Hz,
13
4H), 7.47-7.49 (m, 4H), 7.40-7.42 (m, 2H), 6.37 (s, 2H). C NMR (CDCl3, 600 MHz) δ ppm
169.94, 144.09, 134.39, 131.24, 129.54, 128.95, 128.74, 127.37, 97.35, 43.51, 38.42, 38.41,
30.81, 28.93, 28.92, 24.18, 23.00, 14.06, 10.70, 10.69. TOF MS (FD+): m/z (%): 562.36
(100)[M]+.

C8H17
O
N
C10H21
Br
Br
C10H21
C8H17
N
O
5b
N,N’-Di(2-octyldodecyl)-3,7-di(4-bromophenyl)-2,6-dioxo-1,2,5,6-tetrahydrobenzo[1,2-
b:4,5-b’]dipyrrole (5b). 5b was prepared following the same procedure as 5a-2. Yield 60%. 1H
NMR (CDCl3, 600 MHz) δ ppm 7.60 (d, J= 9.0 Hz, 4H), 7.57 (d, J= 8.4 Hz, 4H), 6.29 (s, 2H).
13C NMR (CDCl3, 600 MHz) δ ppm 169.50, 144.31, 134.46, 132.01, 130.90, 130.03, 126.24,
123.58, 97.09, 43.99, 37.10, 34.65, 34.51, 31.92, 31.89, 31.77, 31.58, 30.00, 29.67, 29.65, 29.60,
29.37, 29.35, 29.31, 29.05, 26.69, 25.26, 22.68, 22.66, 22.64, 20.65, 14.06. TOF MS (FD+): m/z
(%): 1056.5 (100)[M]+.
PBDPDP-B.
A mixture of the di-bromoBDPP (0.300 g, 0.284 mmol), Pd2(dba)3 (13 mg), PPh3 (8 mg),
K3PO4 (0.241 g, 1.14 mmol) and Aliquat 336 (0.3 mL) was degassed and added toluene (10 mL)
and H2O (1.5 mL). The resulting mixture was heated at reflux under nitrogen for 3 days. After
cooling to room temperature, the mixture was dropped to methanol to precipitate. The solid was
collected by filter. After Soxhlet extraction with methanol, acetone, hexane, the solid was
extracted with chloroform. On being concentrated, the chloroform solution was dropped into
methanol to precipitate. Polymer PBDPDP-B (0.22 g, 79.4 %) was collected by filter as a dark
brown solid with metallic luster. 1H NMR (CD2Cl4, 600 MHz) δ ppm 7.44-7.88 (br, 12H), 6.47 (s,
2H), 3.57 (br, 4H), 1.84 (br, 2H), 1.65 (br, 8H), 1.14-1.44 (br, 56H), 0.87-0.96 (br, 12H).
PBDPDP-T.
The preparation of polymer PBDPDP-T (Blue purple solid, 0.21 g, 75.5 %) was followed
1
the same procedure as that of PBDPDP-B. H NMR (CD2Cl4, 600 MHz) δ ppm 7.73-7.82 (br,

8H), 7.45-7.48 (br, 2H), 6.45 (s, 2H), 3.56 (br, 4H), 1.83 (br, 2H), 1.64 (br, 8H), 1.25-1.36 (br,
56H), 0.87-0.90 (br, 12H).
Device Fabrication and Measurements
Transistors were fabricated in the bottom gate, bottom contact configuration on heavily-doped n-
type Si substrates as the gate and thermally grown 200 nm silicon dioxide as the dielectric layer
(Silicon Quest, dry oxide). The source and drain electrodes were patterned using standard photo-
lithography and formed on SiO2 with e-beam evaporation of 3 nm of nickel and 47 nm of gold.
Prior to casting, devices were cleaned in acetone and isopropanol and dried in an oven at 120°C
for 15 min. The samples were then surface-activated with acid hydrolysis, dried and then
exposed for 0.5 hrs to UV light in air. The devices were surface treated with DTS for 20 min by
immersion in a 1% by volume of DTS in toluene. The devices were then cleaned by rinsing with
toluene and dried under nitrogen flow followed spin-coating of the polymer. Polymer films were
spin-cast at 4000-5000 RPM in a glove box from 10mg/mL solutions in chloroform. Samples
were dried at 60 ºC for 0.5 hrs and then annealed at the desired temperature for 10 min in a glove
box. FET mobility measurements were performed in a glovebox using a Keithley 4200
Semiconductor Parametric Analyzer and a Signotone Micromanipulator S-1160 probe station.
Samples measured had channel lengths of 5ꢀm and channel widths of 1mm.

100
80
60
40
20
0
5a-1
5a-2
100
200
300
400
500
600
700
Temperature (oC)
Figure S1. TGA curves of 5a-1 and 5a-2. (10 oC/min, under N2 )
10
107.2 oC
5
61.4 oC
0
91.6 oC
-5
138.0 oC
-10
0
50
100
150
200
250
Temperature (oC)
Figure S2. DSC curve of 5a-2. (10 oC/min, under N2, 2nd circle)

Fc
5a-2
5a-1
-2.0
-1.5
-1.0
-0.5
0.0
Potential (V)
0.5
1.0
1.5
2.0
Figure S3. Cyclic voltammetry curves of 5a-1, 5a-2. (DCM, 50 mV/s, Fc,
ferrocene/ferrocenium)
0.01
1E-3
1E-4
1E-5
1E-6
80
120
160
200
240
280
Temperture (oC)
Figure S4. Mobility dependence on annealing temperature (PBDPDP-B, 10 min in glovebox).

0.1
0.01
1E-3
1E-4
1E-5
1E-6
p
n
80
160
240
80
160
240
Temperature (oC)
Figure S5. Mobility dependence on annealing temperature (PBDPDP-T, 10 min in glovebox).