Wang et al.
Anthracene Derivatives Substituted with Phenyl or Pentafluorophenyl for Organic Thin Film Transistors
to high charge mobility.8 For example, the recent work by
Park showed that the anthracene derivatives have stacked
in a two-dimensional columnar array by efficient ꢂ-orbital
overlap of the adjacent molecules owing to the substituted
aromatics (thiophene and phenylenevinylene).6
handled under moisture-free atmosphere. 2,6-Dibromo-
9,10-bis(triisopropylsilylethynyl) anthracene (TIPSAntB)
was prepared according to the literature method.6ꢀ13ꢀ14
2.2. Synthesis
Recently, fluorination of aromatic rings was discovered
to afford high quality of single crystal. Particularly, the
type and strength of intermolecular interaction can con-
sequently change the stacking geometry in crystals.9ꢀ10
Furthermore, the fluorinated aromatics could work as
withdrawing substituents and vary the energies of
HOMO or LUMO levels of the molecules.11 Facchetti
et al. reported n-type semiconductor with unique crys-
tal structure of thiophene oligomer end-functionalized
with perfluorobenzene.12 The oligomer showed good pla-
narity, closely ꢂ-stacked packing and high mobility of
0.5 cm2/V·s with current on/off ratio over 108.
2.2.1. Synthesis of 2,6-Bisphenyl-9,10-
Bis(triisopropylsilylethynyl)Anthracene
(TIPSAntP)
Into two-neck flask were added TIPSAntB (0.50 g,
0.72 mmol) and phenylboronic acid (0.19 g, 1.6 mmol) in
6 ml of anhydrous toluene. Pd(PPh3ꢃ4 (0.02 g, 2% mol)
was transferred into the mixture. Subsequently, Na2CO3
(2 M, 0.38 g, 3.61 mmol) and the phase transfer catalyst
Aliquat 336 (0.15 g, 0.36 mmol) in toluene were added
ꢀ
to the mixtures. After reaction at 90 C for 2 days, the
mixture was poured into saturated NaHCO3 solution and
extracted with ethyl acetate. The organic layer was washed
with brine and then dried over MgSO4. The crude product
was purified by column chromatography with hexane. The
yellow solid was obtained with the yield of 61%. 1H-NMR
(CDCl3, 300 MHz, ppm) ꢄ = 8ꢁ92 (s, 2H), 8.71 (d, 2H),
7.95 (d, 2H), 7.85 (d, 4H), 7.54 (t, 4H), 7.42 (d, 2H), 1.25
(m, 42). 13C-NMR (CDCl3, 300 MHz, ppm) ꢄ = 140ꢁ57,
138.99, 132.74, 132.02, 128.93, 127.90, 127.74, 127.40,
126.81, 124.99, 118.73, 105.09, 103.42, 18.98, 11.57. MS
(EI): m/z 690 (M+).
To date, none n-type TIPS-anthracene with fluori-
nated aromatic substituents have been reported. Therefore,
in this contribution, TIPS-anthracene derivatives contain-
ing pentafluorophenyl were synthesized. For comparison,
TIPS-anthracene derivatives with phenyl were synthesized
as well. Their thermal property, optical property, electro-
chemical property and crystal packing structures were sys-
tematically investigated. Hopefully, in the expectation of
the purpose of design and synthesis of the compounds,
Delivered by Ingenta to: Rice University
the side chain could bring different behavior of each com-
IP: 195.34.79.129 On: Tue, 14 Jun 2016 03:38:55
pound, and ultimately to realize them in OTFTs.
Copyright: American Scientific Publishers
2.2.2. Synthesis of 2,6-Bispentafluophenyl-9,10-
Bis(triisopropylsilylethynyl)Anthracene
(TIPSAntFP)
2. EXPERIMENTAL DETAILS
2.1. Instruments and Reagents
Two-neck flask was charged with TIPSAntB (0.30 g,
0.33 mmol), pentafluophenyboronic acid (0.20,
0.73 mmol) and toluene (8 ml) under nitrogen atmosphere.
Nitrogen was bubbled through the solution for 30 min. To
the solution, Pd2(dba)3 (0.02 g, 0.022 mmol), CsF (0.26 g,
1.72 mmol), Ag2O (0.24 g, 1.03 mmol), and P(t-Bu)3
(0.014 g, 0.07 mmol) were added with a ꢀgentle flow of
nitrogen. The mixture was stirred at 100 C for 2 days.
The resulting mixture was filtered through a pad of Celite
and washed with CHCl3. After column chromatography
with hexane, the yellow solid was obtained with the yield
1H, 13C NMR and 19F NMR spectra were recorded
using Bruker DPX-300 spectrometer. GC-MS spectra were
recorded on Hewlett-Packard 5890A mass spectrome-
ter. Differential scanning calorimetry (DSC) and thermal
gravimetric analysis (TGA) were performed by using a
Universal V4.3A TA instrument under N2 atmosphere with
ꢀ
a heating rate of 10 C/min, respectively. UV-vis absorp-
tion spectra were recorded on a Shimadzu UV-2550 spec-
trophotometer. Photoluminescent (PL) emissions spectra
were measured by PerkinElmer LS55 fluorometer. Cyclic
voltammetry (CV) was carried out on a BAS100W electro-
chemical instrument with a three-electrode cell in a solu-
tion of Bu4NBF4 (0.10 M) in 1,2-dichlorobenzene at a scan
rate of 50 mV/s. The measurements were calibrated using
ferrocene as a standard. The single crystals were grown
from hexane and chloroform for X-ray analysis. Crystal-
lography was performed on a Bruker SMART Apex II
X-ray Diffractometer.
1
of 45%. H-NMR (CDCl3, 300 MHz, ppm) ꢄ = 8ꢁ84 (s,
2H), 8.73 (d, 2H), 7.69 (d, 2H), 1.24 (m, 42). 19F-NMR
(CDCl3ꢃ ꢄ = −143ꢁ22 (4F), −154ꢁ96 (2F), −162ꢁ34 (4F).
MS (EI): m/z 871 (M+).
2.2.3. Synthesis of 2,6-Bisphenylacetylene-9,10-
Bis(triisopropylsilylethynyl)Anthracene
(TIPSAntPA)
Chemical reagents were purchased from Aldrich Chem.
Co. and TCI Co. and were used without further purifi-
cation. Solvents were purified by normal procedure and
To a suspension of TIPSAntB (0.45 g, 0.65 mmol),
PdCl2(PPh3ꢃ2 (47.5 mg, 0.068 mmol), and CuI (13.81 mg,
0.073 mmol) in THF (32 ml) were added Hunig’s base
J. Nanosci. Nanotechnol. 11, 4532–4539, 2011
4533