Upload
others
View
0
Download
0
Embed Size (px)
Citation preview
1
Supplementary Information
Architecting layered molecular packing in substituted benzobisbenzothiophene (BBBT) semiconductor crystals
Toshiki Higashino,*a Shunto Arai,b Satoru Inoue,b Seiji Tsuzuki,c Yukihiro Shimoi,c
Sachio Horiuchi,a Tatsuo Hasegawa,*b Reiko Azumia
E-mail: [email protected]
a Electronics and Photonics Research Institute, National Institute of Advanced Industrial
Science and Technology (AIST), Tsukuba, 305-8565, Japan. b Department of Applied Physics, The University of Tokyo, Tokyo, 113-8656, Japan. c Research Center for Computational Design of Advanced Functional Materials
(CD-FMat), National Institute of Advanced Industrial Science and Technology (AIST),
Tsukuba, 305-8568, Japan.
Electronic Supplementary Material (ESI) for CrystEngComm.This journal is © The Royal Society of Chemistry 2020
2
Synthesis
Commercially available materials were used as received. Anhydrous solvents
(dimethyl sulfoxide: DMSO and pyridine) were purchased from Wako Pure Chemical
Industries. All reactions were conducted under argon atmosphere. For thin-layer
chromatography (TLC) analysis, Merck pre-coated glass plates (TLC Silica gel 60
F254) were used. Silica gel used in chromatographic separations was obtained from
Wako Pure Chemical Industries (Wakogel® C-200). 1H NMR (400 MHz) and 13C NMR
(100 MHz) spectra were measured with a Bruker AVANCE 400 spectrometer with
CDCl3 as a solvent using Me4Si or residual solvent as an internal standard.
Scheme S1 Synthesis of diC10-BBBT and Ph-BBBT-C10.
2-(4-Decylphenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (4a)
A mixture of 1-bromo-4-decylbenzene (7.43 g, 25.0 mmol, 1.0 eq.), Pd(dppf)Cl2 (1.02 g,
1.25 mmol, 5 mol%), potassium acetate (9.81 g, 100 mmol, 4.0 eq.), and
bis(pinacolato)diboron (9.52 g, 37.5 mmol, 1.5 eq.) in anhydrous DMSO (70 mL) was
stirred for 24 h at 80 °C. After cooling down to room temperature, the reaction mixture
was poured into a NH4Cl solution, and then filtered through Celite. The residue was
washed with EtOAc, and the filtrate was extracted with EtOAc. The combined organic
layer was washed with water and brine, dried over Na2SO4, filtered, and concentrated
3
under reduced pressure. The residue was subjected to silica gel column chromatography
(hexane, Rf = 0.3), to afford 4a (7.60 g, 22.1 mmol, yield 88%) as a colourless oil.
GC/MS (EI) m/z = 344; 1H NMR (400 MHz, CDCl3) δ 7.72 (d, J = 8.0 Hz, 2H), 7.19 (d,
J = 8.0 Hz, 2H), 2.61 (t, J = 8.0 Hz, 2H), 1.64-1.56 (m, 2H), 1.34 (s, 12H), 1.33-1.22 (m,
14H), 0.88 (t, J = 7.2 Hz, 3H).
2-([1,1'-Biphenyl]-4-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (4b)
A mixture of 4-bromo-1,1'-biphenyl (5.83 g, 25.0 mmol, 1.0 eq.), Pd(dppf)Cl2 (1.02 g,
1.25 mmol, 5 mol%), potassium acetate (9.81 g, 100 mmol, 4.0 eq.), and
bis(pinacolato)diboron (9.52 g, 37.5 mmol, 1.5 eq.) in anhydrous DMSO (70 mL) was
stirred for 24 h at 80 °C. After cooling down to room temperature, the reaction mixture
was poured into a NH4Cl solution, and then filtered through Celite. The residue was
washed with EtOAc, and the filtrate was extracted with EtOAc. The combined organic
layer was washed with water and brine, dried over Na2SO4, filtered, and concentrated
under reduced pressure. The residue was subjected to silica gel column chromatography
(CH2Cl2:hexane = 1:2, Rf = 0.5) and recrystallized from hexane, to afford 4b (6.33 g,
22.6 mmol, yield 90%) as a white solid. GC/MS (EI) m/z = 344; 1H NMR (400 MHz,
CDCl3) δ 7.72 (d, J = 8.0 Hz, 2H), 7.19 (d, J = 8.0 Hz, 2H), 2.61 (t, J = 8.0 Hz, 2H),
1.64-1.56 (m, 2H), 1.34 (s, 12H), 1.33-1.22 (m, 14H), 0.88 (t, J = 7.2 Hz, 3H).
4,4''-Didecyl-2',5'-bis(methylsulfinyl)-1,1':4',1''-terphenyl (5a)
A mixture of 1,4-dibromo-2,5-bis(methylsulfinyl)benzene (3)S1 (0.360 g, 1.00 mmol,
1.0 eq.), 4a (1.03 g, 3.00 mmol, 3.0 eq.), Pd(dppf)Cl2 (0.082 g, 0.10 mmol, 10 mol%),
potassium carbonate (0.829 g, 6.00 mmol, 6.0 eq.), and benzyltriethylammonium
chloride (0.228 g, 1.00 mmol, 1.0 eq.) in toluene/water (32/8 mL) was stirred for 24 h at
90 °C. After cooling down to room temperature, to the reaction mixture was slowly
added a 2N-HCl solution, and then filtered through Celite. The residue was washed with
CHCl3, and the filtrate was extracted with CHCl3. The combined organic layer was
4
washed with water and brine, dried over Na2SO4, filtered, and concentrated under
reduced pressure. The residue was subjected to silica gel column chromatography
(CHCl3, Rf = 0.2). The resulting solid was washed with MeOH, to afford 5a (0.56 g,
0.88 mmol, yield 88%) as a white solid. GC/MS (EI) m/z = 635; 1H NMR (400 MHz,
CDCl3) δ 8.06 (s, 2H), 7.38 (d, J = 8.4 Hz, 4H), 7.28 (d, J = 8.4 Hz, 4H), 2.67 (t, J = 7.6
Hz, 4H), 2.40 (s, 6H), 1.70-1.62 (m, 4H), 1.38-1.25 (m, 28H), 0.89 (t, J = 6.8 Hz, 6H).
4-Decyl-2',5'-bis(methylsulfinyl)-1,1':4',1'':4'',1'''-quaterphenyl (5b)
A mixture of 1,4-dibromo-2,5-bis(methylsulfinyl)benzene (3)S1 (0.360 g, 1.00 mmol,
1.0 eq.), 4a (0.517 g, 1.50 mmol, 1.5 eq.), 4b (0.420 g, 1.50 mmol, 1.5 eq.), Pd(dppf)Cl2
(0.082 g, 0.10 mmol, 10 mol%), potassium carbonate (0.829 g, 6.00 mmol, 6.0 eq.), and
benzyltriethylammonium chloride (0.228 g, 1.00 mmol, 1.0 eq.) in toluene/water (32/8
mL) was stirred for 24 h at 90 °C. After cooling down to room temperature, to the
reaction mixture was slowly added a 2N-HCl solution, and then filtered through Celite.
The residue was washed with CHCl3, and the filtrate was extracted with CHCl3. The
combined organic layer was washed with water and brine, dried over Na2SO4, filtered,
and concentrated under reduced pressure. The residue was subjected to silica gel
column chromatography (CHCl3, Rf = 0.2). The resulting solid was washed with MeOH,
to afford 5b (0.17 g, 0.30 mmol, yield 30%) as a white solid. GC/MS (EI) m/z = 570; 1H
NMR (400 MHz, CDCl3) δ 8.12 (s, 1H), 8.10 (s, 1H), 7.73 (d, J = 8.4 Hz, 2H),
7,69-7.65 (m, 2H), 7.56 (d, J = 8.4 Hz, 2H), 7.52-7.47 (m, 2H), 7.43-7.38 (m, 2H), 7.30
(d, J = 8.4 Hz, 2H), 2.68 (t, J = 7.6 Hz, 2H), 2.45 (s, 3H), 2.41 (s, 3H), 1.71-1.63 (m,
2H), 1.38-1.25 (m, 14H), 0.89 (t, J = 6.8 Hz, 3H).
2,8-Didecyl-benzo[1,2-b:4,5-b']bis[b]benzothiophene (diC10-BBBT)
A mixture of 5a (0.254 g, 0.400 mmol, 1.0 eq.), phosphorus pentoxide (34 mg, 0.24
mmol, 0.6 eq.) and trifluoromethanesulfonic acid (8 mL) was stirred for 72 h at room
5
temperature. The reaction mixture was poured into ice-water (100 mL). The yellow
precipitate was collected by suction filtration and dried under vacuum. The residue was
assumed to be the sulfonium salt. Demethylation of the solid was achieved by refluxing
in anhydrous pyridine (20 mL) for 12 h. After cooling down to room temperature, the
reaction mixture was diluted by water. The resulting precipitate was collected by
suction filtration and was purified by being passed through silica gel column (CHCl3
eluent) and recrystallization from toluene/EtOH, to afford diC10-BBBT (68 mg, 0.12
mmol, yield 30%) as a white solid. M.p. 208 °C; GC/MS (EI) m/z = 570; 1H NMR (400
MHz, CDCl3) δ 8.52 (s, 2H), 8.10 (d, J = 8.0 Hz, 2H), 7.66 (s, 2H), 7.30 (dd, J = 8.0,
1.6 Hz, 2H), 2.77 (t, J = 7.6 Hz, 4H), 1.76-1.66 (m, 4H), 1.42-1.24 (m, 28H), 0.88 (t, J =
6.8 Hz, 6H).
2-Decyl-8-phenyl-benzo[1,2-b:4,5-b']bis[b]benzothiophene (Ph-BBBT-C10)
A mixture of 5b (0.154 g, 0.270 mmol, 1.0 eq.), phosphorus pentoxide (38 mg, 0.27
mmol, 1.0 eq.) and trifluoromethanesulfonic acid (8 mL) was stirred for 72 h at room
temperature. The reaction mixture was poured into ice-water (100 mL). The yellow
precipitate was collected by suction filtration and dried under vacuum. The residue was
assumed to be the sulfonium salt. Demethylation of the solid was achieved by refluxing
in anhydrous pyridine (20 mL) for 12 h. After cooling down to room temperature, the
reaction mixture was diluted by water. The resulting precipitate was collected by
suction filtration and was purified by being passed through silica gel column (CHCl3
eluent) and recrystallization from toluene, to afford Ph-BBBT-C10 (44 mg, 0.087
mmol, yield 32%) as a white solid. M.p. 347 °C; GC/MS (EI) m/z = 506; 1H NMR (400
MHz, CDCl3) δ 8.59 (s, 1H), 8.56 (s, 1H), 8.26 (d, J = 8.0 Hz, 1H), 8.12 (d, J = 8.0 Hz,
1H), 8.08 (s, 1H), 7.75-7.67 (m, 4H), 7.53-7.47 (m, 2H), 7.40 (tt, J = 7.6, 1.6 Hz, 1H),
7.32 (dd, J = 8.0, 1.6 Hz, 1H), 2.78 (t, J = 7.6 Hz, 2H), 1.76-1.67 (m, 2H), 1.42-1.24 (m,
14H), 0.88 (t, J = 6.8 Hz, 3H).
6
Solvent solubilities and thermal properties
Fig. S1 TG-DTA and DSC curves of diC10-BBBT and Ph-BBBT-C10.
7
Fig. S2 Room-temperature solubilities and phase transition temperatures of
diC10-BBBT, Ph-BBBT-C10, and their BTBT analogs.S2-S5
8
Crystal structures
Table S1 Crystallographic data.
Crystals diC10-BBBT Ph-BBBT-C10
Empirical formula C38H50S2 C34H34S2
Formula weight 570.93 506.76
Crystal shape colorless plate colorless plate
Crystal size (mm3) 0.18 × 0.14 × 0.086 0.24 × 0.24 × 0.010
Crystal system monoclinic monoclinic
Space group C2/c P21/c
a (Å) 70.5573(12) 57.3030(16)
b (Å) 4.29828(11) 7.80425(19)
c (Å) 10.8138(3) 6.13566(16)
α (°) 90 90
β (°) 91.4263(18) 92.479(2)
γ (°) 90 90
V (Å3) 3278.54(14) 2741.34(12)
Z 4 4
Total refls. 17114 36899
Uniq. refls. (Rint) 3723 (0.0216) 5149 (0.0556)
Uniq. refls. (I > 2σ(I)) 3212 3703
Refined params. 281 377
Dcalc (g/cm3) 1.157 1.228
R1, wR2 (I > 2σ(I)) 0.0329, 0.0907 0.0654, 0.1540
R1, wR2 (all data) 0.0397, 0.0950 0.0859, 0.1675
GOF 1.033 1.038
Temperature (K) 296 296
CCDC number 1964819 1964820
9
Hirshfeld Surface Analysis
Fig. S3 The Hirshfeld surfaces for BBBT (phase A and phase B),S6,S7 diC4-BBBT,S6
diC10-BBBT, and Ph-BBBT-C10. Red areas and letters indicate intermolecular short
contacts.
Fig. S4 The fingerprint plots for BBBT (phase A and phase B), S6,S7 diC4-BBBT, S6
diC10-BBBT, and Ph-BBBT-C10
10
Intermolecular Interaction Energy
Fig. S5 Molecular arrangements and intermolecular interaction energies between the
central black-colored molecule and another in BBBT (phase A).S6
Fig. S6 Molecular arrangements and intermolecular interaction energies between the
central black-colored molecule and another in BBBT (phase B).S7
11
Fig. S7 Molecular arrangements and intermolecular interaction energies between the
central black-colored molecule and another in diC4-BBBT.S6
Fig. S8 Molecular arrangements and intermolecular interaction energies between the
central black-colored molecule and another in diC10-BBBT.
12
Fig. S9 Molecular arrangements and intermolecular interaction energies between the
central black-colored molecule and another in Ph-BBBT-C10.
13
Thin-film properties
Fig. S10 (a)(d) Optical images, (b)(e) crossed-Nicols polarized micrographs and (c)(f)
AFM height profiles of the blade-coated thin films: (a)(b)(c) diC10-BBBT and (d)(e)(f)
Ph-BBBT-C10.
Fig. S11 (a) Optical image and (b) crossed-Nicols polarized micrographs of
large-area, single-domain, and single-bilayer Ph-BBBT-C10 ultrathin film obtained by
blade-coating method. The patterned yellow rods are evaporated gold.
14
TFT properties
Fig. S12 (a)(b) Crossed-Nicols polarized micrographs of the solution-crystallized TFT
devices and (c)(d) plots of mobility as a function of VG in the saturation region: (a)(c)
diC10-BBBT and (b)(d) Ph-BBBT-C10.
15
References
S1. (a) Gao, P.; Feng, X.; Yang, X.; Enkelmann, V.; Baumgarten, M.; Mullen, K.
Conjugated Ladder-Type Heteroacenes Bearing Pyrrole and Thiophene Ring
Units: Facile Synthesis and Characterization. J. Org. Chem. 2008, 73, 9207–
9213.; (b) Kim, J.; Han, A.-R.; Seo, J. H.; Oh, J. H.; Yang, C. β-Alkyl Substituted
Dithieno[2,3-d;2′,3′-d′]Benzo[1,2-b;4,5-b′]Dithiophene Semiconducting Materials
and Their Application to Solution-Processed Organic Transistors. Chem. Mater.
2012, 24, 3464–3472.
S2. Inoue, S.; Minemawari, H.; Tsutsumi, J.; Chikamatsu, M.; Yamada, T.; Horiuchi,
S.; Tanaka, M.; Kumai, R.; Yoneya, M.; Hasegawa, T. Effects of Substituted
Alkyl Chain Length on Solution-Processable Layered Organic Semiconductor
Crystals. Chem. Mater. 2015, 27, 3809–3812.
S3. Iino, H.; Usui, T.; Hanna, J. Liquid Crystals for Organic Thin-Film Transistors.
Nat. Commun. 2015, 6, 6828:1-8.
S4. Ebata, H.; Izawa, T.; Miyazaki, E.; Takimiya, K.; Ikeda, M.; Kuwabara, H.; Yui,
T. Highly Soluble [1]Benzothieno[3,2-b]Benzothiophene (BTBT) Derivatives for
High-Performance, Solution-Processed Organic Field-Effect Transistors. J. Am.
Chem. Soc. 2007, 129, 15732–15733.
S5. Minemawari, H.; Tanaka, M.; Tsuzuki, S.; Inoue, S.; Yamada, T.; Kumai, R.;
Shimoi, Y.; Hasegawa, T. Enhanced Layered-Herringbone Packing Due to Long
Alkyl Chain Substitution in Solution-Processable Organic Semiconductors. Chem.
Mater. 2017, 29, 1245–1254.
S6. Gao, P.; Beckmann, D.; Tsao, H. N.; Feng, X.; Enkelmann, V.; Pisula, W.; Müllen,
K. Benzo[1,2-b:4,5-b′]Bis[b]Benzothiophene as Solution Processible Organic
Semiconductor for Field-Effect Transistors. Chem. Commun. 2008, 1548–1550.
S7. Ebata, H.; Miyazaki, E.; Yamamoto, T.; Takimiya, K. Synthesis, Properties, and
Structures of Benzo[1,2-b:4,5-b′]Bis[b]Benzothiophene and
Benzo[1,2-b:4,5-b′]Bis[b]Benzoselenophene. Org. Lett. 2007, 9, 4499–4502.