Full-color Tunable Photoluminescent Ionic Liquid Crystals Based on
Supporting Information
Full-color Tunable Photoluminescent Ionic Liquid Crystals Based on Tripodal Pyridinium, Pyrimidinium, and Quinolinium Salts Kana Tanabe,† Yuko Suzui,‡ Miki Hasegawa,‡ and Takashi Kato*,† †
Department of Chemistry and Biotechnology, School of Engineering, The University of Tokyo, Hongo,
Bunkyo-ku, Tokyo 113-8656, Japan; ‡Department of Chemistry and Biological Science, College of Science and Engineering, Aoyama-Gakuin Univerisity, 5-10-1 Fuchinobe, Sagamihara, Kanagawa 229-8558, Japan
E-mail: [email protected]
Contents S1. Materials and Syntheses (Scheme S1) S2. Polarizing Optical Microscopic Image of Py1–3, Pm1–3 and Q1–3 (Figure S1) S3. Solvent Effects on the Photophysical Properties of Py1–3 (Table S1) S4. Fluorescent Lifetimes of Pm1–3 and Q1–3 (Table S2)
S1. Materials and Syntheses All reagents and solvents were purchased from Aldrich, Tokyo Kasei, Kanto Chemical, or Wako, and used as received.
All reactions were performed under an Ar atmosphere in dry solvents, unless otherwise noted.
Scheme S1. Synthetic routes for electron-donating moieties. C12H25Br K2CO3
OH
OC12H25
OH
NBS
OC12H25 DMF
OC12H25 Br
30%
OCH3 Br
OCH3
Br
C12H25Br K2CO3
OH
CH2Cl2
OC12H25 Br
n-BuLi
O B O O
OC12H25 THF
DMF OH
Br
N
C12H25 C12H25
DMF 7c, 46%
S1
OC12H25
OC12H25 O B O
OC12H25 7b, 98%
96%
NH2
THF
OC12H25 O B O 8a, 62%
C12H25Br K2CO3 Br
O B O O
7a, 90%
OH
BBr3
OCH3
OC12H25
THF
n-BuLi
OC12H25 OC12H25 8b 60%
n-BuLi
O B O O
O B
THF
N
O
C12H25 C12H25
8c, 49%
1-Bromo-4-N,N-didodecylaminobenzene (7c). To a stirred solution of 4-bromoaniline (10 mmol, 1.72 g) and 1-bromododecane (35 mmol, 8.72 g) in dry DMF (20 mL) was added K2CO3 (30 mmol, 4.15 g), and the mixture was heated to 120 ºC. After stirred for 10 h, the reaction mixture was cooled to room temperature, and poured into water. The product was extracted eith hexane and ethyl acetate, washed with brine, and dried over anhydrous Na2SO4. After filtration and evaporation, the product was purified by column chromatography (silica, hexane as an eluent) to afford 7c as a colorless oil (yield = 2.33 g, 46%). 1
H NMR (400 MHz, CDCl3): δ 7.23 (d, J = 8.8 Hz, 2H), 6.47 (d, J = 8.8 Hz, 2H), 3.19 (t, J = 7.6 Hz, 4H),
1.60–1.50 (m, 4H), 1.30–1.20 (m, 36H), 0.88 (t, J = 6.8 Hz, 6H).
13
C{1H} NMR (100 MHz, CDCl3): δ
147.06, 131.74, 113.25, 106.70, 51.12, 31.94, 29.67, 29.65, 29.62, 29.53, 29.37, 27.14, 27.06, 22.71, 14.13. MS (MALDI): m/z 507.95 (calcd [M+H]+ = 508.35). Anal. calcd for C30H54BrN: C, 70.84; H, 10.70; N, 2.75%; found: C, 70.84; H, 10.70; N, 2.85%. 4-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)-3,4-didodecyloxybenzene (8a). To a stirred solution of 7a (4.0 mmol, 2.10 g) in dry THF (40 mL) was slowly added n-buthyl lithium (5.0 mmol, 3.4 mL).
After
stirred for 60 min at 78 ºC, 2-isopropoxy-4,4,5,5-Tetramethyl-1,3,2-dioxaborolane (7.0 mmol, 1.30 g) at –78 ºC was added to the reaction mixture. The mixture was slowly warmed to room temperature. After the mixture became to be transparent solution, cooled to –78 ºC and then stirred for 12h. After warmed to room temperature, the mixture was poured into water. The product was extracted with CH2Cl2, washed with brine, and dried over Na2SO4. After filtration and evaoration, the product was purified by column chromatography (silica, hexane/CH2Cl2 = 1/4 as an eluent) to afford 8a as a white solid (yield = 1.43 g, 62%). 1
H NMR (400 MHz, CDCl3): δ 7.38 (dd, J = 8.0 Hz, J = 1.6 Hz, 1H), 7.29 (d, J = 1.6 Hz, 1H), 6.87 (d, J =
8.0 Hz, J = 1.6 Hz, 1H), 4.05–3.98 (m, 4H), 1.85–1.78 (m, 4H), 1.50–1.20 (m, 36H), 1.33 (s, 12H), 0.88 (t, J = 6.8 Hz, J = 1.6 Hz, 1H).
13
C{1H} NMR (100 MHz, CDCl3): δ 151.89, 148.45, 128.57, 119.30, 112.59,
83.49, 69.16, 68.79, 31.90, 29.69, 29.68, 29.63, 29.60, 29.43, 29.40, 29.37, 29.35, 29.16, 26.03, 25.98, 24.81, 22.67, 14.09. MS (MALDI): m/z 572.18 (calcd [M]+ = 572.50). Anal. calcd for C36H65BO4: C, 75.50; H, 11.44; found: C, 75.37; H, 11.49%. 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-3,4,5-tridodecyloxybenzene
(8b)
and
4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-4-N,N-didodecyloxybenzene (8c) were prepared in similar manners to compound 2a. Spectroscopic data of these compounds are shown below. 4-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)-3,4,5-tridodecyloxybenzene (8b). White solid (yield = 60%).
1
H NMR (400 MHz, CDCl3): δ 6.99 (s, 2H), 4.03–3.94 (m, 6H), 1.85–1.70 (m, 6H), 1.50–1.20
(m, 54H), 1.33 (s, 12H), 0.88 (t, J = 6.8 Hz, 9H).
13
C{1H} NMR (100 MHz, CDCl3): δ 152.58, 141.12,
112.56, 83.71, 73.33, 69.05, 31.94, 31.92, 30.35, 29.74, 29.72, 29.70, 29.66, 29.61, 29.48, 29.42, 29.39, 29.36, 26.12, 24.83, 22.69, 14.11. MS (MALDI): m/z 755.83 (calcd [M]+ = 756.68). C48H89BO5: C, 76.15; H, 11.85; found: C, 76.61; H, 11.95%.
S2
Anal. calcd for
4-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)-4-N,N-didodecyloxybenzene (8c). (yield = 49%).
1
Colorless oil
H NMR (400 MHz, CDCl3): δ 7.64 (d, J = 8.8 Hz, 2H), 6.59 (d, J = 8.8 Hz, 2H), 3.26 (t,
J = 7.6 Hz, 4H), 1.63–1.53 (m, 4H), 1.32–1.22 (m, 36H), 1.31 (s, 12H), 0.88 (t, J = 6.8 Hz, 4H).
13
C{1H}
NMR (100 MHz, CDCl3): δ 150.20, 136.27, 110.52, 82.92, 50.76, 31.89, 29.63, 29.61, 29.58, 29.49, 29.33, 27.14, 27.08, 24.75, 22.62, 14.08. MS (MALDI): m/z 556.29 (calcd [M+H]+ = 556.53). Anal. calcd for C36H66BNO2: C, 77.81; H, 11.97; N, 2.52; found: C, 75.84; H, 11.98, N, 2.59%. 4-(3,4-Didodecyloxyphenyl)pyridine (1a).
To a stirred solution of 7a (841 mg, 1.60 mmol) and
4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridine (338 mg, 1.65 mmol) in THF (10 mL) was added Pd(PPh3)4 (127 mg, 0.11 mmol) and aqueous K2CO3 (2.0 M, 5 mL; Ar bubbled before use). The mixture was stirred for 12 h at 60 °C. After cooling to room temperature, the reaction mixture was poured into water, and extracted with CH2Cl2, three times. The combined organic layers were washed with brine, and dried over anhydrous Na2SO4.
After filtration and evaporation, the product was purified by column
chromatography (silica, ethyl acetate/hexane = 1/3 as an eluent), washed with methanol, and dried under vacuum to provide 1a as a white solid (yield = 438 mg, 52%).
1
H NMR (400 MHz, CDCl3): δ 8.61 (d, J
= 4.4 Hz, 1H), 8.60 (d, J = 4.4 Hz, 1H), 7.46 (d, J = 4.4 Hz, 1H), 7.45 (d, J = 4.4 Hz, 1H), 7.20 (dd, J = 8.4 Hz, J = 2.0 Hz, 1H), 7.16 (d, J = 2.0 Hz, 1H), 6.96 (d, J = 8.4 Hz, 1H), 4.09–4.02 (m, 4H), 1.88–1.80 (m, 4H), 1.50–1.20 (m, 36H), 0.88 (t, J = 6.4 Hz, 6H).
13
C{1H} NMR (100 MHz, CDCl3): δ 150.35, 150.11,
149.50, 148.09, 130.65, 121.14, 119.78, 113.79, 112.67, 69.58, 69.22, 31.90, 29.68, 29.64, 29.62, 29.41, 29.40, 29.35, 29.31, 29.21, 26.03, 26.01, 22.67, 14.09. MS (MALDI): m/z 524.49 (calcd [M+H]+ = 524.45). Anal. calcd for C35H57NO2: C, 80.25; H, 10.97, N: 2.67; found: C, 80.04; H, 11.10, N, 2.74%. 4-[4-(N,N-didodecylamino)phenyl]pyridine (1c) was prepared in similar manners to compound 1a. Spectroscopic data of these compounds are shown below. 4-[4-(N,N-Didodecylamino)phenyl]pyridine (1c). White solid (yield = 14%).
1
H NMR (400 MHz,
CDCl3): δ 8.54 (d, J = 6.0 Hz, 2H), 7.55 (d, J = 8.8 Hz, 2H), 7.45 (d, J = 6.0 Hz, 2H), 6.70 (d, J = 8.8 Hz, 2H), 3.31 (t, J = 7.2 Hz, 4H), 1.65–1.55 (m, 4H), 1.40–1.25 (m, 36 H), 0.88 (t, J = 6.4 Hz, 6H).
13
C{1H}
NMR (100 MHz, CDCl3): δ 149.89, 148.87, 148.14, 127.74, 123.62, 120.07, 111.69, 51.03, 31.91, 29.65, 29.64, 29.62, 29.59, 29.51, 29.34, 27.22, 27.14, 22.68, 14.10.
MS (MALDI): m/z 507.63 (calcd [M+H]+ =
507.47). Anal. calcd for C35H58N2: C, 82.94; H, 11.53, N: 5.53; found: C, 77.80; H, 10.89, N, 5.06%. 4-(3,4-Didodecyloxyphenyl)pyrimidine
(2a).
To
a
stirred
solution
of
1-bromo-3,4-didodecyloxybenzene (1.05 g, 2.0 mmol) in THF (5 mL) was added 1.57 M of n-BuLi (1.4 mL, 2.2 mmol) at –78°C and stirred for 1h. Pyrimidine (176 mg, 2.2 mmol) was added to the reacting mixture, and the solution was stirred for 12 h at room temperature, then poured into water and extracted with CH2Cl2, three times.
The combined organic layers were washed with brine, and dried over anhydrous Na2SO4.
After filtration and evaporation, the product was purified by column chromatography (silica, hexane/ethy acetate = 3/1 as an eluent), washed with methanol, and dried under vacuum to provide 2a as a white solid
S3
(yield =166 mg, 16%).
1
H NMR (400 MHz, CDCl3): δ 9.20 (d, J = 1.2 Hz, 1H), 8.69 (d, J = 5.6 Hz, 1H),
7.74 (d, J = 2.4 Hz, 1H), 7.64 (dd, J = 5.6 Hz, J = 1.2 Hz, 1H), 7.62 (dd, J = 8.4 Hz, J = 2.4 Hz, 1H), 6.96 (d, J =8.4 Hz, 1H), 4.11 (t, J = 6.8 Hz, 2H), 4.07 (t, J = 6.8 Hz, 2H), 1.88–1.82 (m, 4H), 1.38–1.23 (m, 36H), 0.88 (t, J = 6.8 Hz, 6H).
13
C{1H} NMR (100 MHz, CDCl3): δ 163.50, 158.94, 157.04, 152.01, 149.47,
128.94, 120.33, 116.22, 113.04, 112.14, 69.41, 69.13, 31.92, 29.70, 29.66, 29.63, 29.61, 29.42, 29.40, 29.36, 29.27, 29.15, 26.03, 25.99, 22.68, 14.10.
MS (MALDI): m/z 525.62 (calcd [M+H]+ = 525.44).
Anal.
calcd for C34H56N2O2: C, 77.81; H, 10.76, N: 5.34; found: C, 77.78; H, 10.96, N, 5.34%. 4-(3,4,5-tridodecyloxyphenyl)pyrimidine (2b) and 4-[4-(N,N-didodecylamino)phenyl]pyrimidine (2c) were prepared in similar manners to compound 2a. Spectroscopic data of these compounds are shown below. 4-(3,4,5-Tridodecyloxyphenyl)pyrimidine (2b).
White solid (yield = 11%).
1
H NMR (400 MHz,
CDCl3): δ 9.22 (s, 1H), 8.72 (d, J = 5.6 Hz, 1H), 7.64 (d, J = 5.6 Hz, 1H), 7.32 (s, 2H), 4.10–4.03 (m, 6H), 1.88–1.82 (m, 6H), 1.50–1.25 (m, 54H), 0.88 (t, J = 6.8 Hz, 9H).
13
C{1H} NMR (100 MHz, CDCl3): δ
163.64, 158.93, 157.21, 153.61, 141.19, 131.25, 116.65, 105.80, 73.58, 69.37, 31.94, 31.92, 30.34, 29.75, 29.72, 29.69, 29.63, 29.58, 29.40, 29.35, 26.10, 22.68, 14.10. MS (MALDI): m/z 709.86 (calcd [M+H]+ = 709.62). Anal. calcd for C46H80N2O3: C, 77.91; H, 11.37, N: 3.95; found: C, 77.28; H, 10.51, N, 3.51%. 4-[4-(N,N-Didodecylamino)phenyl]pyrimidine (2c). White solid (yield = 14%).
1
H NMR (400 MHz,
CDCl3): δ 9.10 (d, J = 1.2 Hz, 1H), 8.56 (d, J = 5.6 Hz, 1H), 7.98 (d, J = 8.8 Hz, 2H), 7.54 (dd, J = 5.6 Hz, J = 1.2 Hz, 1H), 6.68 (d, J = 8.8 Hz, 2H), 3.32 (t, J = 7.6 Hz, 4H), 1.65–1.55 (m, 4H), 1.45–1.20 (m, 36 H), 0.88 (t, J = 6.8 Hz, 6H).
13
C{1H} NMR (100 MHz, CDCl3): δ 163.58, 158.80, 156.39, 150.31, 128.42,
122.22, 114.83, 111.23, 50.95, 32.76, 31.86, 29.60, 29.58, 29.55, 29.45, 29.30, 27.18, 27.05, 22.64, 14.07. MS (MALDI): m/z 507.75 (calcd [M+H]+ = 507.46). Anal. calcd for C34H57N3: C, 80.41; H, 11.31, N: 8.27; found: C, 78.82; H, 9.43, N, 7.15%. 4-(3,4-Didodecyloxyphenyl)quinoline (3a).
To a stirred solution of 8a (802 mg, 1.4 mmol) and
4-bromoquinoline (270 mg, 1.3 mmol) in THF (6 mL) was added Pd(PPh3)4 (150 mg, 0.13 mmol) and aqueous K2CO3 (2.0 M, 5 mL; Ar bubbled before use). The mixture was stirred for 12 h at 60 °C.
After
cooling to room temperature, the reaction mixture was poured into water, and extracted with CH2Cl2, three times. The combined organic layers were washed with brine, and dried over anhydrous Na2SO4.
After
filtration and evaporation, the product was purified by column chromatography (silica, hexane/ethyl acetate = 2/1 as an eluent), washed with methanol, and dried under vacuum to provide 3a as a white solid (yield = 553 mg, 69%).
1
H NMR (400 MHz, CDCl3): δ8.92 (d, J = 4.4 Hz, 1H), 8.16 (d, J = 8.4 Hz, 1H), 8.01 (d,
J = 8.4 Hz, 1H), 7.72 (dd, J = 8.4 Hz, J = 7.2 Hz, 1H), 7.51 (dd, J = 8.4 Hz, J = 7.2 Hz, 1H), 7.33 (d, J = 4.4 Hz, 1H), 7.06–7.00 (m, 3H), 4.09 (t, J = 6.4 Hz, 2H), 4.03 (t, J = 6.4 Hz, 2H), 1.90–1.80 (m, 4H), 1.55–1.25 (m, 36H), 0.90–0.86 (m, 6H).
13
C{1H} NMR (100 MHz, CDCl3): δ 149.98, 149.52, 149.00, 148.75,
148.46, 130.53, 129.83, 129.20, 126.95, 126.45, 126.01, 122.23, 121.23, 115.32, 113.49, 69.46, 69.30, 31.93,
S4
31.91, 29.71, 29.68, 29.67, 29.65, 29.62, 29.45, 29.43, 29.37, 29.35, 29.30, 26.08, 26.03, 22.68, 14.12. MS (MALDI): m/z 574.48 (calcd [M]•+ = 574.46). Anal. calcd for C39H59NO2: C, 81.62; H, 10.36, N: 2.44; found: C, 81.79; H, 10.96, N, 2.58%. 4-(3,4,5-tridodecyloxyphenyl)quinoline (3b) and 4-[4-(N,N-didodecylamino)phenyl]quinoline (3c) were prepared in similar manners to compound 3a. Spectroscopic data of these compounds are shown below. 4-(3,4,5-Tridodecyloxyphenyl)quinoline (3b).
White solid (yield = 84%).
1
H NMR (400 MHz,
CDCl3) δ 8.92 (d, J = 4.0 Hz, 1H), 8.17 (d, J = 8.4 Hz, 1H), 8.01 (d, J = 8.0 Hz, 1H), 7.73 (dd, J = 8.0 Hz, J = 7.2 Hz, 1H), 7.52 (dd, J = 8.4 Hz, J = 7.2 Hz, 1H), 7.35 (d, J = 4.0 Hz, 1H), 6.67 (s, 2H), 4.56 (t, J = 6.4 Hz, 2H), 3.99 (t, J = 6.4 Hz, 4H), 1.80–1.75 (m, 6H), 1.65–1.25 (m, 54H), 0.89–0.87 (m, 9H).
13
C{1H}
NMR (100 MHz, CDCl3): δ 153.16, 149.86, 148.81, 148.64, 138.45, 132.89, 129.77, 129.27, 126.86, 126.54, 126.02, 121.10, 108.24, 73.60, 69.31, 31.94, 31.90, 30.40, 29.77, 29.75, 29.70, 29.68, 29.64, 29.62, 29.40, 29.35, 26.16, 26.08, 22.69, 22.67, 14.09. MS (MALDI): m/z 758.91 (calcd [M+H]+ = 758.65). Anal. calcd for C51H83NO3: C, 80.79; H, 11.03, N: 1.85; found: C, 80.46; H, 11.89, N, 1.56%. 4-[4-(N,N-Didodecylamino)phenyl]quinoline (3c). Orange oil (yield = 93%).
1
H NMR (400 MHz,
CDCl3): δ 8.88 (d, J = 4.8 Hz, 1H), 8.16–8.12 (m, 2H), 7.72–7.67 (m, 1H), 7.51–7.46 (m, 1H), 7.40 (d, J = 8.8 Hz, 2H), 7.31 (d, J = 4.8 Hz, 1H), 6.76 (d, J = 8.8 Hz, 2H), 3.33 (t, J = 8.0 Hz, 4H), 1.70–1.60 (m, 4H), 1.40–1.20 (m, 36H), 0.88 (m, 6H).
13
C{1H} NMR (100 MHz, CDCl3): δ 149.98, 148.89, 148.86, 148.24,
130.77, 129.68, 128.97, 127.05, 126.31, 126.02, 124.08, 120.83, 111.24, 51.06, 31.90, 29.68, 29.66, 29.63, 29.61, 29.54, 29.34, 27.25, 27.18, 22.67, 14.10. MS (MALDI): m/z 556.74 (calcd [M]•+ = 556.48).
Anal.
Calcd for C39H60N2: C, 84.11; H, 10.86, N: 5.03; found: C, 76.72; H, 10.45, N, 4.67%. This compound was not further purified and used as-is in the next reaction. 1,3,5-Tris(4-(3,4-didodecyloxyphenyl)pyridiniummethyl)benzene Bromide (4a). A mixture of 1a (262 mg, 0.50 mmol) and 1,3,5-tris(bromomethyl)benzene (54 mg, 0.15 mmol) in 12 mL of dry THF/CH3CN (1:2, v/v) was stirred for 12 h at 60 °C. After cooling to room temperature, the reaction mixture was poured into acetone. The formed precipitate was separated by filtration, and washed with acetone, and dried under vacuum to afford 4a as a yellow waxy solid (yield = 235 mg, 81%).
1
H NMR (400 MHz, CDCl3): δ
10.10, (d, J = 6.4 Hz, 6H), 9.17 (s, 3H), 8.12 (d, J = 6.4 Hz, 6H), 7.38 (d, J = 8.0 Hz, 3H), 7.21 (s, 3H), 6.97 (d, J = 8.0 Hz, 3H), 5.85 (s, 6H), 4.08–4.03 (m, 12H), 1.87–1.72 (m, 18H), 1,50–1.20 (m, 162H), 0.88 (t, J = 13
C{1H} NMR (100 MHz, CDCl3): δ 156.06, 153.54, 149.95, 145.13, 135.43, 133.32,
6.4 Hz, 27 H)..
125.13, 123.94, 121.88, 113.17, 111.77, 69.59, 69.14, 61.84, 31.88, 29.68, 29.68, 29.63, 29.61, 29.59, 29.57, 29.38, 29.32, 29.16, 28.95, 25.95, 25.91, 22.65, 14.08. The other tripodal salts having bromide anions (4c, 5a–c and 6a–c) were prepared in similar manners to compound 4a.
Spectroscopic data of these compounds are shown below.
1,3,5-Tris(4-(4-N,N-didodecylaminophenyl)pyridiniummethyl)benzene Bromide (4c). Yellow solid (yield = 99%).
1
H NMR (400 MHz, CDCl3): δ 9.84 (d, J = 6.8 Hz, 6H), 9.17 (s, 3H), 7.96 (d, J = 6.8 Hz,
S5
6H), 7.66 (d, J = 9.2 Hz, 6H), 6.67 (d, J = 9.2 Hz, 6H), 5.72 (s, 6H), 3.34 (t, J = 7.6 Hz, 12H), 1.90–1.82 (m, 12H), 1.50–1.20 (m, 96H), 0.88 (t, J = 6.4 Hz, 18H).
13
C{1H} NMR (100 MHz, CDCl3): δ 154.94,
151.66, 144.25, 135.77, 133.11, 129.64, 121.39, 118.24, 112.07, 51.15, 50.39, 31.92, 29.65, 29.64, 29.60, 29.47, 29.35, 29.26, 27.27, 27.08, 24.77, 22.70, 14.14. 1,3,5-Tris(4-(3,4-didodecyloxyphenyl)pyrimidiniummethyl)benzene Bromide (5a). (yield = 83%).
Yellow solid
1
H NMR (400 MHz, CDCl3): δ 10.60 (s, 3H), 10.35 (d, J = 6.0 Hz, 3H), 9.35 (s, 3H),
8.20 (d, J = 6.0 Hz, 3H), 7.84 (dd, J = 8.8 Hz, J = 2.0 Hz, 3H), 7.81 (d, J = 2.0 Hz, 3H), 6.96 (d, J = 8.8 Hz, 3H), 5.88 (s, 6H), 4.09 (t, J = 6.4 Hz, 6H), 4.06 (t, J = 6.4 Hz, 6H), 1.90–1.82 (m, 12H), 1.50–1.20 (m, 96H), 0.88 (t, J = 6.4 Hz, 18H).
13
C{1H} NMR (100 MHz, CDCl3): δ 168.91, 156.26, 152.75, 150.51, 149.84,
134.97, 133.79, 129.71, 124.80, 124.65, 116.86, 112.62, 69.44, 69.35, 58.59, 31.91, 29.72, 29.68, 29.63, 29.59, 29.43, 29.36, 29.35, 29.11, 28.90, 25.98, 25.90, 22.67, 14.10. 1,3,5-Tris(4-(3,4,5-tridodecyloxyphenyl)pyrimidiniummethyl)benzene Bromide (5b). (yield = 66%).
Yellow solid
1
H NMR (400 MHz, CDCl3): δ 10.70 (s, 3H), 10.52 (d, J = 6.4 Hz, 3H), 9.43 (s, 3H),
8.23 (d, J = 6.4 Hz, 3H), 7.49 (s, 6H), 5.88 (s, 6H), 4.14 (t, J = 6.4 Hz, 6H), 4.04 (t, J = 6.4 Hz, 12H), 1.90–1.82 (m, 18H), 1.50–1.20 (m, 162H), 0.88 (m, 27H).
13
C{1H} NMR (100 MHz, CDCl3): δ 169.28,
153.79, 152.68, 151.01, 145.64, 134.86, 133.95, 126.54, 117.36, 107.78, 73.96, 69.57, 58.66, 31.89, 30.37, 29.71, 29.69, 29.66, 29.64, 29.61, 29.49, 29.39, 29.35, 29.34, 29.24, 26.04, 25.94, 22.66, 14.08. 1,3,5-Tris(4-(4-N,N-didodecylaminophenyl)pyrimidiniummethyl)benzene Bromide (5c). solid (yield = 81%).
Yellow
1
H NMR (400 MHz, CDCl3): δ 10.19 (s, 3H), 9.93 (d, J = 6.4 Hz, 3H), 9.25 (s, 3H),
8.08 (d, J = 9.2 Hz, 6H), 7.87 (d, J = 6.4 Hz, 6H), 6.65 (d, J = 9.2 Hz, 6H), 5.73 (s, 6H), 3.38 (t, J = 7.6 Hz, 12H), 1.80–1.72 (m, 12H), 1.50–1.20 (m, 96H), 0.88 (t, J = 6.4 Hz, 18H).
13
C{1H} NMR (100 MHz,
CDCl3): δ 166.68, 153.69, 152.04, 150.67, 148.23, 144.95, 135.32, 134.70, 133.38, 132.32, 118.74, 114.34, 111.97, 67.98, 57.75, 51.30, 33.88, 31.86, 29.59, 29.57, 29.55, 29.37, 29.29, 27.31, 26.98, 22.64, 20.63, 14.08. 1,3,5-Tris(4-(3,4-didodecyloxyphenyl)quinoliniummethyl)benzene Bromide (6a). = 82%).
1
Orange solid (yield
H NMR (400 MHz, CDCl3): δ 10.68 (d, J = 6.4 Hz, 3H), 9.26 (d, J = 8.8 Hz, 3H), 8.91 (s, 3H),
8.30 (dd, J = 8.8 Hz, J = 7.2 Hz, 3H), 8.29 (d, J = 8.4 Hz, 3H), 8.04 (J = 6.4 Hz, 3H), 7.75 (dd, J = 8.4 Hz, J = 7.2 Hz, 3H), 7.14 (d, J = 8.8 Hz, 3H), 7.13 (s, 3H), 7.05 (d, J = 8.8 Hz, 3H), 6.41 (s, 6H), 4.11 (t, J = 6.4 Hz, 6H), 4.04 (t, J = 6.4 Hz, 6H), 1.95–1.80 (m, 12H), 1.50–1.20 (m, 108H), 0.90–0.85 (m, 18H).
13
C{1H}
NMR (100 MHz, CDCl3): δ 159.58, 151.98, 149.68, 148.90, 138.25, 136.80, 134.55, 131.77, 129.69, 129.10, 128.21, 127.00, 123.71, 122.49, 120.89, 115.02, 113.20, 69.75, 69.28, 59.02, 31.94, 29.73, 29.68, 29.65, 29.46, 29.44, 29.38, 29.26, 29.14, 26.05, 22.70, 14.13. 1,3,5-Tris(4-(3,4,5-didodecyloxyphenyl)quinoliniummethyl)benzene Bromide (6b). (yield = 34%).
1
Orange solid
H NMR (400 MHz, CDCl3): δ 10.63 (d, J = 6.4 Hz, 3H), 9.25 (d, J = 8.8 Hz, 3H), 8.91
(s, 3H), 8.34–8.24 (m, 6H), 8.08 (d, J = 6.4 Hz, 3H), 7.78 (dd, J = 8.8 Hz, J = 7.6 Hz, 3H), 6.78 (s, 6H), 6.43
S6
(s, 6H), 4.08 (t, J = 6.4 Hz, 6H), 4.00 (t, J = 6.4 Hz, 6H), 1.85–1.77 (m, 18H), 1.50–1.20 (m, 162H), 0.88 (m, 27H).
13
C{1H} NMR (100 MHz, CDCl3): δ159.96, 153.77, 148.97, 140.72, 138.22, 136.85, 134.49,
131.80, 129.83, 129.52, 129.11, 128.43, 122.78, 120.85, 108.63, 73.79, 69.67, 59.13, 31.94, 31.91, 30.41, 29.76, 29.74, 29.70, 29.65, 29.63, 29,61, 29.43, 29.39, 29.37, 29.35, 26.11, 22.69, 22.67, 14.09. 1,3,5-Tris(4-(4-N,N-didodecyloxyphenyl)quinoliniummethyl)benzene Bromide (6c). Red solid (yield = 81%).
1
H NMR (400 MHz, CDCl3): δ10.48 (d, J = 6.4 Hz, 3H), 9.15 (d, J = 8.8 Hz, 3H), 8.87 (s, 3H),
8.34 (d, J = 8.4 Hz, 3H), 8.25 (dd, J = 8.8 Hz, J = 8.0 Hz, 3H), 7.96 (d, J = 6.4 Hz, 3H), 7.66 (dd, J = 8.8 Hz, J = 8.0 Hz, 3H), 7.52 (d, J = 8.8 Hz, 6H), 6.78 (d, J = 8.8 Hz, 6H), 6.31 (s, 6H), 3.38 (t, J = 6.4 Hz, 6H), 1.85–1.77 (m, 12H), 1.50–1.20 (m, 108H), 0.87 (t, J = 6.8 Hz, 27H).
13
C{1H} NMR (100 MHz, CDCl3):
δ 138.37, 136.25, 134.73, 132.53, 131.57, 129.27, 128.77, 127.39, 120.83, 120.76, 120.59, 111.76, 58.48, 51.13, 31.87, 29.92, 29.62, 29.59, 29.57, 29.48, 29.29, 27.21, 27.09, 22.64, 14.08. 1,3,5-Tris(4-(3,4-didodecyloxyphenyl)pyridiniummethyl)benzene Hexafluorophosphate (Py1). To a stirred solution of 4a (96.4 mg, 0.05 mmol) in MeOH (5 mL) was added dropwise a solution of NH4PF6 (81.5 mg, 0.50 mmol) in water (0.5 mL). The formed precipitate was separated by filtration, and washed with water and methanol, successively.
The residue was dissolved into chloroform and filtered. After
evaporation of the solvent, the residue was dried under vacuum to afford Py1 as a yellow waxy solid (yield = 67 mg, 63%).
1
H NMR (400 MHz, CDCl3): δ 8.84 (d, J = 6.4 Hz, 6H), 8.08 (d, J = 6.4 Hz, 6H), 7.96 (s,
3H), 7.39 (dd, J = 8.4 Hz, J = 2.0 Hz, 3H), 7.23 (d, J = 2.0 Hz, 3H), 6.96 (d, J = 8.4 Hz, 3H), 5.56 (s, 6H), 4.09–4.03 (m, 12H), 1.85–1.82 (m, 12H), 1.50–1.25 (m, 108H), 0.89–0.86 (m, 18H).
13
C{1H} NMR (100
MHz, CDCl3): δ 157.02, 153.91, 150.10, 143.71, 135.63, 131.79, 124.93, 124.34, 122.24, 113.24, 111.99, 69.63, 69.21, 62.69, 31.94, 29.74, 29.71, 29.68, 29.66, 29.64, 29.47, 29.40, 29.38, 29.22, 29.01, 26.02, 25.98, 22.70, 14.13.
MS (MALDI): m/z 1974.35 (calcd [M–PF6–3H]+ = 1974.29).
Anal. calcd for
C114H180F18N3O6P3: C, 64.48; H, 8.54; N, 1.98%; found: C, 64.46; H, 8.51; N, 2.27%. The other tripodal salts having hexafluorophosphate anions (Py3, Pm1–3, and Q1–3) were prepared in similar manners to compound Py1. Spectroscopic data of these compounds are shown below. 1,3,5-Tris(4-(4-N,N-didodecylaminophenyl)pyridiniummethyl)benzene Hexafluorophosphate (Py3). Yellow waxy solid (yield = 84%).
1
H NMR (400 MHz, CDCl3): δ 8.86 (d, J = 6.8 Hz, 6H), 8.16 (s, 3H),
7.95 (d, J = 6.8 Hz, 6H), 7.70 (d, J = 9.2 Hz, 6H), 6.68 (d, J = 9.2 Hz, 6H), 5.47 (s, 6H), 3.34 (t, J = 7.6 Hz, 12H), 1.80–1.72 (m, 12H), 1.50–1.20 (m, 96H), 0.88 (t, J = 6.4 Hz, 18H).
13
C{1H} NMR (100 MHz,
CDCl3): δ 155.49, 151.95, 142.96, 135.97, 131.82, 129.93, 121.50, 117.86, 112.16, 51.18, 31.93, 29.65, 29.63, 29.59, 29.47, 29.35, 27.27, 27.07, 22.69, 14.13. MS (MALDI): m/z 1924.75 (calcd [M–PF6–2H]+ = 1924.36).
Anal. calcd for C114H183F18N6P3: C, 66.06; H, 8.90; N, 4.05%; found: C, 66.27; H, 8.85; N,
4.41%. 1,3,5-Tris(4-(3,4-didodecyloxyphenyl)pyrimidiniummethyl)benzene Yellow waxy solid (yield = 75%).
1
Hexafluorophosphate
(Pm1).
H NMR (400 MHz, CDCl3): δ 9.42 (s, 3H), 8.78 (d, J = 6.4 Hz, 3H),
S7
8.09 (s, 3H), 7.91 (d, J = 4.8 Hz, 3H), 7.60–7.50 (m, 6H), 6.75 (d, J = 8.4 Hz, 3H), 5.65 (s, 6H), 3.96 (t, J = 6.4 Hz, 6H), 3.87 (t, J = 6.4 Hz, 6H), 1.80–1.72 (m, 12H), 1.50–1.20 (m, 96H), 0.88 (t, J = 6.4 Hz, 18H). 13
C{1H} NMR (100 MHz, CDCl3): δ 179.33, 168.99, 155.94, 151.88, 149.51, 148.94, 134.76, 132.50,
124.62, 124.52, 117.11, 112.43, 69.15, 59.25, 31.94, 29.80, 29.77, 29.69, 29.61, 29.54, 29.42, 29.40, 29.20, 29.03, 26.08, 25.99, 22.70, 14.12. MS (MALDI): m/z 1978.73 (calcd [M–PF6–2H]+ = 1978.29).
Anal.
calcd for C111H177F18N6O6P3: C, 62.69; H, 8.39; N, 3.95%; found: C, 62.73; H, 8.25; N, 3.94%. 1,3,5-Tris(4-(3,4,5-tridodecyloxyphenyl)pyrimidiniummethyl)benzene Hexafluorophosphate (Pm2). Yellow waxy solid (yield = 80%).
1
H NMR (400 MHz, CDCl3): δ 9.59 (s, 3H), 9.04 (d, J = 6.4 Hz, 3H),
8.21 (s, 3H), 8.13 (d, J = 6.4 Hz, 3H), 7.45 (s, 6H), 5.71 (s, 6H), 4.10 (t, J = 6.4 Hz, 6H), 4.02 (t, J = 6.4 Hz, 12H), 1.80–1.72 (m, 18H), 1.50–1.20 (m, 162H), 0.88 (m, 27H).
13
C{1H} NMR (100 MHz, CDCl3): δ
169.83, 153.81, 151.88, 149.54, 145.76, 134.76, 132.90, 126.61, 117.82, 108.04, 76.70, 73.99, 59.37, 31.95, 30.43, 29.77, 29.74, 29.71, 29.70, 29.68, 29.65, 29.56, 29.47, 29.40, 29.30, 26.14, 26.13, 22.71, 14.12. MS (MALDI): m/z 2531.96 (calcd [M–PF6–H]+ = 2531.84). Anal. calcd for C147H249F18N6O9P3: C, 65.89; H, 9.37; N, 3.14%; found: C, 66.34; H, 9.24; N, 3.23%. 1,3,5-Tris(4-(4-N,N-didodecyloxyphenyl)pyrimidiniummethyl)benzene Hexafluorophosphate (Pm3). Yellow waxy solid (yield = 84%).
1
H NMR (400 MHz, CDCl3): δ 9.17 (s, 3H), 8.61 (d, J = 6.4 Hz, 3H),
8.14–8.04 (m, 9H), 7.79 (d, J = 6.4 Hz, 3H), 6.65 (d, J = 10.0 Hz, 3H), 5.41 (s, 6H), 3.38 (t, J = 7.6 Hz, 12H), 1.80–1.72 (m, 12H), 1.50–1.20 (m, 96H), 0.88 (t, J = 6.4 Hz, 18H).
13
C{1H} NMR (100 MHz,
CDCl3): δ 166.82, 154.02, 151.17, 146.37, 135.41, 132.69, 132.24, 118.57, 114.53, 112.16, 58.44, 51.40, 31.91, 29.65, 29.63, 29.61, 29.58, 29.42, 29.35, 27.28, 27.02, 22.70, 14.15. MS (MALDI): m/z 1929.40 (calcd [M–PF6]+ = 1929.36). Anal. calcd for C111H180F18N9P3: C, 64.23; H, 8.74; N, 6.07%; found: C, 64.36; H, 8.67; N, 6.00%. 1,3,5-Tris(4-(3,4-didodecyloxyphenyl)quinoliniummethyl)benzene Orange waxy solid (yield = 89%).
1
Hexafluorophosphate
(Q1).
H NMR (400 MHz, CDCl3): δ 9.08 (d, J = 6.4 Hz, 3H), 8.35 (d, J =
8.0 Hz, 3H), 8.34 (d, J = 8.8 Hz, 3H), 8.01 (dd, J = 8.0 Hz, J = 7.6 Hz, 3H), 7.86 (d, J = 6.4 Hz, 3H), 7.76 (dd, J = 8.8 Hz, J = 7.6 Hz, 3H), 7.67 (s, 3H), 7.18 (s, 3H), 7.14 (d, 8.4 Hz, 3H), 7.03 (d, J = 8.4 Hz, 3H), 6.05 (s, 6H), 4.09 (t, J = 6.4 Hz, 6H), 4.03 (t, J = 6.4 Hz, 6H), 1.96–1.72 (m, 12H), 1.50–1.20 (m, 162H), 0.92–0.82 (m, 27H).
13
C{1H} NMR (100 MHz, CDCl3): δ 160.70, 151.94, 149.72, 147.18, 138.66,
136.07, 134.96, 129.79, 129.56, 129.39, 128.46, 127.00, 123.76, 122.27, 118.94, 114.96, 113.18, 69.57, 69.26, 59.47, 31.94, 29.74, 29.69, 29.67, 29.49, 29.46, 29.39, 29.25, 29.15, 26.05, 26.04, 14.13. MS (MALDI): m/z 2124.89 (calcd [M–PF6–2H]+ = 2125.35). Anal. calcd for C126H186F18N3O6P3: C, 66.56; H, 8.25; N, 1.85; found: C, 66.11; H, 8.11; N, 1.32%. 1,3,5-Tris(4-(3,4,5-tridodecyloxyphenyl)quinoliniummethyl)benzene Orange waxy solid (yield = 54%).
1
Hexafluorophosphate
(Q2).
H NMR (400 MHz, CDCl3): δ 9.06 (d, J = 6.4 Hz, 3H), 8.38 (d, J =
8.8 Hz, 3H), 8.37 (d, J = 8.8 Hz, 3H), 8.03 (dd, J = 8.8 Hz, J = 7.6 Hz, 3H), 7.80 (dd, J = 8.8 Hz, J = 7.6 Hz,
S8
3H), 6.81 (s, 6H), 6.07 (s, 6H), 4.07 (t, J = 6.4 Hz, 6H), 4.00 (t, J = 6.4 Hz, 6H), 1.80–1.72 (m, 18H), 1.50–1.20 (m, 162H), 0.88 (m, 27H).
13
C{1H} NMR (100 MHz, CDCl3): δ 161.21, 153.74, 147.15,
140.57, 138.68, 136.19, 134.87, 129.96, 129.65, 129.57, 129.48, 128.72, 122.54, 118.84, 108.54, 73.75, 69.52, 59.49, 31.96, 31.93, 30.43, 29.79, 29.73, 29.68, 29.66, 29.47, 29.42, 29.38, 26.14, 26.12, 22.69, 14.12. MS (MALDI): m/z 2679.45 (calcd [M–PF6]+ = 2679.91). Anal. calcd for C162H258F18N3O9P3: C, 68.83; H, 9.20; N, 1.49%; found: C, 68.53; H, 9.08; N, 1.84%. 1,3,5-Tris(4-(4-N,N-didodecylaminophenyl)quinoliniummethyl)benzene Hexafluorophosphate (Q3). Red waxy solid (yield = 97%).
1
H NMR (400 MHz, CDCl3): δ 8.97 (d, J = 6.4 Hz, 3H), 8.41 (d, J = 8.0
Hz, 3H), 8.23 (d, J = 8.8 Hz, 3H), 7.96 (dd, J = 8.0 Hz, J = 8.0 Hz, 3H), 7.82 (d, J = 6.4 Hz, 3H), 7.72–7.67 (m, 6H), 7.57 (d, J = 8.8 Hz, 6H), 6.79 (d, J = 8.8 Hz, 6H), 5.94 (s, 6H), 3.37 (t, J = 6.4 Hz, 12H), 1.80–1.72 (m, 12H), 1.50–1.20 (m, 108H), 0.87 (m, 18H).
13
C{1H} NMR (100 MHz, CDCl3): δ 160.17, 150.78,
146.20, 138.67, 135.62, 135.31, 132.85, 129.81, 128.96, 128.86, 127.55, 120.77, 120.47, 118.77, 111.93, 59.08, 51.18, 31.90, 29.67, 29.65, 29.63, 29.60, 29.51, 29.33, 27.27, 27.12, 22.67, 14.11. MS (MALDI): m/z 2071.89 (calcd [M–PF6–4H]+ = 2072.39). Anal. calcd for C126H189F18N6P3: C, 68.08; H, 8.57; N, 3.78%; found: C, 67.89; H, 8.66; N, 3.79%.
S3. Polarizing Optical Microscopic Image of Py1–3, Pm1–3 and Q1–3
Figure S1. Polarized optical micrographs of the tripodal salts (a) Py1 at 235 ºC, (b) Py2 at 170 ºC, (c) Py3 at 100 ºC, (d) Pm1 at 100 ºC, (e) Pm2 at 200 ºC, (f) Pm3 at 140 ºC, (g) Q1 at 100 ºC, (h) Q2 at 180 ºC and (i) Q3 at 100 ºC in the Col phases. Arrows indicate the directions of polarizer and analyzer axes.
S9
S3. Solvent Effects on the Photophysical Properties of Py1–3
Table S1. Solvent Effects on the Photophysical Properties of Tripodal Pyridinium Salts Py1–3 Py1 solvent
a
Py2
Py3
ET(30) λabs
λem
λabs
λem
λabs
λem
cyclohexane
30.9
372
509
370
508
430
548
toluene
33.9
378
507
379
526
447
498
THF
37.4
374
506
363
507
444
522
chloroform
39.1
386
505
379
526
460
510
dichloromethane
39.4
386
511
375
518
463
530
DMF
43.2
371
515
357
514
446
540
DMSO
45.1
371
514
356
515
445
541
acetonitrile
45.6
370
523
360
523
449
548
λabs: wavelengths of absorption maxima (nm); λem: wavelengths of emission maxima (nm).
S4. Fluorescent Lifetimes of Pm1–3 and Q1–3 Table S2. Fluorescent Lifetimes of the Tripodal Pyrimidinium and Quinolinium Salts in Thin Films as-spincoated filma compound
annealed filmb
λem / nm τ1 / ns
τ2 / ns
A1
A2
χ
τ1 / ns
τ2 / ns
A1
A2
χ
Pm1
495–633
6.2
11.81
0.90
0.10
1.018
3.8
9.8
0.92
0.08
1.112
Pm2
513–650
Full-color Tunable Photoluminescent Ionic Liquid Crystals Based on Tripodal Pyridinium, Pyrimidinium, and Quinolinium Salts Kana Tanabe,† Yuko Suzui,‡ Miki Hasegawa,‡ and Takashi Kato*,† †
Department of Chemistry and Biotechnology, School of Engineering, The University of Tokyo, Hongo,
Bunkyo-ku, Tokyo 113-8656, Japan; ‡Department of Chemistry and Biological Science, College of Science and Engineering, Aoyama-Gakuin Univerisity, 5-10-1 Fuchinobe, Sagamihara, Kanagawa 229-8558, Japan
E-mail: [email protected]
Contents S1. Materials and Syntheses (Scheme S1) S2. Polarizing Optical Microscopic Image of Py1–3, Pm1–3 and Q1–3 (Figure S1) S3. Solvent Effects on the Photophysical Properties of Py1–3 (Table S1) S4. Fluorescent Lifetimes of Pm1–3 and Q1–3 (Table S2)
S1. Materials and Syntheses All reagents and solvents were purchased from Aldrich, Tokyo Kasei, Kanto Chemical, or Wako, and used as received.
All reactions were performed under an Ar atmosphere in dry solvents, unless otherwise noted.
Scheme S1. Synthetic routes for electron-donating moieties. C12H25Br K2CO3
OH
OC12H25
OH
NBS
OC12H25 DMF
OC12H25 Br
30%
OCH3 Br
OCH3
Br
C12H25Br K2CO3
OH
CH2Cl2
OC12H25 Br
n-BuLi
O B O O
OC12H25 THF
DMF OH
Br
N
C12H25 C12H25
DMF 7c, 46%
S1
OC12H25
OC12H25 O B O
OC12H25 7b, 98%
96%
NH2
THF
OC12H25 O B O 8a, 62%
C12H25Br K2CO3 Br
O B O O
7a, 90%
OH
BBr3
OCH3
OC12H25
THF
n-BuLi
OC12H25 OC12H25 8b 60%
n-BuLi
O B O O
O B
THF
N
O
C12H25 C12H25
8c, 49%
1-Bromo-4-N,N-didodecylaminobenzene (7c). To a stirred solution of 4-bromoaniline (10 mmol, 1.72 g) and 1-bromododecane (35 mmol, 8.72 g) in dry DMF (20 mL) was added K2CO3 (30 mmol, 4.15 g), and the mixture was heated to 120 ºC. After stirred for 10 h, the reaction mixture was cooled to room temperature, and poured into water. The product was extracted eith hexane and ethyl acetate, washed with brine, and dried over anhydrous Na2SO4. After filtration and evaporation, the product was purified by column chromatography (silica, hexane as an eluent) to afford 7c as a colorless oil (yield = 2.33 g, 46%). 1
H NMR (400 MHz, CDCl3): δ 7.23 (d, J = 8.8 Hz, 2H), 6.47 (d, J = 8.8 Hz, 2H), 3.19 (t, J = 7.6 Hz, 4H),
1.60–1.50 (m, 4H), 1.30–1.20 (m, 36H), 0.88 (t, J = 6.8 Hz, 6H).
13
C{1H} NMR (100 MHz, CDCl3): δ
147.06, 131.74, 113.25, 106.70, 51.12, 31.94, 29.67, 29.65, 29.62, 29.53, 29.37, 27.14, 27.06, 22.71, 14.13. MS (MALDI): m/z 507.95 (calcd [M+H]+ = 508.35). Anal. calcd for C30H54BrN: C, 70.84; H, 10.70; N, 2.75%; found: C, 70.84; H, 10.70; N, 2.85%. 4-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)-3,4-didodecyloxybenzene (8a). To a stirred solution of 7a (4.0 mmol, 2.10 g) in dry THF (40 mL) was slowly added n-buthyl lithium (5.0 mmol, 3.4 mL).
After
stirred for 60 min at 78 ºC, 2-isopropoxy-4,4,5,5-Tetramethyl-1,3,2-dioxaborolane (7.0 mmol, 1.30 g) at –78 ºC was added to the reaction mixture. The mixture was slowly warmed to room temperature. After the mixture became to be transparent solution, cooled to –78 ºC and then stirred for 12h. After warmed to room temperature, the mixture was poured into water. The product was extracted with CH2Cl2, washed with brine, and dried over Na2SO4. After filtration and evaoration, the product was purified by column chromatography (silica, hexane/CH2Cl2 = 1/4 as an eluent) to afford 8a as a white solid (yield = 1.43 g, 62%). 1
H NMR (400 MHz, CDCl3): δ 7.38 (dd, J = 8.0 Hz, J = 1.6 Hz, 1H), 7.29 (d, J = 1.6 Hz, 1H), 6.87 (d, J =
8.0 Hz, J = 1.6 Hz, 1H), 4.05–3.98 (m, 4H), 1.85–1.78 (m, 4H), 1.50–1.20 (m, 36H), 1.33 (s, 12H), 0.88 (t, J = 6.8 Hz, J = 1.6 Hz, 1H).
13
C{1H} NMR (100 MHz, CDCl3): δ 151.89, 148.45, 128.57, 119.30, 112.59,
83.49, 69.16, 68.79, 31.90, 29.69, 29.68, 29.63, 29.60, 29.43, 29.40, 29.37, 29.35, 29.16, 26.03, 25.98, 24.81, 22.67, 14.09. MS (MALDI): m/z 572.18 (calcd [M]+ = 572.50). Anal. calcd for C36H65BO4: C, 75.50; H, 11.44; found: C, 75.37; H, 11.49%. 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-3,4,5-tridodecyloxybenzene
(8b)
and
4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-4-N,N-didodecyloxybenzene (8c) were prepared in similar manners to compound 2a. Spectroscopic data of these compounds are shown below. 4-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)-3,4,5-tridodecyloxybenzene (8b). White solid (yield = 60%).
1
H NMR (400 MHz, CDCl3): δ 6.99 (s, 2H), 4.03–3.94 (m, 6H), 1.85–1.70 (m, 6H), 1.50–1.20
(m, 54H), 1.33 (s, 12H), 0.88 (t, J = 6.8 Hz, 9H).
13
C{1H} NMR (100 MHz, CDCl3): δ 152.58, 141.12,
112.56, 83.71, 73.33, 69.05, 31.94, 31.92, 30.35, 29.74, 29.72, 29.70, 29.66, 29.61, 29.48, 29.42, 29.39, 29.36, 26.12, 24.83, 22.69, 14.11. MS (MALDI): m/z 755.83 (calcd [M]+ = 756.68). C48H89BO5: C, 76.15; H, 11.85; found: C, 76.61; H, 11.95%.
S2
Anal. calcd for
4-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)-4-N,N-didodecyloxybenzene (8c). (yield = 49%).
1
Colorless oil
H NMR (400 MHz, CDCl3): δ 7.64 (d, J = 8.8 Hz, 2H), 6.59 (d, J = 8.8 Hz, 2H), 3.26 (t,
J = 7.6 Hz, 4H), 1.63–1.53 (m, 4H), 1.32–1.22 (m, 36H), 1.31 (s, 12H), 0.88 (t, J = 6.8 Hz, 4H).
13
C{1H}
NMR (100 MHz, CDCl3): δ 150.20, 136.27, 110.52, 82.92, 50.76, 31.89, 29.63, 29.61, 29.58, 29.49, 29.33, 27.14, 27.08, 24.75, 22.62, 14.08. MS (MALDI): m/z 556.29 (calcd [M+H]+ = 556.53). Anal. calcd for C36H66BNO2: C, 77.81; H, 11.97; N, 2.52; found: C, 75.84; H, 11.98, N, 2.59%. 4-(3,4-Didodecyloxyphenyl)pyridine (1a).
To a stirred solution of 7a (841 mg, 1.60 mmol) and
4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridine (338 mg, 1.65 mmol) in THF (10 mL) was added Pd(PPh3)4 (127 mg, 0.11 mmol) and aqueous K2CO3 (2.0 M, 5 mL; Ar bubbled before use). The mixture was stirred for 12 h at 60 °C. After cooling to room temperature, the reaction mixture was poured into water, and extracted with CH2Cl2, three times. The combined organic layers were washed with brine, and dried over anhydrous Na2SO4.
After filtration and evaporation, the product was purified by column
chromatography (silica, ethyl acetate/hexane = 1/3 as an eluent), washed with methanol, and dried under vacuum to provide 1a as a white solid (yield = 438 mg, 52%).
1
H NMR (400 MHz, CDCl3): δ 8.61 (d, J
= 4.4 Hz, 1H), 8.60 (d, J = 4.4 Hz, 1H), 7.46 (d, J = 4.4 Hz, 1H), 7.45 (d, J = 4.4 Hz, 1H), 7.20 (dd, J = 8.4 Hz, J = 2.0 Hz, 1H), 7.16 (d, J = 2.0 Hz, 1H), 6.96 (d, J = 8.4 Hz, 1H), 4.09–4.02 (m, 4H), 1.88–1.80 (m, 4H), 1.50–1.20 (m, 36H), 0.88 (t, J = 6.4 Hz, 6H).
13
C{1H} NMR (100 MHz, CDCl3): δ 150.35, 150.11,
149.50, 148.09, 130.65, 121.14, 119.78, 113.79, 112.67, 69.58, 69.22, 31.90, 29.68, 29.64, 29.62, 29.41, 29.40, 29.35, 29.31, 29.21, 26.03, 26.01, 22.67, 14.09. MS (MALDI): m/z 524.49 (calcd [M+H]+ = 524.45). Anal. calcd for C35H57NO2: C, 80.25; H, 10.97, N: 2.67; found: C, 80.04; H, 11.10, N, 2.74%. 4-[4-(N,N-didodecylamino)phenyl]pyridine (1c) was prepared in similar manners to compound 1a. Spectroscopic data of these compounds are shown below. 4-[4-(N,N-Didodecylamino)phenyl]pyridine (1c). White solid (yield = 14%).
1
H NMR (400 MHz,
CDCl3): δ 8.54 (d, J = 6.0 Hz, 2H), 7.55 (d, J = 8.8 Hz, 2H), 7.45 (d, J = 6.0 Hz, 2H), 6.70 (d, J = 8.8 Hz, 2H), 3.31 (t, J = 7.2 Hz, 4H), 1.65–1.55 (m, 4H), 1.40–1.25 (m, 36 H), 0.88 (t, J = 6.4 Hz, 6H).
13
C{1H}
NMR (100 MHz, CDCl3): δ 149.89, 148.87, 148.14, 127.74, 123.62, 120.07, 111.69, 51.03, 31.91, 29.65, 29.64, 29.62, 29.59, 29.51, 29.34, 27.22, 27.14, 22.68, 14.10.
MS (MALDI): m/z 507.63 (calcd [M+H]+ =
507.47). Anal. calcd for C35H58N2: C, 82.94; H, 11.53, N: 5.53; found: C, 77.80; H, 10.89, N, 5.06%. 4-(3,4-Didodecyloxyphenyl)pyrimidine
(2a).
To
a
stirred
solution
of
1-bromo-3,4-didodecyloxybenzene (1.05 g, 2.0 mmol) in THF (5 mL) was added 1.57 M of n-BuLi (1.4 mL, 2.2 mmol) at –78°C and stirred for 1h. Pyrimidine (176 mg, 2.2 mmol) was added to the reacting mixture, and the solution was stirred for 12 h at room temperature, then poured into water and extracted with CH2Cl2, three times.
The combined organic layers were washed with brine, and dried over anhydrous Na2SO4.
After filtration and evaporation, the product was purified by column chromatography (silica, hexane/ethy acetate = 3/1 as an eluent), washed with methanol, and dried under vacuum to provide 2a as a white solid
S3
(yield =166 mg, 16%).
1
H NMR (400 MHz, CDCl3): δ 9.20 (d, J = 1.2 Hz, 1H), 8.69 (d, J = 5.6 Hz, 1H),
7.74 (d, J = 2.4 Hz, 1H), 7.64 (dd, J = 5.6 Hz, J = 1.2 Hz, 1H), 7.62 (dd, J = 8.4 Hz, J = 2.4 Hz, 1H), 6.96 (d, J =8.4 Hz, 1H), 4.11 (t, J = 6.8 Hz, 2H), 4.07 (t, J = 6.8 Hz, 2H), 1.88–1.82 (m, 4H), 1.38–1.23 (m, 36H), 0.88 (t, J = 6.8 Hz, 6H).
13
C{1H} NMR (100 MHz, CDCl3): δ 163.50, 158.94, 157.04, 152.01, 149.47,
128.94, 120.33, 116.22, 113.04, 112.14, 69.41, 69.13, 31.92, 29.70, 29.66, 29.63, 29.61, 29.42, 29.40, 29.36, 29.27, 29.15, 26.03, 25.99, 22.68, 14.10.
MS (MALDI): m/z 525.62 (calcd [M+H]+ = 525.44).
Anal.
calcd for C34H56N2O2: C, 77.81; H, 10.76, N: 5.34; found: C, 77.78; H, 10.96, N, 5.34%. 4-(3,4,5-tridodecyloxyphenyl)pyrimidine (2b) and 4-[4-(N,N-didodecylamino)phenyl]pyrimidine (2c) were prepared in similar manners to compound 2a. Spectroscopic data of these compounds are shown below. 4-(3,4,5-Tridodecyloxyphenyl)pyrimidine (2b).
White solid (yield = 11%).
1
H NMR (400 MHz,
CDCl3): δ 9.22 (s, 1H), 8.72 (d, J = 5.6 Hz, 1H), 7.64 (d, J = 5.6 Hz, 1H), 7.32 (s, 2H), 4.10–4.03 (m, 6H), 1.88–1.82 (m, 6H), 1.50–1.25 (m, 54H), 0.88 (t, J = 6.8 Hz, 9H).
13
C{1H} NMR (100 MHz, CDCl3): δ
163.64, 158.93, 157.21, 153.61, 141.19, 131.25, 116.65, 105.80, 73.58, 69.37, 31.94, 31.92, 30.34, 29.75, 29.72, 29.69, 29.63, 29.58, 29.40, 29.35, 26.10, 22.68, 14.10. MS (MALDI): m/z 709.86 (calcd [M+H]+ = 709.62). Anal. calcd for C46H80N2O3: C, 77.91; H, 11.37, N: 3.95; found: C, 77.28; H, 10.51, N, 3.51%. 4-[4-(N,N-Didodecylamino)phenyl]pyrimidine (2c). White solid (yield = 14%).
1
H NMR (400 MHz,
CDCl3): δ 9.10 (d, J = 1.2 Hz, 1H), 8.56 (d, J = 5.6 Hz, 1H), 7.98 (d, J = 8.8 Hz, 2H), 7.54 (dd, J = 5.6 Hz, J = 1.2 Hz, 1H), 6.68 (d, J = 8.8 Hz, 2H), 3.32 (t, J = 7.6 Hz, 4H), 1.65–1.55 (m, 4H), 1.45–1.20 (m, 36 H), 0.88 (t, J = 6.8 Hz, 6H).
13
C{1H} NMR (100 MHz, CDCl3): δ 163.58, 158.80, 156.39, 150.31, 128.42,
122.22, 114.83, 111.23, 50.95, 32.76, 31.86, 29.60, 29.58, 29.55, 29.45, 29.30, 27.18, 27.05, 22.64, 14.07. MS (MALDI): m/z 507.75 (calcd [M+H]+ = 507.46). Anal. calcd for C34H57N3: C, 80.41; H, 11.31, N: 8.27; found: C, 78.82; H, 9.43, N, 7.15%. 4-(3,4-Didodecyloxyphenyl)quinoline (3a).
To a stirred solution of 8a (802 mg, 1.4 mmol) and
4-bromoquinoline (270 mg, 1.3 mmol) in THF (6 mL) was added Pd(PPh3)4 (150 mg, 0.13 mmol) and aqueous K2CO3 (2.0 M, 5 mL; Ar bubbled before use). The mixture was stirred for 12 h at 60 °C.
After
cooling to room temperature, the reaction mixture was poured into water, and extracted with CH2Cl2, three times. The combined organic layers were washed with brine, and dried over anhydrous Na2SO4.
After
filtration and evaporation, the product was purified by column chromatography (silica, hexane/ethyl acetate = 2/1 as an eluent), washed with methanol, and dried under vacuum to provide 3a as a white solid (yield = 553 mg, 69%).
1
H NMR (400 MHz, CDCl3): δ8.92 (d, J = 4.4 Hz, 1H), 8.16 (d, J = 8.4 Hz, 1H), 8.01 (d,
J = 8.4 Hz, 1H), 7.72 (dd, J = 8.4 Hz, J = 7.2 Hz, 1H), 7.51 (dd, J = 8.4 Hz, J = 7.2 Hz, 1H), 7.33 (d, J = 4.4 Hz, 1H), 7.06–7.00 (m, 3H), 4.09 (t, J = 6.4 Hz, 2H), 4.03 (t, J = 6.4 Hz, 2H), 1.90–1.80 (m, 4H), 1.55–1.25 (m, 36H), 0.90–0.86 (m, 6H).
13
C{1H} NMR (100 MHz, CDCl3): δ 149.98, 149.52, 149.00, 148.75,
148.46, 130.53, 129.83, 129.20, 126.95, 126.45, 126.01, 122.23, 121.23, 115.32, 113.49, 69.46, 69.30, 31.93,
S4
31.91, 29.71, 29.68, 29.67, 29.65, 29.62, 29.45, 29.43, 29.37, 29.35, 29.30, 26.08, 26.03, 22.68, 14.12. MS (MALDI): m/z 574.48 (calcd [M]•+ = 574.46). Anal. calcd for C39H59NO2: C, 81.62; H, 10.36, N: 2.44; found: C, 81.79; H, 10.96, N, 2.58%. 4-(3,4,5-tridodecyloxyphenyl)quinoline (3b) and 4-[4-(N,N-didodecylamino)phenyl]quinoline (3c) were prepared in similar manners to compound 3a. Spectroscopic data of these compounds are shown below. 4-(3,4,5-Tridodecyloxyphenyl)quinoline (3b).
White solid (yield = 84%).
1
H NMR (400 MHz,
CDCl3) δ 8.92 (d, J = 4.0 Hz, 1H), 8.17 (d, J = 8.4 Hz, 1H), 8.01 (d, J = 8.0 Hz, 1H), 7.73 (dd, J = 8.0 Hz, J = 7.2 Hz, 1H), 7.52 (dd, J = 8.4 Hz, J = 7.2 Hz, 1H), 7.35 (d, J = 4.0 Hz, 1H), 6.67 (s, 2H), 4.56 (t, J = 6.4 Hz, 2H), 3.99 (t, J = 6.4 Hz, 4H), 1.80–1.75 (m, 6H), 1.65–1.25 (m, 54H), 0.89–0.87 (m, 9H).
13
C{1H}
NMR (100 MHz, CDCl3): δ 153.16, 149.86, 148.81, 148.64, 138.45, 132.89, 129.77, 129.27, 126.86, 126.54, 126.02, 121.10, 108.24, 73.60, 69.31, 31.94, 31.90, 30.40, 29.77, 29.75, 29.70, 29.68, 29.64, 29.62, 29.40, 29.35, 26.16, 26.08, 22.69, 22.67, 14.09. MS (MALDI): m/z 758.91 (calcd [M+H]+ = 758.65). Anal. calcd for C51H83NO3: C, 80.79; H, 11.03, N: 1.85; found: C, 80.46; H, 11.89, N, 1.56%. 4-[4-(N,N-Didodecylamino)phenyl]quinoline (3c). Orange oil (yield = 93%).
1
H NMR (400 MHz,
CDCl3): δ 8.88 (d, J = 4.8 Hz, 1H), 8.16–8.12 (m, 2H), 7.72–7.67 (m, 1H), 7.51–7.46 (m, 1H), 7.40 (d, J = 8.8 Hz, 2H), 7.31 (d, J = 4.8 Hz, 1H), 6.76 (d, J = 8.8 Hz, 2H), 3.33 (t, J = 8.0 Hz, 4H), 1.70–1.60 (m, 4H), 1.40–1.20 (m, 36H), 0.88 (m, 6H).
13
C{1H} NMR (100 MHz, CDCl3): δ 149.98, 148.89, 148.86, 148.24,
130.77, 129.68, 128.97, 127.05, 126.31, 126.02, 124.08, 120.83, 111.24, 51.06, 31.90, 29.68, 29.66, 29.63, 29.61, 29.54, 29.34, 27.25, 27.18, 22.67, 14.10. MS (MALDI): m/z 556.74 (calcd [M]•+ = 556.48).
Anal.
Calcd for C39H60N2: C, 84.11; H, 10.86, N: 5.03; found: C, 76.72; H, 10.45, N, 4.67%. This compound was not further purified and used as-is in the next reaction. 1,3,5-Tris(4-(3,4-didodecyloxyphenyl)pyridiniummethyl)benzene Bromide (4a). A mixture of 1a (262 mg, 0.50 mmol) and 1,3,5-tris(bromomethyl)benzene (54 mg, 0.15 mmol) in 12 mL of dry THF/CH3CN (1:2, v/v) was stirred for 12 h at 60 °C. After cooling to room temperature, the reaction mixture was poured into acetone. The formed precipitate was separated by filtration, and washed with acetone, and dried under vacuum to afford 4a as a yellow waxy solid (yield = 235 mg, 81%).
1
H NMR (400 MHz, CDCl3): δ
10.10, (d, J = 6.4 Hz, 6H), 9.17 (s, 3H), 8.12 (d, J = 6.4 Hz, 6H), 7.38 (d, J = 8.0 Hz, 3H), 7.21 (s, 3H), 6.97 (d, J = 8.0 Hz, 3H), 5.85 (s, 6H), 4.08–4.03 (m, 12H), 1.87–1.72 (m, 18H), 1,50–1.20 (m, 162H), 0.88 (t, J = 13
C{1H} NMR (100 MHz, CDCl3): δ 156.06, 153.54, 149.95, 145.13, 135.43, 133.32,
6.4 Hz, 27 H)..
125.13, 123.94, 121.88, 113.17, 111.77, 69.59, 69.14, 61.84, 31.88, 29.68, 29.68, 29.63, 29.61, 29.59, 29.57, 29.38, 29.32, 29.16, 28.95, 25.95, 25.91, 22.65, 14.08. The other tripodal salts having bromide anions (4c, 5a–c and 6a–c) were prepared in similar manners to compound 4a.
Spectroscopic data of these compounds are shown below.
1,3,5-Tris(4-(4-N,N-didodecylaminophenyl)pyridiniummethyl)benzene Bromide (4c). Yellow solid (yield = 99%).
1
H NMR (400 MHz, CDCl3): δ 9.84 (d, J = 6.8 Hz, 6H), 9.17 (s, 3H), 7.96 (d, J = 6.8 Hz,
S5
6H), 7.66 (d, J = 9.2 Hz, 6H), 6.67 (d, J = 9.2 Hz, 6H), 5.72 (s, 6H), 3.34 (t, J = 7.6 Hz, 12H), 1.90–1.82 (m, 12H), 1.50–1.20 (m, 96H), 0.88 (t, J = 6.4 Hz, 18H).
13
C{1H} NMR (100 MHz, CDCl3): δ 154.94,
151.66, 144.25, 135.77, 133.11, 129.64, 121.39, 118.24, 112.07, 51.15, 50.39, 31.92, 29.65, 29.64, 29.60, 29.47, 29.35, 29.26, 27.27, 27.08, 24.77, 22.70, 14.14. 1,3,5-Tris(4-(3,4-didodecyloxyphenyl)pyrimidiniummethyl)benzene Bromide (5a). (yield = 83%).
Yellow solid
1
H NMR (400 MHz, CDCl3): δ 10.60 (s, 3H), 10.35 (d, J = 6.0 Hz, 3H), 9.35 (s, 3H),
8.20 (d, J = 6.0 Hz, 3H), 7.84 (dd, J = 8.8 Hz, J = 2.0 Hz, 3H), 7.81 (d, J = 2.0 Hz, 3H), 6.96 (d, J = 8.8 Hz, 3H), 5.88 (s, 6H), 4.09 (t, J = 6.4 Hz, 6H), 4.06 (t, J = 6.4 Hz, 6H), 1.90–1.82 (m, 12H), 1.50–1.20 (m, 96H), 0.88 (t, J = 6.4 Hz, 18H).
13
C{1H} NMR (100 MHz, CDCl3): δ 168.91, 156.26, 152.75, 150.51, 149.84,
134.97, 133.79, 129.71, 124.80, 124.65, 116.86, 112.62, 69.44, 69.35, 58.59, 31.91, 29.72, 29.68, 29.63, 29.59, 29.43, 29.36, 29.35, 29.11, 28.90, 25.98, 25.90, 22.67, 14.10. 1,3,5-Tris(4-(3,4,5-tridodecyloxyphenyl)pyrimidiniummethyl)benzene Bromide (5b). (yield = 66%).
Yellow solid
1
H NMR (400 MHz, CDCl3): δ 10.70 (s, 3H), 10.52 (d, J = 6.4 Hz, 3H), 9.43 (s, 3H),
8.23 (d, J = 6.4 Hz, 3H), 7.49 (s, 6H), 5.88 (s, 6H), 4.14 (t, J = 6.4 Hz, 6H), 4.04 (t, J = 6.4 Hz, 12H), 1.90–1.82 (m, 18H), 1.50–1.20 (m, 162H), 0.88 (m, 27H).
13
C{1H} NMR (100 MHz, CDCl3): δ 169.28,
153.79, 152.68, 151.01, 145.64, 134.86, 133.95, 126.54, 117.36, 107.78, 73.96, 69.57, 58.66, 31.89, 30.37, 29.71, 29.69, 29.66, 29.64, 29.61, 29.49, 29.39, 29.35, 29.34, 29.24, 26.04, 25.94, 22.66, 14.08. 1,3,5-Tris(4-(4-N,N-didodecylaminophenyl)pyrimidiniummethyl)benzene Bromide (5c). solid (yield = 81%).
Yellow
1
H NMR (400 MHz, CDCl3): δ 10.19 (s, 3H), 9.93 (d, J = 6.4 Hz, 3H), 9.25 (s, 3H),
8.08 (d, J = 9.2 Hz, 6H), 7.87 (d, J = 6.4 Hz, 6H), 6.65 (d, J = 9.2 Hz, 6H), 5.73 (s, 6H), 3.38 (t, J = 7.6 Hz, 12H), 1.80–1.72 (m, 12H), 1.50–1.20 (m, 96H), 0.88 (t, J = 6.4 Hz, 18H).
13
C{1H} NMR (100 MHz,
CDCl3): δ 166.68, 153.69, 152.04, 150.67, 148.23, 144.95, 135.32, 134.70, 133.38, 132.32, 118.74, 114.34, 111.97, 67.98, 57.75, 51.30, 33.88, 31.86, 29.59, 29.57, 29.55, 29.37, 29.29, 27.31, 26.98, 22.64, 20.63, 14.08. 1,3,5-Tris(4-(3,4-didodecyloxyphenyl)quinoliniummethyl)benzene Bromide (6a). = 82%).
1
Orange solid (yield
H NMR (400 MHz, CDCl3): δ 10.68 (d, J = 6.4 Hz, 3H), 9.26 (d, J = 8.8 Hz, 3H), 8.91 (s, 3H),
8.30 (dd, J = 8.8 Hz, J = 7.2 Hz, 3H), 8.29 (d, J = 8.4 Hz, 3H), 8.04 (J = 6.4 Hz, 3H), 7.75 (dd, J = 8.4 Hz, J = 7.2 Hz, 3H), 7.14 (d, J = 8.8 Hz, 3H), 7.13 (s, 3H), 7.05 (d, J = 8.8 Hz, 3H), 6.41 (s, 6H), 4.11 (t, J = 6.4 Hz, 6H), 4.04 (t, J = 6.4 Hz, 6H), 1.95–1.80 (m, 12H), 1.50–1.20 (m, 108H), 0.90–0.85 (m, 18H).
13
C{1H}
NMR (100 MHz, CDCl3): δ 159.58, 151.98, 149.68, 148.90, 138.25, 136.80, 134.55, 131.77, 129.69, 129.10, 128.21, 127.00, 123.71, 122.49, 120.89, 115.02, 113.20, 69.75, 69.28, 59.02, 31.94, 29.73, 29.68, 29.65, 29.46, 29.44, 29.38, 29.26, 29.14, 26.05, 22.70, 14.13. 1,3,5-Tris(4-(3,4,5-didodecyloxyphenyl)quinoliniummethyl)benzene Bromide (6b). (yield = 34%).
1
Orange solid
H NMR (400 MHz, CDCl3): δ 10.63 (d, J = 6.4 Hz, 3H), 9.25 (d, J = 8.8 Hz, 3H), 8.91
(s, 3H), 8.34–8.24 (m, 6H), 8.08 (d, J = 6.4 Hz, 3H), 7.78 (dd, J = 8.8 Hz, J = 7.6 Hz, 3H), 6.78 (s, 6H), 6.43
S6
(s, 6H), 4.08 (t, J = 6.4 Hz, 6H), 4.00 (t, J = 6.4 Hz, 6H), 1.85–1.77 (m, 18H), 1.50–1.20 (m, 162H), 0.88 (m, 27H).
13
C{1H} NMR (100 MHz, CDCl3): δ159.96, 153.77, 148.97, 140.72, 138.22, 136.85, 134.49,
131.80, 129.83, 129.52, 129.11, 128.43, 122.78, 120.85, 108.63, 73.79, 69.67, 59.13, 31.94, 31.91, 30.41, 29.76, 29.74, 29.70, 29.65, 29.63, 29,61, 29.43, 29.39, 29.37, 29.35, 26.11, 22.69, 22.67, 14.09. 1,3,5-Tris(4-(4-N,N-didodecyloxyphenyl)quinoliniummethyl)benzene Bromide (6c). Red solid (yield = 81%).
1
H NMR (400 MHz, CDCl3): δ10.48 (d, J = 6.4 Hz, 3H), 9.15 (d, J = 8.8 Hz, 3H), 8.87 (s, 3H),
8.34 (d, J = 8.4 Hz, 3H), 8.25 (dd, J = 8.8 Hz, J = 8.0 Hz, 3H), 7.96 (d, J = 6.4 Hz, 3H), 7.66 (dd, J = 8.8 Hz, J = 8.0 Hz, 3H), 7.52 (d, J = 8.8 Hz, 6H), 6.78 (d, J = 8.8 Hz, 6H), 6.31 (s, 6H), 3.38 (t, J = 6.4 Hz, 6H), 1.85–1.77 (m, 12H), 1.50–1.20 (m, 108H), 0.87 (t, J = 6.8 Hz, 27H).
13
C{1H} NMR (100 MHz, CDCl3):
δ 138.37, 136.25, 134.73, 132.53, 131.57, 129.27, 128.77, 127.39, 120.83, 120.76, 120.59, 111.76, 58.48, 51.13, 31.87, 29.92, 29.62, 29.59, 29.57, 29.48, 29.29, 27.21, 27.09, 22.64, 14.08. 1,3,5-Tris(4-(3,4-didodecyloxyphenyl)pyridiniummethyl)benzene Hexafluorophosphate (Py1). To a stirred solution of 4a (96.4 mg, 0.05 mmol) in MeOH (5 mL) was added dropwise a solution of NH4PF6 (81.5 mg, 0.50 mmol) in water (0.5 mL). The formed precipitate was separated by filtration, and washed with water and methanol, successively.
The residue was dissolved into chloroform and filtered. After
evaporation of the solvent, the residue was dried under vacuum to afford Py1 as a yellow waxy solid (yield = 67 mg, 63%).
1
H NMR (400 MHz, CDCl3): δ 8.84 (d, J = 6.4 Hz, 6H), 8.08 (d, J = 6.4 Hz, 6H), 7.96 (s,
3H), 7.39 (dd, J = 8.4 Hz, J = 2.0 Hz, 3H), 7.23 (d, J = 2.0 Hz, 3H), 6.96 (d, J = 8.4 Hz, 3H), 5.56 (s, 6H), 4.09–4.03 (m, 12H), 1.85–1.82 (m, 12H), 1.50–1.25 (m, 108H), 0.89–0.86 (m, 18H).
13
C{1H} NMR (100
MHz, CDCl3): δ 157.02, 153.91, 150.10, 143.71, 135.63, 131.79, 124.93, 124.34, 122.24, 113.24, 111.99, 69.63, 69.21, 62.69, 31.94, 29.74, 29.71, 29.68, 29.66, 29.64, 29.47, 29.40, 29.38, 29.22, 29.01, 26.02, 25.98, 22.70, 14.13.
MS (MALDI): m/z 1974.35 (calcd [M–PF6–3H]+ = 1974.29).
Anal. calcd for
C114H180F18N3O6P3: C, 64.48; H, 8.54; N, 1.98%; found: C, 64.46; H, 8.51; N, 2.27%. The other tripodal salts having hexafluorophosphate anions (Py3, Pm1–3, and Q1–3) were prepared in similar manners to compound Py1. Spectroscopic data of these compounds are shown below. 1,3,5-Tris(4-(4-N,N-didodecylaminophenyl)pyridiniummethyl)benzene Hexafluorophosphate (Py3). Yellow waxy solid (yield = 84%).
1
H NMR (400 MHz, CDCl3): δ 8.86 (d, J = 6.8 Hz, 6H), 8.16 (s, 3H),
7.95 (d, J = 6.8 Hz, 6H), 7.70 (d, J = 9.2 Hz, 6H), 6.68 (d, J = 9.2 Hz, 6H), 5.47 (s, 6H), 3.34 (t, J = 7.6 Hz, 12H), 1.80–1.72 (m, 12H), 1.50–1.20 (m, 96H), 0.88 (t, J = 6.4 Hz, 18H).
13
C{1H} NMR (100 MHz,
CDCl3): δ 155.49, 151.95, 142.96, 135.97, 131.82, 129.93, 121.50, 117.86, 112.16, 51.18, 31.93, 29.65, 29.63, 29.59, 29.47, 29.35, 27.27, 27.07, 22.69, 14.13. MS (MALDI): m/z 1924.75 (calcd [M–PF6–2H]+ = 1924.36).
Anal. calcd for C114H183F18N6P3: C, 66.06; H, 8.90; N, 4.05%; found: C, 66.27; H, 8.85; N,
4.41%. 1,3,5-Tris(4-(3,4-didodecyloxyphenyl)pyrimidiniummethyl)benzene Yellow waxy solid (yield = 75%).
1
Hexafluorophosphate
(Pm1).
H NMR (400 MHz, CDCl3): δ 9.42 (s, 3H), 8.78 (d, J = 6.4 Hz, 3H),
S7
8.09 (s, 3H), 7.91 (d, J = 4.8 Hz, 3H), 7.60–7.50 (m, 6H), 6.75 (d, J = 8.4 Hz, 3H), 5.65 (s, 6H), 3.96 (t, J = 6.4 Hz, 6H), 3.87 (t, J = 6.4 Hz, 6H), 1.80–1.72 (m, 12H), 1.50–1.20 (m, 96H), 0.88 (t, J = 6.4 Hz, 18H). 13
C{1H} NMR (100 MHz, CDCl3): δ 179.33, 168.99, 155.94, 151.88, 149.51, 148.94, 134.76, 132.50,
124.62, 124.52, 117.11, 112.43, 69.15, 59.25, 31.94, 29.80, 29.77, 29.69, 29.61, 29.54, 29.42, 29.40, 29.20, 29.03, 26.08, 25.99, 22.70, 14.12. MS (MALDI): m/z 1978.73 (calcd [M–PF6–2H]+ = 1978.29).
Anal.
calcd for C111H177F18N6O6P3: C, 62.69; H, 8.39; N, 3.95%; found: C, 62.73; H, 8.25; N, 3.94%. 1,3,5-Tris(4-(3,4,5-tridodecyloxyphenyl)pyrimidiniummethyl)benzene Hexafluorophosphate (Pm2). Yellow waxy solid (yield = 80%).
1
H NMR (400 MHz, CDCl3): δ 9.59 (s, 3H), 9.04 (d, J = 6.4 Hz, 3H),
8.21 (s, 3H), 8.13 (d, J = 6.4 Hz, 3H), 7.45 (s, 6H), 5.71 (s, 6H), 4.10 (t, J = 6.4 Hz, 6H), 4.02 (t, J = 6.4 Hz, 12H), 1.80–1.72 (m, 18H), 1.50–1.20 (m, 162H), 0.88 (m, 27H).
13
C{1H} NMR (100 MHz, CDCl3): δ
169.83, 153.81, 151.88, 149.54, 145.76, 134.76, 132.90, 126.61, 117.82, 108.04, 76.70, 73.99, 59.37, 31.95, 30.43, 29.77, 29.74, 29.71, 29.70, 29.68, 29.65, 29.56, 29.47, 29.40, 29.30, 26.14, 26.13, 22.71, 14.12. MS (MALDI): m/z 2531.96 (calcd [M–PF6–H]+ = 2531.84). Anal. calcd for C147H249F18N6O9P3: C, 65.89; H, 9.37; N, 3.14%; found: C, 66.34; H, 9.24; N, 3.23%. 1,3,5-Tris(4-(4-N,N-didodecyloxyphenyl)pyrimidiniummethyl)benzene Hexafluorophosphate (Pm3). Yellow waxy solid (yield = 84%).
1
H NMR (400 MHz, CDCl3): δ 9.17 (s, 3H), 8.61 (d, J = 6.4 Hz, 3H),
8.14–8.04 (m, 9H), 7.79 (d, J = 6.4 Hz, 3H), 6.65 (d, J = 10.0 Hz, 3H), 5.41 (s, 6H), 3.38 (t, J = 7.6 Hz, 12H), 1.80–1.72 (m, 12H), 1.50–1.20 (m, 96H), 0.88 (t, J = 6.4 Hz, 18H).
13
C{1H} NMR (100 MHz,
CDCl3): δ 166.82, 154.02, 151.17, 146.37, 135.41, 132.69, 132.24, 118.57, 114.53, 112.16, 58.44, 51.40, 31.91, 29.65, 29.63, 29.61, 29.58, 29.42, 29.35, 27.28, 27.02, 22.70, 14.15. MS (MALDI): m/z 1929.40 (calcd [M–PF6]+ = 1929.36). Anal. calcd for C111H180F18N9P3: C, 64.23; H, 8.74; N, 6.07%; found: C, 64.36; H, 8.67; N, 6.00%. 1,3,5-Tris(4-(3,4-didodecyloxyphenyl)quinoliniummethyl)benzene Orange waxy solid (yield = 89%).
1
Hexafluorophosphate
(Q1).
H NMR (400 MHz, CDCl3): δ 9.08 (d, J = 6.4 Hz, 3H), 8.35 (d, J =
8.0 Hz, 3H), 8.34 (d, J = 8.8 Hz, 3H), 8.01 (dd, J = 8.0 Hz, J = 7.6 Hz, 3H), 7.86 (d, J = 6.4 Hz, 3H), 7.76 (dd, J = 8.8 Hz, J = 7.6 Hz, 3H), 7.67 (s, 3H), 7.18 (s, 3H), 7.14 (d, 8.4 Hz, 3H), 7.03 (d, J = 8.4 Hz, 3H), 6.05 (s, 6H), 4.09 (t, J = 6.4 Hz, 6H), 4.03 (t, J = 6.4 Hz, 6H), 1.96–1.72 (m, 12H), 1.50–1.20 (m, 162H), 0.92–0.82 (m, 27H).
13
C{1H} NMR (100 MHz, CDCl3): δ 160.70, 151.94, 149.72, 147.18, 138.66,
136.07, 134.96, 129.79, 129.56, 129.39, 128.46, 127.00, 123.76, 122.27, 118.94, 114.96, 113.18, 69.57, 69.26, 59.47, 31.94, 29.74, 29.69, 29.67, 29.49, 29.46, 29.39, 29.25, 29.15, 26.05, 26.04, 14.13. MS (MALDI): m/z 2124.89 (calcd [M–PF6–2H]+ = 2125.35). Anal. calcd for C126H186F18N3O6P3: C, 66.56; H, 8.25; N, 1.85; found: C, 66.11; H, 8.11; N, 1.32%. 1,3,5-Tris(4-(3,4,5-tridodecyloxyphenyl)quinoliniummethyl)benzene Orange waxy solid (yield = 54%).
1
Hexafluorophosphate
(Q2).
H NMR (400 MHz, CDCl3): δ 9.06 (d, J = 6.4 Hz, 3H), 8.38 (d, J =
8.8 Hz, 3H), 8.37 (d, J = 8.8 Hz, 3H), 8.03 (dd, J = 8.8 Hz, J = 7.6 Hz, 3H), 7.80 (dd, J = 8.8 Hz, J = 7.6 Hz,
S8
3H), 6.81 (s, 6H), 6.07 (s, 6H), 4.07 (t, J = 6.4 Hz, 6H), 4.00 (t, J = 6.4 Hz, 6H), 1.80–1.72 (m, 18H), 1.50–1.20 (m, 162H), 0.88 (m, 27H).
13
C{1H} NMR (100 MHz, CDCl3): δ 161.21, 153.74, 147.15,
140.57, 138.68, 136.19, 134.87, 129.96, 129.65, 129.57, 129.48, 128.72, 122.54, 118.84, 108.54, 73.75, 69.52, 59.49, 31.96, 31.93, 30.43, 29.79, 29.73, 29.68, 29.66, 29.47, 29.42, 29.38, 26.14, 26.12, 22.69, 14.12. MS (MALDI): m/z 2679.45 (calcd [M–PF6]+ = 2679.91). Anal. calcd for C162H258F18N3O9P3: C, 68.83; H, 9.20; N, 1.49%; found: C, 68.53; H, 9.08; N, 1.84%. 1,3,5-Tris(4-(4-N,N-didodecylaminophenyl)quinoliniummethyl)benzene Hexafluorophosphate (Q3). Red waxy solid (yield = 97%).
1
H NMR (400 MHz, CDCl3): δ 8.97 (d, J = 6.4 Hz, 3H), 8.41 (d, J = 8.0
Hz, 3H), 8.23 (d, J = 8.8 Hz, 3H), 7.96 (dd, J = 8.0 Hz, J = 8.0 Hz, 3H), 7.82 (d, J = 6.4 Hz, 3H), 7.72–7.67 (m, 6H), 7.57 (d, J = 8.8 Hz, 6H), 6.79 (d, J = 8.8 Hz, 6H), 5.94 (s, 6H), 3.37 (t, J = 6.4 Hz, 12H), 1.80–1.72 (m, 12H), 1.50–1.20 (m, 108H), 0.87 (m, 18H).
13
C{1H} NMR (100 MHz, CDCl3): δ 160.17, 150.78,
146.20, 138.67, 135.62, 135.31, 132.85, 129.81, 128.96, 128.86, 127.55, 120.77, 120.47, 118.77, 111.93, 59.08, 51.18, 31.90, 29.67, 29.65, 29.63, 29.60, 29.51, 29.33, 27.27, 27.12, 22.67, 14.11. MS (MALDI): m/z 2071.89 (calcd [M–PF6–4H]+ = 2072.39). Anal. calcd for C126H189F18N6P3: C, 68.08; H, 8.57; N, 3.78%; found: C, 67.89; H, 8.66; N, 3.79%.
S3. Polarizing Optical Microscopic Image of Py1–3, Pm1–3 and Q1–3
Figure S1. Polarized optical micrographs of the tripodal salts (a) Py1 at 235 ºC, (b) Py2 at 170 ºC, (c) Py3 at 100 ºC, (d) Pm1 at 100 ºC, (e) Pm2 at 200 ºC, (f) Pm3 at 140 ºC, (g) Q1 at 100 ºC, (h) Q2 at 180 ºC and (i) Q3 at 100 ºC in the Col phases. Arrows indicate the directions of polarizer and analyzer axes.
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S3. Solvent Effects on the Photophysical Properties of Py1–3
Table S1. Solvent Effects on the Photophysical Properties of Tripodal Pyridinium Salts Py1–3 Py1 solvent
a
Py2
Py3
ET(30) λabs
λem
λabs
λem
λabs
λem
cyclohexane
30.9
372
509
370
508
430
548
toluene
33.9
378
507
379
526
447
498
THF
37.4
374
506
363
507
444
522
chloroform
39.1
386
505
379
526
460
510
dichloromethane
39.4
386
511
375
518
463
530
DMF
43.2
371
515
357
514
446
540
DMSO
45.1
371
514
356
515
445
541
acetonitrile
45.6
370
523
360
523
449
548
λabs: wavelengths of absorption maxima (nm); λem: wavelengths of emission maxima (nm).
S4. Fluorescent Lifetimes of Pm1–3 and Q1–3 Table S2. Fluorescent Lifetimes of the Tripodal Pyrimidinium and Quinolinium Salts in Thin Films as-spincoated filma compound
annealed filmb
λem / nm τ1 / ns
τ2 / ns
A1
A2
χ
τ1 / ns
τ2 / ns
A1
A2
χ
Pm1
495–633
6.2
11.81
0.90
0.10
1.018
3.8
9.8
0.92
0.08
1.112
Pm2
513–650
