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147.62, 144.22, 141.69, 139.58, 136.20, 135.81, 131.24, 129.97,
128.99, 127.66, 123.29, 111.36, 51.29, 32.05, 27.55, 27.15, 23.00,
14.36 ppm; HRMS (ESI): m/z calcd for C52H67N4S2: 811.4807
[(M+H)]+; found: 811.4794.
2,5- and 9,10-positions in extending the effective p-conjuga-
tion, which strengthened the ICT interactions, narrowed the
energy band-gap, and lowered the LUMO level. Moreover,
upon the incorporation of vinyl groups between the DTP and
N,N-dihexylaniline units at the 2,5-positions, unexpected hyp-
sochromic shifts were observed for both the absorption and
photoluminescence maxima. These results suggested that the
optoelectronic properties of the regioisomeric semiconductors
were greatly affected by the substitution pattern.
4,4’-(Dithieno[2,3-a:3’,2’-c]phenazine-8,11-diyl)bis(N,N-dihexy-
laniline) (2)
1
Yield: 21% (38 mg); dark-red solid; H NMR (400 MHz, CDCl3): d=
7.99 (s, 2H), 7.97 (d, J=4 Hz, 4H), 7.77 (d, J=4 Hz, 2H), 7.75 (d, J=
4 Hz, 2H), 6.89 (d, J=8 Hz, 4H), 3.42 (t, J=8 Hz, 8H), 1.73 (m, 8H),
1.41 (m, 24H), 0.96 ppm (m, 12H); 13C NMR (100 MHz, CDCl3): d=
147.88, 140.53, 138.27, 138.08, 136.47, 136.31, 132.43, 130.22,
128.87, 125.58, 123.24, 111.35, 51.41, 32.09, 27.65, 27.21, 23.02,
14.40 ppm; HRMS (ESI): m/z calcd for C52H67N4S2: 811.4807
[(M+H)]+; found: 811.4796.
Experimental Section
Materials and Reagents
All of the chemicals and reagents were purchased from commercial
sources and used as received. Anhydrous THF was distilled from
sodium benzophenone ketyl. CH2Cl2 and N,N-dimethylformamide
(DMF) were distilled from CaH2. All of the reactions and manipula-
tions were performed under a nitrogen atmosphere by using stan-
dard inert-atmosphere and Schlenk techniques. N,N-dihexyl-4-vinyl-
aniline[22] and N,N-dihexyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-
2-yl)aniline[23] and intermediates DTP1, DTP2, and DTP3[14] were
prepared according to literature procedures.
4,4’-(Dithieno[2,3-a:3’,2’-c]phenazine-2,5-diyl)bis(N,N-dihexyla-
niline) (3)
1
Yield: 28% (50 mg); dark-red solid; H NMR (400 MHz, CDCl3): d=
8.34 (s, 2H), 8.28–8.25 (m, 2H), 7.80–7.78 (m, 2H), 7.64 (d, J=8 Hz,
4H), 6.66 (d, J=8 Hz, 4H), 3.31 (t, 8H), 1.63 (m, 8H), 1.36 (m, 24H),
0.95 ppm (m, 12H); 13C NMR (100 MHz, CDCl3): d=148.20, 144.19,
141.72, 139.97, 135.39, 133.93, 129.56, 129.37, 127.51, 121.09,
117.15, 111.78, 51.31, 32.02, 27.55, 27.13, 23.01, 14.38 ppm; HRMS
(ESI): m/z calcd for C52H67N4S2: 811.4807 [(M+H)]+; found: 811.4793.
Measurements and Characterization
1H NMR (400 MHz) and 13C NMR (100 MHz) spectra were recorded
in CDCl3 or [D6]DMSO. Chemical shifts are expressed in ppm down-
field of tetramethylsilane (TMS). The splitting patterns are designat-
ed as follows: s (singlet), d (doublet), t (triplet), m (multiplet). UV/
Vis absorption spectra were recorded on a dual-beam spectropho-
tometer (Shimadzu UV-2550). PL spectra were recorded on a Shi-
madzu RF-5301PC spectrometer. The samples were prepared as
dilute solutions in quartz cuvettes (path length: 1 cm). CV meas-
urements were performed by using a typical three-electrode elec-
trochemical cell in a 0.1m solution of tetrabutylammonium hexa-
fluorophosphate in anhydrous CH2Cl2 at a scan rate of 50 mVsÀ1 at
RT under a nitrogen atmosphere. A glassy carbon electrode was
used as the working electrode; Pt wire was used as the counter
electrode; and a Ag/Ag+ electrode was used as the reference elec-
trode.
General Procedure for the Synthesis of Isomers 4–6
A flask was charged with dibromide (0.10 g, 0.22 mmol), N,N-dihex-
yl-4-vinylaniline (0.16 g, 0.55 mmol), Pd(OAc)2 (10 mg, 0.04 mmol),
Bu4NBr (71 mg, 0.22 mmol), KOAc (210 mg, 2.2 mmol), and DMF
(10 mL). The flask was degassed and purged with N2 gas and the
mixture was heated at 1008C for 24 h under a N2 atmosphere.
Then, the solution was filtered and the filtrate was poured into dis-
tilled water and extracted with CH2Cl2. The organic layer was dried
with anhydrous magnesium sulfate and concentrated under
vacuum. The crude product was purified by column chromatogra-
phy on silica gel (petroleum ether/CH2Cl2, 2:1 v/v).
4,4’-(Dithieno[2,3-a:3’,2’-c]phenazine-9,10-diylbis(ethene-2,1-
diyl))bis(N,N-dihexylaniline) (4)
General Procedure for the Synthesis of Isomers 1–3
1
Yield: 42% (80 mg); red solid; H NMR (400 MHz, CDCl3): d=8.30 (s,
2H), 7.73 (d, J=8 Hz, 2H), 7.66 (d, J=8 Hz, 2H), 7.48 (d, J=9.6 Hz,
4H), 6.67 (d, J=8 Hz, 4H), 3.32 (t, J=8 Hz, 8H), 1.63 (m, 8H), 1.36
(m, 24H), 0.94 ppm (m, 12H); 13C NMR (100 MHz, CDCl3): d=
148.39, 141.86, 140.55, 139.41, 136.18, 135.76, 134.00, 129.95,
128.67, 124.74, 123.99, 123.29, 120.55, 111.77, 51.37, 32.02, 27.57,
27.12, 22.99, 14.35 ppm; HRMS (ESI): m/z calcd for C56H71N4S2:
863.5120 [(M+H)]+; found: 863.5117.
Under a nitrogen atmosphere, dibromide (100 mg, 0.22 mmol),
N,N-dihexyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolanyl)aniline
(190 mg, 0.49 mmol), [Pd(PPh3)4] (30 mg, 0.03 mmol), and K2CO3
(1.8 g, 10 mmol) were mixed together in water (5 mL), and toluene
(15 mL) in a 100 mL Schlenk flask. The mixture was stirred and
heated at 858C overnight. When the reaction was complete, the
mixture was extracted three times with CH2Cl2. The combined or-
ganic solution was washed with brine and dried over anhydrous
sodium sulfate. After removal of the solvent, the residue was puri-
fied by flash column chromatography on silica gel (CH2Cl2/petrole-
um ether, 1:2) to afford the desired product.
4,4’-(Dithieno[2,3-a:3’,2’-c]phenazine-8,11-diylbis(ethene-2,1-
diyl))bis(N,N-dihexylaniline) (5)
1
Yield: 37% (70 mg); green solid; H NMR (400 MHz, CDCl3): d=8.35
(s, 1H), 8.31 (s, 1H), 8.05 (s, 2H), 7.78 (d, J=4 Hz, 2H), 7.74 (d, J=
4 Hz, 2H), 7.63–7.55 (m, 4H), 6.72 (d, J=8 Hz, 4H), 3.33 (t, J=8 Hz,
8H), 1.65 (m, 8H), 1.37(m, 24H), 0.93 ppm (m, 12H); 13C NMR
(100 MHz, CDCl3): d=148.09, 139.94, 138.13, 136.44, 136.03, 134.37,
130.67, 130.07, 128.48, 125.68, 124.48, 123.26, 119.34, 111.91, 51.39,
32.03, 27.63, 27.16, 23.00, 14.35 ppm; HRMS (ESI): m/z calcd for
C56H71N4S2: 863.5120 [(M+H)]+; found: 863.5120.
4,4’-(Dithieno[2,3-a:3’,2’-c]phenazine-9,10-diyl)bis(N,N-dihexy-
laniline) (1)
1
Yield: 23% (40 mg); red solid; H NMR (400 MHz, CDCl3): d=8.25 (s,
2H), 7.74 (d, J=4 Hz, 2H), 7.69 (d, J=4 Hz, 2H), 7.27 (d, J=8 Hz,
4H), 6.61 (d, J=8 Hz, 4H), 3.29 (t, J=8 Hz, 8H), 1.62 (m, 8H), 1.35
(m, 24H), 0.94 ppm (m, 12H); 13C NMR (100 MHz, CDCl3): d=
Chem. Asian J. 2016, 11, 874 – 881
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