S1
Electronic Supplementary Information
for
Synthesis of Carbazole-Based BODIPY Dimer Showing
Red Fluorescence in the Solid State
Chihiro Maeda,* Takumi Todaka, Tomomi Ueda and Tadashi Ema*
Division of Applied Chemistry, Graduate School of Natural Science and Technology, Okayama University,
Tsushima, Okayama 700-8530, Japan. E-mail: [email protected]: [email protected]
Table of Contents
[A] Instrumentation and Materials……………………………………………………….. S2
[B] Experimental Procedures and Compound Data………………………………….…… S2
[C] References………………...…………………………………………………………. S11
[D] NMR Spectra……………...…………………………………………………………. S12
[E] Fluorescence Lifetime………………………………………………………………. S32
[F] X-ray Crystal Structures……………………………………………………………. S34
Electronic Supplementary Material (ESI) for Organic & Biomolecular Chemistry.This journal is © The Royal Society of Chemistry 2017
S2
[A] Instrumentation and Materials1H and 13C NMR spectra were taken on a JEOL ECS-400 spectrometer, and chemical shifts are
reported as the delta scale in ppm using a solvent residual peak as an internal reference ( = 7.260
for 1H NMR, 77.00 for 13C NMR, in CDCl3). UV/vis absorption spectra were recorded on a
Shimadzu UV-2600 spectrophotometer. Fluorescence spectra were recorded on a JASCO FP-750 or
on a Hamamatsu Photonics C9920-02 spectrometer by the photon-counting method using an
integration sphere. HR mass spectra were taken on a Bruker micrOTOF. Unless otherwise noted,
materials obtained from commercial suppliers were used without further purification.
[B] Experimental Procedures and Compound Data
Scheme S1 Synthesis of 2a–c and 7
Synthesis of 5a and 6a. A flask containing 3,6-di-tert-butyl-1-bromocarbazole (3a)[S1] (359 mg,
1.00 mmol), benzobisthiazole (4)[S2] (48.1 mg, 251 mol), Pd(OAc)2 (22.5 mg, 100 mol), CuBr2
(22.3 mg, 100 mol), HP(t-Bu)3BF4 (58.0 mg, 200 mol), and Cs2CO3 (163 mg, 500 mol) was
purged with N2, charged with mesitylene (4 mL), and degassed. The mixture was heated at 160 C
for 16 h under N2. After cooling to rt, the mixture was diluted with CHCl3, washed with water, and
evaporated. Excess mesitylene was removed by distillation. The residue was purified by silica gel
chromatography with CHCl3 and recrystallized from CHCl3/MeOH to give 5a as a yellow solid
(34.5 mg, 46.2 mol, 18%) and 6a as a yellow solid (34.2 mg, 72.8 mol, 29%).
Compound data for 5a: 1H NMR (CDCl3, 400 MHz) δ = 10.72 (s,
2H, NH), 8.69 (s, 2H, Hf), 8.28 (d, J = 1.6 Hz, 2H, Hd), 8.15 (s, 2H,
Hc), 8.01 (d, J = 1.2 Hz, 2H, He), 7.59 (dd, J = 1.8, 8.6 Hz, 1H, Hb),
7.56 (d, J = 8.8 Hz, 1H, Ha), 1.57 (s, 18H, t-Bu), and 1.50 ppm (s,
18H, t-Bu); 13C NMR (CDCl3, 100 MHz) δ = 169.21, 152.24, 142.91, 142.27, 138.52, 136.31,
133.17, 125.03, 124.40, 122.97, 122.72, 120.17, 116.45, 115.09, 114.77, 110.82, 34.85, 34.81, and
32.07 ppm; HR-MS (APCl): m/z = 745.3426. calcd for C48H49N4S2: 745.3404 [MH]–.
S3
Compound data for 6a: 1H NMR (CDCl3, 400 MHz) δ = 10.73 (s, 1H,
NH), 9.08 (s, 1H, Hg), 8.72 (s, 1H, Hf or Hh), 8.67 (s, 1H, Hf or Hh), 8.28 (d,
J = 2.0 Hz, 1H, Hd), 8.14 (s, 1H, Hc), 7.97 (d, J = 2.0 Hz, 1H, He), 7.58 (dd,
J = 1.6, 8.4 Hz, 1H, Hb), 7.55 (d, J = 8.8 Hz, 1H, Ha), 1.54 (s, 9H, t-Bu), and 1.49 ppm (s, 9H, t-
Bu); 13C NMR (CDCl3, 100 MHz) δ = 154.70, 152.70, 142.98, 142.32, 138.51, 136.33, 133.27,
125.09, 124.44, 123.11, 122.70, 120.39, 116.47, 115.94, 115.15, 114.93, 110.81, 34.84, 34.82, and
32.07 ppm; HR-MS (APCI): m/z = 470.1708. calcd for C28H28N3S2: 470.1719 [M+H]+.
Synthesis of 2a. 5a (25.8 mg, 34.5 mol) was dissolved in dry
toluene (4.0 mL). Diisopropylethylamine (0.66 mL, 3.8 mmol) and
then BF3·OEt2 (0.24 mL, 1.9 mmol) were added, and the mixture
was heated at 80 C for 2 h under N2. After the solvents were removed, the residue was purified by
silica gel chromatography with CHCl3/hexane to give 2a as an orange solid (27.7 mg, 32.9 mol,
95%).1H NMR (CDCl3, 400 MHz) δ = 9.06 (s, 2H, Hf), 8.43 (d, J = 1.2 Hz, 2H, Hd), 8.14 (d, J = 1.6 Hz,
2H, Hc), 7.90 (d, J = 8.4 Hz, 2H, Ha), 7.78 (d, J = 1.6 Hz, 2H, He), 7.68 (dd, J = 1.8, 8.2 Hz, 2H, Hb),
1.51 (s, 18H, t-Bu), and 1.50 ppm (s, 18H, t-Bu); 13C NMR (CDCl3, 100 MHz) δ = 170.02, 144.37,
143.05, 142.38, 141.81, 139.64, 130.46, 126.33, 126.19, 125.52, 124.07, 119.62, 117.06, 113.87,
113.69, 107.72, 35.08, 34.91, 32.01, and 31.91 ppm; HR-MS (APCI): m/z = 842.3450. calcd for
C48H48N4S2B2F4: 842.3464 [M]−; UV/Vis (CH2Cl2) max () = 300 (17800), 342 (24000), 360
(23100), and 517 nm (54500 mol−1dm3cm−1).
Synthesis of 7. 6a (14.8 mg, 31.5 mol) was dissolved in dry CH2Cl2
(6.0 mL). Diisopropylethylamine (0.66 mL, 3.8 mmol) and then BF3·OEt2
(0.24 mL, 1.9 mmol) were added, and the mixture was stirred for 24 h under N2. After the solvents
were removed, the residue was passed through silica gel chromatography with CHCl3 to give 7 as
an orange solid (12.4 mg, 24.0 mol, 76%).1H NMR (CDCl3, 400 MHz) δ = 9.19 (s, 2H, Hg, Hh), 8.64 (s, 1H, Hf), 8.44 (d, J = 1.6 Hz, 1H,
Hd), 8.14 (d, J = 1.6 Hz, 1H, Hc), 7.89 (d, J = 8.4 Hz, 1H, Ha), 7.83 (d, J = 1.6 Hz, 1H, He), 7.66 (dd,
J = 2.2, 8.6 Hz, 1H, Hb), 1.53 (s, 9H, t-Bu), and 1.49 ppm (s, 9H, t-Bu); 13C NMR (CDCl3, 100
MHz) δ = 169.52, 157.03, 151.89, 144.09, 142.69, 142.07, 141.81, 139.46, 135.38, 128.15, 125.96,
125.74, 125.39, 124.02, 119.44, 116.94, 116.58, 113.96, 113.63, 107.95, 35.06, 34.86, 31.99, and
31.97 ppm; HR-MS (APCI): m/z = 517.1628. calcd for C28H26N3S2BF2: 517.1629 [M]+; UV/Vis
(CH2Cl2) max () = 293 (7400), 306 (7900), 336 (15500), and 417 nm (14100 mol−1dm3cm−1).
S4
Synthesis of 3b. To a solution of 3,6-bis(2,4,6-trimethylphenyl)carbazole[S3]
(807 mg, 2.00 mmol) in CHCl3 (20 mL) was added N-bromosuccinimide (356
mg, 2.00 mmol) at 0 °C, and the mixture was stirred for 3 h in the dark. The
mixture was passed through a pad of silica gel with CHCl3 and evaporated. The residue was
purified by silica gel chromatography with CHCl3/hexane to give 3b as a white solid (950 mg, 1.97
mmol, 98%).1H NMR (CDCl3, 400 MHz) δ = 8.31 (s, 1H, NH), 7.76 (d, J = 0.8 Hz, 1H, Hc), 7.72 (s, 1H, Hd),
7.57 (d, J = 8.0 Hz, 1H, Ha), 7.37 (d, J = 1.2 Hz, 1H, He), 7.24 (dd, J = 1.2, 8.4 Hz, 1H, Hb), 6.984
(s, 2H, m-Mes), 6.975 (s, 2H, m-Mes), 2.359 (s, 3H, p-Mes), 2.355 (s, 3H, p-Mes), 2.06 (s, 6H, o-
Mes), and 2.05 ppm (s, 6H, o-Mes); 13C NMR (CDCl3, 100 MHz) δ = 139.29, 138.38, 138.34,
137.33, 136.58, 136.38, 136.29, 133.95, 133.23, 129.23, 128.19, 128.13, 128.08, 124.90, 124.05,
121.31, 120.05, 111.02, 104.02, 20.96, and 20.87 ppm; HR-MS (APCI): m/z = 482.1316. calcd for
C30H27NBr: 482.1314 [MH]−.
Synthesis of 5b and 6b. A flask containing 3b (483 mg, 1.00 mmol), 4 (48.8 mg, 254 mol),
Pd(OAc)2 (23.4 mg, 104 mol), CuBr2 (23.2 mg, 10.4 mol), HP(t-Bu)3BF4 (57.6 mg, 199 mol),
and Cs2CO3 (164 mg, 503 mol) was purged with N2, charged with mesitylene (4 mL), and
degassed. The mixture was heated at 160 C for 16 h under N2. After cooling to rt, the mixture was
diluted with CHCl3, washed with water, and evaporated. Excess mesitylene was removed by
distillation. The residue was purified by silica gel chromatography with CHCl3 and GPC with
CHCl3 to give 5b as a brown solid (58.0 mg, 58.3 mol, 23%) and 6b as a brown solid (50.0 mg,
84.2 mol, 33%).
Compound data for 5b: 1H NMR (CDCl3, 400 MHz) δ = 11.07
(s, 2H, NH), 8.76 (s, 2H, Hf), 7.97 (s, 2H, Hd), 7.86 (s, 2H, Hc),
7.79 (d, J = 0.8 Hz, 2H, He), 7.71 (d, J = 8.4 Hz, 2H, Ha), 7.30 (dd,
J = 1.6, 8.4 Hz, 2H, Hb), 7.06 (s, 4H, m-Mes), 7.00 (s, 4H, m-Mes), 2.41 (s, 6H, p-Mes), 2.37 (s, 6H,
p-Mes), 2.14 (s, 12H, o-Mes), and 2.09 ppm (s, 12H, o-Mes); 13C NMR (CDCl3) δ = 168.85, 152.23,
139.53, 139.04, 138.71, 136.93, 136.74, 136.62, 136.43, 133.30, 133.01, 132.17, 128.29, 128.10,
126.88, 125.17, 124.34, 122.95, 121.11, 115.76, 114.97, 111.35, 21.10, 21.03, and 20.99 ppm; HR-
MS (APCl): m/z = 993.3994. calcd for C68H57N4S2: 993.4030 [MH]–.
Compound data for 6b: 1H NMR (CDCl3) δ = 11.05 (s, 1H, NH), 9.09 (s,
1H, Hg), 8.79 (s, 1H, Hf or Hh), 8.67 (s, 1H, Hf or Hh), 7.96 (s, 1H, Hd),
7.85 (s, 1H, Hc), 7.74 (s, 1H, He), 7.71 (d, J = 8.0 Hz, 1H, Ha), 7.29 (dd, J = 1.0, 8.6 Hz, 1H, Hb),
7.05 (s, 2H, m-Mes), 7.00 (s, 2H, m-Mes), 2.40 (s, 3H, p-Mes), 2.37 (s, 3H, p-Mes), 2.13 (s, 6H, o-
S5
Mes), and 2.08 ppm (s, 6H, o-Mes); 13C NMR (CDCl3) δ = 168.76, 152.11, 139.46, 138.92, 138.64,
136.95, 136.78, 136.64, 136.45, 133.18, 132.84, 132.01, 128.24, 128.19, 128.05, 126.78, 125.03,
124.25, 122.81, 121.01, 115.67, 114.94, 111.36, 21.13, 21.09, and 21.04 ppm; HR-MS (APCl): m/z
= 592.1911. calcd for C38H30N3S2: 592.1887 [MH]–.
Synthesis of 2b. 5b (33.6 mg, 33.8 mol) was dissolved in dry
toluene (4.0 mL). Diisopropylethylamine (0.66 mL, 3.8 mmol) and
then BF3·OEt2 (0.24 mL, 1.9 mmol) were added, and the mixture
was heated at 80 C for 2.5 h under N2. After the solvents were removed, the residue was purified
by silica gel chromatography with CHCl3 and recrystallized from CHCl3/MeOH to give 2b as an
orange solid (34.2 mg, 31.3 mol, 93%).1H NMR (CDCl3, 400 MHz) δ = 9.17 (s, 2H, Hf), 8.12 (d, J = 0.8 Hz, 2H, Hd), 8.04 (d, J = 8.4 Hz,
2H, Ha), 7.86 (s, 2H, Hc), 7.73 (d, J = 0.8 Hz, 2H, He), 7.39 (dd, J = 1.8, 7.8 Hz, 2H, Hb), 7.05 (s,
4H, m-Mes), 7.00 (s, 4H, m-Mes), 2.40 (s, 6H, p-Mes), 2.37 (s, 6H, p-Mes), 2.11 (s, 12H, Me), and
2.09 ppm (s, 12H, Me); 13C NMR (CDCl3, 100 MHz) δ = 170.12, 142.55, 142.40, 139.88, 139.32,
137.75, 137.45, 136.54, 134.44, 132.88, 130.75, 129.98, 129.36, 128.46, 128.12, 126.39, 124.39,
124.06, 121.63, 114.23, 114.13, 108.64, 21.06, and 20.98 ppm; HR-MS (APCI): m/z = 1090.4091.
calcd for C68H56N4S2B2F4: 1090.4094 [M]−; UV/Vis (CH2Cl2) max () = 302 (25800), 343 (28000),
362 (27100), and 516 nm (52300 mol−1dm3cm−1).
Synthesis of 5c and 6c. A flask containing 3,6-bis(3,5-di-tert-butylphenyl)-1-bromocarbaozle
(3c)[S4] (624 mg, 1.00 mmol), 4 (48.9 mg, 255 mol), Pd(OAc)2 (22.2 mg, 98.7 mol), CuBr2 (22.3
mg, 100 mol), HP(t-Bu)3BF4 (58.4 mg, 201 mol), and Cs2CO3 (163 mg, 500 mol) was purged
with N2, charged with mesitylene (4 mL), and degassed. The mixture was heated at 160 C for 16 h
under N2. After cooling to rt, the mixture was diluted with CHCl3, washed with water, and
evaporated. Excess mesitylene was removed by distillation. The residue was purified by silica gel
chromatography with CHCl3 and GPC with CHCl3 to give 5c as a yellow solid (160 mg, 125 mol,
49%) and 6c as a yellow solid (76.3 mg, 104 mol, 41%).
Compound data for 5c: 1H NMR (CDCl3) δ = 10.99 (s, 2H, NH),
8.74 (s, 2H, Hf), 8.45 (d, J = 1.2 Hz, 2H, Hd), 8.35 (s, 2H, Hc), 8.19
(d, J = 1.6 Hz, 2H, He), 7.78 (dd, J = 1.6, 8.4 Hz, 2H, Hb), 7.73 (d, J
= 8.8 Hz, 2H, Ha), 7.61 (d, J = 2.0 Hz, 4H, o-Ar), 7.56 (d, J = 1.2 Hz, 4H, o-Ar), 7.54 (t, J = 1.6 Hz,
2H, p-Ar), 7.46 (t, J = 1.8 Hz, 2H, p-Ar), 1.49 (s, 36H, t-Bu), and 1.44 ppm (s, 36H, t-Bu); 13C
NMR (CDCl3) δ = 168.73, 152.15, 151.48, 151.14, 141.53, 141.16, 139.63, 137.27, 135.14, 134.67,
S6
133.27, 126.66, 125.49, 123.34, 122.63, 122.16, 121.97, 121.31, 120.82, 119.25, 115.71, 114.85,
111.47, 35.14, 35.04, 31.71, and 31.65 ppm; HR-MS (APCl): m/z = 1273.7152. calcd for
C88H97N4S2: 1273.7160 [M−H]−.
Compound data for 6c: 1H NMR (CDCl3) δ = 11.02 (s, 1H, NH), 9.10 (s,
1H, Hg), 8.79 (s, 1H, Hf or Hh), 8.69 (s, 1H, Hf or Hh), 8.47 (s, 1H, Hd), 8.37
(s, 1H, Hc), 8.17 (s, 1H, He), 7.78 (d, J = 8.8 Hz, 1H, Hb), 7.73 (d, J = 8.4 Hz, 1H, Ha), 7.59 (d, J =
1.6 Hz, 2H, o-Ar), 7.56 (s, 2H, o-Ar), 7.52 (t, J = 1.2 Hz, 1H, p-Ar), 7.46 (t, J = 1.6 Hz, 1H, p-Ar),
1.46 (s, 18H, t-Bu), and 1.44 ppm (s, 18H, t-Bu); 13C NMR (CDCl3) δ = 168.90, 154.27, 152.10,
151.38, 151.11, 141.55, 140.92, 139.49, 137.08, 135.03, 134.38, 132.82, 126.56, 125.26, 123.27,
122.31, 121.95, 121.93, 121.17, 120.77, 119.19, 115.54, 115.38, 114.77, 111.32, 35.06, 35.02, and
31.68 ppm; HR-MS (APCl): m/z = 734.3594. calcd for C48H52N3S2: 734.3597 [M+H]+.
Synthesis of 2c. 5c (51.0 mg, 40.0 mol) was dissolved in dry
toluene (4.0 mL). Diisopropylethylamine (0.66 mL, 3.8 mmol) and
then BF3·OEt2 (0.24 mL, 1.9 mmol) were added, and the mixture
was heated at 80 C for 1 h under N2. After the solvents were removed, the residue was purified by
silica gel chromatography with CHCl3 to give 2c as a red solid (49.0 mg, 35.7 mol, 89%).1H NMR (CDCl3, 400 MHz) δ = 9.17 (s, 2H, Hf), 8.61 (d, J = 0.8 Hz, 2H, Hd), 8.38 (d, J = 1.2 Hz,
2H, Hc), 8.07−8.05 (m, 4H, Ha, He), 7.87 (dd, J = 1.6, 8.4 Hz, 2H, Hb), 7.58 (d, J = 1.2 Hz, 4H, o-
Ar), 7.55 (s, 6H, o-Ar, p-Ar), 7.48 (t, J = 1.6 Hz, 2H, p-Ar), 1.48 (s, 36H, t-Bu), and 1.44 ppm (s,
36H, t-Bu); 13C NMR (CDCl3) δ = 170.06, 151.73, 151.20, 143.00, 142.45, 141.36, 140.28, 136.46,
135.30, 130.69, 128.36, 127.74, 126.41, 124.70, 122.64, 122.04, 121.77, 121.02, 119.94, 114.36,
114.02, 108.56, 35.14, 35.06, and 31.65 ppm; HR-MS (APCl): m/z = 1370.7176. calcd for
C88H96N4S2B2F4: 1370.7229 [M]−; UV/Vis (CH2Cl2) max () = 257 (88400), 351 (30000), 369
(32900), and 530 nm (48400 mol−1dm3cm−1).
Scheme S2 Synthesis of 2d–g
S7
Synthesis of 5d. A flask containing 6a (117 mg, 249 mol), 3b
(256 mg, 531 mol), Pd(OAc)2 (11.0 mg, 48.9 mol), CuBr2 (12.2
mg, 54.7 mol), HP(t-Bu)3BF4 (30.0 mg, 103 mol), and Cs2CO3
(81.2 mg, 249 mol) was purged with N2, charged with mesitylene
(2 mL), and degassed. The mixture was heated at 160 C for 48 h under N2. After cooling to rt, the
mixture was diluted with CHCl3, washed with water, and evaporated. Excess mesitylene was
removed by distillation. The residue was purified by silica gel chromatography with CHCl3 and
recrystallized from CHCl3/MeOH. The crude product was purified by GPC with CHCl3 to give 5d
as a yellow solid (58.5 mg, 67.2 mol, 27%).1H NMR (CDCl3) δ = 11.07 (s, 1H, NH), 10.76 (s, 1H, NH), 8.74 (s, 1H, Hf or Hg), 8.68 (s, 1H,
Hf or Hg), 8.29 (d, J = 1.2 Hz, 1H, Hd), 8.15 (s, 1H, Hc), 8.00 (d, J = 2.0 Hz, 1H, He), 7.97 (s, 1H,
Hi), 7.87 (s, 1H, Hj), 7.79 (d, J = 1.2 Hz, 1H, Hh), 7.73 (d, J = 8.4 Hz, 1H, Hl), 7.58 (dd, J = 1.6, 8.4
Hz, 1H, Hb), 7.56 (d, J = 8.4 Hz, 1H, Ha), 7.31 (dd, J = 1.4, 8.2 Hz, 1H, Hk), 7.06 (s, 2H, m-Mes),
7.01 (s, 2H, m-Mes), 2.41 (s, 3H, p-Mes), 2.38 (s, 3H, p-Mes), 2.15 (s, 6H, o-Mes), 2.10 (s, 6H, o-
Mes), 1.56 (s, 9H, t-Bu), and 1.49 ppm (s, 9H, t-Bu); 13C NMR (CDCl3) δ = 169.19, 168.56, 152.15,
151.96, 142.72, 142.07, 139.48, 138.93, 138.67, 138.31, 136.94, 136.78, 136.66, 136.46, 136.12,
133.09, 133.04, 132.81, 131.99, 128.24, 128.17, 128.05, 126.77, 125.00, 124.80, 124.37, 124.19,
122.86, 122.47, 121.02, 120.21, 116.39 115.71, 114.83, 114.78, 111.36, 110.77, 34.79, 32.04, 21.15,
and 21.06 ppm; HR-MS (APCl): m/z = 871.3834. calcd for C58H55N4S2: 871.3863 [M+H] +.
Synthesis of 2d. 5d (25.6 mg, 29.4 mol) was dissolved in dry
toluene (4.0 mL). Diisopropylethylamine (0.66 mL, 3.8 mmol) and
then BF3·OEt2 (0.24 mL, 1.9 mmol) were added, and the mixture
was heated at 80 C for 3 h under N2. After the solvents were removed, the residue was purified by
silica gel chromatography with CHCl3 to give 2d as a red solid (23.8 mg, 24.6 mol, 84%).1H NMR (CDCl3) δ = 9.14 (s, 1H, Hf or Hg), 9.12 (s, 1H, Hf or Hg), 8.48 (d, J = 1.6 Hz, 1H, Hd),
8.15 (d, J = 1.6 Hz, 1H, Hc), 8.11 (d, J = 0.8 Hz, 1H, Hi), 8.05 (d, J = 7.6 Hz, 1H, Hl), 7.89−7.86 (m,
3H, Ha, He, Hj), 7.72 (d, J = 1.2 Hz, 1H, Hh), 7.67 (dd, J = 1.6, 8.8 Hz, 1H, Hb), 7.40 (dd, J = 1.4,
8.2 Hz, 1H, Hk), 7.05 (s, 2H, m-Mes), 7.01 (s, 2H, m-Mes), 2.40 (s, 3H, p-Mes), 2.37 (s, 3H, p-Mes),
2.11 (s, 6H, o-Mes), 2.09 (s, 6H, o-Mes), 1.55 (s, 9H, t-Bu), and 1.49 ppm (s, 9H, t-Bu); 13C NMR
(CDCl3) δ = 170.12, 169.88, 144.29, 143.00, 142.48, 142.24, 142.19, 141.56, 139.70, 139.59,
139.28, 137.71, 137.45, 136.58, 134.25, 132.71, 130.57, 130.47, 129.79, 129.25, 128.38, 128.07,
126.60, 126.21, 126.04, 125.53, 124.32, 123.98, 123.91, 121.56, 119.66, 117.08, 114.16, 113.95,
113.53, 108.60, 107.61, 35.09, 34.86, 31.94, 31.90, 21.11, and 21.04 ppm; HR-MS (APCl): m/z =
S8
966.3815. calcd for C58H52N4S2B2F4: 966.3779 [M]−; UV/Vis (CH2Cl2) max () = 306 (17100), 342
(24200), 361 (24600), and 517 nm (52600 mol−1dm3cm−1).
Synthesis of 5e. A flask containing 6a (117 mg, 249 mol), 3c
(311 mg, 499 mol), Pd(OAc)2 (11.2 mg, 49.8 mol), CuBr2 (11.1
mg, 49.8 mol), HP(t-Bu)3BF4 (28.4 mg, 97.9 mol), and Cs2CO3
(82.3 mg, 252 mol) was purged with N2, charged with mesitylene (2 mL), and degassed. The
mixture was heated at 160 C for 48 h under N2. After cooling to rt, the mixture was diluted with
CHCl3, washed with water, and evaporated. Excess mesitylene was removed by distillation. The
residue was purified by silica gel chromatography with CHCl3 and recrystallized from
CHCl3/MeOH. The crude product was purified by GPC with CHCl3 to give 5e as a yellow solid
(82.4 mg, 81.5 mol, 33%).1H NMR (CDCl3) δ = 10.94 (s, 1H, NH), 10.58 (s, 1H, NH), 8.65 (s, 1H, Hf or Hg), 8.60 (s, 1H,
Hf or Hg), 8.40 (d, J = 1.2 Hz, 1H, Hi), 8.24 (d, J = 1.6 Hz, 1H, Hd), 8.20 (s, 1H, Hj), 8.19 (d, J = 1.6
Hz, 1H, Hh), 8.05 (d, J = 1.6 Hz, 1H, Hc), 8.00 (d, J = 2.0 Hz, 1H, He), 7.72 (dd, J = 1.8, 8.2 Hz, 1H,
Hk), 7.63−7.61 (m, 3H, Hl, o-Ar), 7.59−7.56 (m, 3H, Hb, o-Ar), 7.54 (t, J = 1.8 Hz, 1H, p-Ar), 7.51
(d, J = 8.8 Hz, 1H, Ha), 7.47 (t, J = 1.6 Hz, 1H, p-Ar), 1.49 (s, 18H, t-Bu), and 1.45 ppm (s, 36H, t-
Bu); 13C NMR (CDCl3) δ = 168.85, 168.24, 151.94, 151.40, 151.02, 142.29, 141.71, 141.52, 141.01,
139.25, 137.95, 137.06, 135.91, 134.65, 133.92, 132.71, 132.63, 129.02, 128.21, 126.58, 125.28,
125.20, 125.02, 124.57, 123.93, 122.80, 122.58, 122.26, 122.02, 121.25, 120.79, 120.09, 119.07,
116.16, 115.42, 114.56, 114.39, 114.07, 110.79, 110.73, 35.13, 35.02, 34.78, 34.60, 32.13, 31.91,
31.68, and 31.66 ppm; HR-MS (APCl): m/z = 1011.5420. calcd for C68H75N4S2: 1011.5428 [M+H]+.
Synthesis of 2e. 5e (51.7 mg, 51.1 mol) was dissolved in dry
toluene (4.0 mL). Diisopropylethylamine (0.66 mL, 3.8 mmol) and
then BF3·OEt2 (0.24 mL, 1.9 mmol) were added, and the mixture
was heated at 80 C for 1.5 h under N2. After the solvents were removed, the residue was purified
by silica gel chromatography with CHCl3 to give 2e as a red solid (50.4 mg, 45.5 mol, 89%).1H NMR (CDCl3) δ = 9.13 (s, 1H, Hf or Hg), 9.10 (s, 1H, Hf or Hg), 8.58 (s, 1H, Hi), 8.47 (d, J =
1.2 Hz, 1H, Hd), 8.35 (d, J = 1.6 Hz, 1H, Hj), 8.13 (d, J = 1.6 Hz, 1H, Hc), 8.06 (d, J = 1.6 Hz, 1H,
Hh), 8.04 (d, J = 8.4 Hz, 1H, Hl), 7.88−7.84 (m, 3H, Ha, He, Hk), 7.66 (dd, J = 2.0, 8.8 Hz, 1H, Hb),
7.57 (d, J = 1.6 Hz, 2H, o-Ar), 7.54 (m, 3H, o-Ar, p-Ar), 7.48 (t, J = 1.8 Hz, 1H, p-Ar), 1.56 (s, 9H,
t-Bu), 1.49 (s, 9H, t-Bu), 1.47 (s, 18H, Ar), and 1.44 ppm (s, 18H, Ar); 13C NMR (CDCl3) δ =
170.32, 170.08, 151.77, 151.27, 144.30, 143.02, 142.59, 142.30, 141.78, 141.53, 140.40, 140.35,
S9
139.73, 137.72, 136.47, 135.32, 130.66, 130.52, 128.23, 127.65, 126.97, 126.41, 126.35, 126.25,
125.42, 124.75, 124.05, 122.58, 122.05, 121.74, 121.03, 119.90, 119.64, 116.99, 114.23, 113.80,
113.75, 113.69, 35.17, 35.10, 34.87, 32.00, 31.97, and 31.70 ppm; HR-MS (APCl): m/z =
1106.5320. calcd for C68H72N4S2B2F4: 1106.5347 [M]−; UV/Vis (CH2Cl2) max () = 345 (29400),
364 (29700), and 523 nm (54000 mol−1dm3cm−1).
Synthesis of 5f. A flask containing 6b (148 mg, 249 mol), 3c
(311 mg, 499 mol), Pd(OAc)2 (11.3 mg, 50.2 mol), CuBr2 (10.7
mg, 48.0 mol), HP(t-Bu)3BF4 (29.2 mg, 101 mol), and Cs2CO3
(82.2 mg, 252 mol) was purged with N2, charged with mesitylene (2 mL), and degassed. The
mixture was heated at 160 C for 48 h under N2. After cooling to rt, the mixture was diluted with
CHCl3, washed with water, and evaporated. Excess mesitylene was removed by distillation. The
residue was purified by silica gel chromatography with CHCl3 and recrystallized from
CHCl3/MeOH. The crude product was purified by GPC with CHCl3 to give 5f as a yellow solid
(95.2 mg, 83.8 mol, 34%).1H NMR (CDCl3) δ = 11.07 (s, 2H, NH), 8.77 (s, 1H, Hf or Hg), 8.76 (s, 1H, Hf or Hg), 8.47 (d, J
= 1.2 Hz, 1H, Hi), 8.38 (s, 1H, Hj), 8.19 (d, J = 1.2 Hz, 1H, Hh), 7.97 (d, J = 1.2 Hz, 1H, Hd), 7.86 (s,
1H, Hc), 7.80 (d, J = 1.2 Hz, 1H, He), 7.79 (dd, J = 1.6, 7.2 Hz, 1H, Hk), 7.74 (d, J = 8.8 Hz, 2H, Ha,
Hl), 7.60 (d, J = 2.0 Hz, 2H, o-Ar), 7.57 (d, J = 1.6 Hz, 2H, o-Ar), 7.53 (t, J = 1.6 Hz, 1H, p-Ar),
7.46 (t, J = 1.6 Hz, 1H, p-Ar), 7.31 (dd, J = 1.8, 8.2 Hz, 1H, Hb), 7.06 (s, 2H, m-Mes), 7.01 (s, 2H,
m-Mes), 2.41 (s, 3H, p-Mes), 2.37 (s, 3H, p-Mes), 2.15 (s, 6H, p-Mes), 2.09 (s, 6H, p-Mes), 1.48 (s,
18H, t-Bu), and 1.44 ppm (s, 18H, t-Bu); 13C NMR (CDCl3) δ = 168.93, 168.85, 152.31, 152.24,
151.48, 151.21, 141.56, 141.09, 139.74, 139.57, 139.11, 138.75, 137.36, 136.91, 136.80, 136.74,
136.61, 136.42, 135.28, 134.79, 133.37, 133.10, 132.27, 128.33, 128.13, 126.96, 126.84, 125.53,
125.27, 124.41, 123.45, 123.03, 122.70, 122.14, 122.02, 121.32, 121.16, 120.89, 119.42, 115.85,
115.82, 115.00, 114.98, 111.54, 111.38, 35.13, 35.07, 31.68, 31.66, 21.09, 21.03, and 20.97 ppm;
HR-MS (APCl): m/z = 1135.5737. calcd for C78H79N4S2: 1135.5741 [M+H]+.
Synthesis of 2f. 5f (26.0 mg, 22.9 mol) was dissolved in dry
toluene (2.0 mL). Diisopropylethylamine (0.66 mL, 3.8 mmol) and
then BF3·OEt2 (0.24 mL, 1.9 mmol) were added, and the mixture
was heated at 50 C for 3 h under N2. After the solvents were removed, the residue was passed
through a pad of silica gel with CHCl3/hexane and evaporated to dryness. The crude product was
recrystallized from CHCl3/MeOH to give 2f as a red solid (21.6 mg, 17.5 mol, 76%).
S10
1H NMR (CDCl3) δ = 9.182 (s, 1H, Hf or Hg), 9.175 (s, 1H, Hf or Hg), 8.62 (d, J = 1.2 Hz, 1H, Hi),
8.37 (d, J = 1.6 Hz, 1H, Hj), 8.12 (d, J = 0.8 Hz, 1H, Hd), 8.08 (d, J = 1.6 Hz, 1H, Hh), 8.06 (d, J =
8.0 Hz, 2H, Ha, Hl), 7.87 (dd, J = 1.6, 8.8 Hz, 1H, Hk), 7.86 (d, J = 1.2 Hz, 1H, Hc), 7.73 (d, J = 1.2
Hz, 1H, He), 7.57 (d, J = 1.6 Hz, 2H, o-Ar), 7.54 (s, 3H, o-Ar, p-Ar), 7.47 (t, J = 1.8 Hz, 1H, p-Ar),
7.40 (dd, J = 1.4, 8.2 Hz, 1H, Hb), 7.06 (s, 2H, m-Mes), 7.00 (s, 2H, m-Mes), 2.40 (s, 3H, p-Mes),
2.37 (s, 3H, p-Mes), 2.12 (s, 6H, p-Mes), 2.09 (s, 6H, p-Mes), 1.47 (s, 18H, t-Bu), and 1.44 ppm (s,
18H, t-Bu); 13C NMR (CDCl3) δ = 169.99, 151.66, 151.12, 142.85, 142.36, 142.26, 141.27, 140.16,
139.75, 139.28, 137.71, 137.43, 136.57, 136.40, 135.16, 134.25, 132.72, 130.65, 130.60, 129.86,
129.26, 128.38, 128.06, 127.77, 126.25, 124.63, 124.29, 123.95, 122.68, 122.05, 121.74, 121.53,
121.01, 120.01, 114.30, 114.21, 114.06, 114.03, 108.58, 108.48, 35.11, 35.02, 31.62, 21.10, and
21.03 ppm; HR-MS (APCl): m/z = 1230.5693. calcd for C78H76N4S2B2F4: 1230.5662 [M]−; UV/Vis
(CH2Cl2) max () = 347 (27900), 366 (28300), and 523 nm (47600 mol−1dm3 cm−1).
Synthesis of 3,6-bis[3,5-bis(trifluoromethyl)phenyl]carbazole.
3,6-Dibromocarbazole (1.29 g, 3.97 mmol), Pd(PPh3)4 (123 mg, 106
mmol), and Cs2CO3 (5.02 g, 15.4 mmol) in toluene/EtOH/H2O
(17/8/8 mL) was degassed and then heated at 100 C for 14 h under N2. After cooling to rt, the
organic layer was extracted with CH2Cl2 and evaporated. The residue was purified by silica gel
chromatography with CH2Cl2/hexane. Recrystallization from CH2Cl2/hexane gave the product as a
white solid (1.81 g, 3.06 mmol, 77%).1H NMR (CDCl3) δ = 8.40 (d, J = 0.8 Hz, 2H, Hc), 8.37 (s, 1H, NH), 8.15 (s, 4H, o-Ar), 7.86 (s,
2H, p-Ar), 7.73 (dd, J = 1.8, 8.2 Hz, 2H, Hb), and 7.61 ppm (d, J = 8.4 Hz, 2H, Ha); 13C NMR
(CDCl3) δ = 144.13, 140.47, 132.39 (q, J = 35 Hz), 130.73, 127.30, 125.96, 124.24, 123.63 (q, J =
271 Hz), 120.31 (sep, J = 3.8 Hz), 119.44, and 111.75 ppm; HR-MS (APCl): m/z = 590.0817 calcd
for C28H12NF12: 590.0784 [M−H]−.
Synthesis of 3,6-bis[3,5-bis(trifluoromethyl)phenyl]-1-bromocarbazole (3d).
To a solution of 3,6-bis[3,5-bis(trifluoromethyl)phenyl]carbazole
(57.7 mg, 97.6 μmol) in CHCl3 (10 mL) was added N-
bromosuccinimide (18.0 mg, 101 μmol) at 0 °C, and the mixture was
stirred for 6 h in the dark. The mixture was passed through a pad of silica gel with CHCl3, and
evaporated to dryness. The residue was purified by silica gel chromatography with CHCl3/hexane to
give 3d as a white solid (55.9 mg, 83.4 μmol, 85%).1H NMR (CDCl3) δ = 8.51 (s, 1H, NH), 8.37 (d, J = 2.0 Hz, 1H, Hc), 8.33 (d, J = 1.2 Hz, 1H, Hd),
8.14 (s, 2H, o-Ar), 8.12 (s, 2H, o-Ar), 7.884−7.875 (m, 3H, He, p-Ar), 7.78 (dd, J = 1.8, 8.2 Hz, 1H,
S11
Hb), and 7.68 ppm (d, J = 8.4 Hz, 1H, Ha); 13C NMR (CDCl3) δ = 143.81, 142.92, 140.02, 139.07,
132.58 (q, J = 35 Hz), 132.47 (q, J = 35 Hz), 132.15, 131.42, 127.91, 127.36, 126.68, 125.15,
124.62, 123.58 (q, J = 271 Hz), 123.51 (q, J = 271 Hz), 120.84 (sep, J = 3.8 Hz), 120.53 (sep, J =
3.8 Hz), 119.95, 118.53, 112.22, and 105.27 ppm; HR-MS (APCl): m/z = 669.9869 calcd for
C28H11NF12Br: 669.9870 [M−H]−.
Synthesis of 2g. A flask containing 6b (148 mg, 249 mol), 3d
(336 mg, 501 mol), Pd(OAc)2 (11.7 mg, 52.0 mol), CuBr2 (11.5
mg, 51.6 mol), HP(t-Bu)3BF4 (28.6 mg, 98.6 mol), and Cs2CO3
(81.0 mg, 248 mol) was purged with N2, charged with mesitylene (4 mL), and degassed. The
mixture was heated at 160 C for 48 h under N2. After cooling to rt, the mixture was diluted with
CHCl3, washed with water, and evaporated. Excess mesitylene was removed by distillation. The
residue was purified by silica gel chromatography with CHCl3, recrystallized from CHCl3/MeOH,
and then purified by GPC with CHCl3 to give 5g as a crude product. The crude product was
dissolved in dry toluene (4.0 mL). Diisopropylethylamine (0.66 mL, 3.8 mmol) and then BF3·OEt2
(0.24 mL, 1.9 mmol) were added, and the mixture was heated at 80 C for 1.5 h under N2. After the
solvents were removed, the residue was purified by silica gel chromatography with CHCl3/hexane
to give 2g as a red solid (73.6 mg, 57.5 mol, 23%).1H NMR (CDCl3) δ = 9.18 (s, 1H, Hf or Hg), 9.17 (s, 1H, Hf or Hg), 8.64 (d, J = 1.2 Hz, 1H, Hi),
8.46 (d, J = 1.6 Hz, 1H, Hj), 8.21 (s, 2H, o-Ar), 8.18 (s, 2H, o-Ar), 8.15 (d, J = 1.2 Hz, 1H, Hd or
Hh), 8.14 (s, 1H, Hd or Hh), 8.13 (d, J = 7.6 Hz, 1H, He), 8.03 (d, J = 8.4 Hz, 1H, Ha), 7.97 (s, 1H, p-
Ar), 7.91 (dd, J = 1.6, 8.4 Hz, 1H, Hk), 7.90 (s, 1H, p-Ar), 7.86 (s, 1H, Hc), 7.72 (d, J = 0.8 Hz, 1H,
He), 7.40 (dd, J = 1.4, 8.6 Hz, 1H, Hb), 7.06 (s, 2H, m-Mes), 7.01 (s, 2H, m-Mes), 2.41 (s, 3H, p-
Mes), 2.38 (s, 3H, p-Mes), 2.12 (s, 6H, o-Mes), and 2.10 ppm (s, 6H, o-Mes); 13C NMR couldn’t
detect peaks due to serious low solubility; HR-MS (APCl): m/z = 1278.2675. calcd for
C66H40N4S2B2F16: 1278.2650 [M]−; UV/Vis (CH2Cl2) max () = 309 (42500), 343 (29600), 364
(30700), and 515 nm (56700 mol−1dm3cm−1).
[C] References
[S1] C. Maeda, T. Todaka, T. Ueda and T. Ema, Chem.–Eur. J., 2016, 22, 7508.
[S2] J. F. Mike, J. J. Inteman, A. Ellern and M. Jeffries-EL, J. Org. Chem., 2010, 75, 495.
[S3] C. Maeda, T. Todaka and T. Ema, Org. Lett., 2015, 17, 3090.
[S4] C. Maeda, K. Nagahata and T. Ema, Org. Biomol, Chem., 2017, 15, 7783.
S12
[D] NMR spectra
abun
danc
e0
1.0
2.0
3.0
4.0
5.0
6.0
X : parts per Million : Proton
10.0 9.0 8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 0
10.
724
8.
688
8.
286
8.
282
8.
154
8.
008
8.
005
7.
599
7.
594
7.
577
7.
573
7.
568
7.
546
7.
260
1.
569
1.
503
19.1
318
.33
4.48
2.02
2.01
2.00
1.94
1.82
abun
danc
e0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
X : parts per Million : Proton
8.8 8.7 8.6 8.5 8.4 8.3 8.2 8.1 8.0 7.9 7.8 7.7 7.6 7.5 7.4
8.
688
8.
286
8.
282
8.
154
8.
008
8.
005
7.
599
7.
594
7.
577
7.
573
7.
568
7.
546
19.1
3
18.3
3
4.48
2.02
2.01
2.00
1.94
1.82
400 MHz 1H NMR spectrum of 5a in CDCl3
(tho
usan
dths
)0
2.0
4.0
6.0
8.0
10.0
12.0
14.0
16.0
X : parts per Million : Carbon13
170.0 160.0 150.0 140.0 130.0 120.0 110.0 100.0 90.0 80.0 70.0 60.0 50.0 40.0 30.0 20.0 10.0
169
.209
152
.236
142
.909
142
.269
138
.517
136
.312
133
.171
125
.028
124
.398
122
.966
122
.718
120
.169
116
.446
115
.090
114
.766
110
.823
77.
000
34.
852
34.
814
32.
074
100 MHz 13C NMR spectrum of 5a in CDCl3
S13
abun
danc
e0
2.0
4.0
6.0
8.0
10.0
12.0
X : parts per Million : Proton
11.0 10.0 9.0 8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 0
10.
730
9.
083
8.
724
8.
667
8.
281
8.
276
8.
141
7.
976
7.
971
7.
591
7.
586
7.
569
7.
566
7.
560
7.
538
7.
260
1.
541
1.
486
9.66
9.24
2.01
0.94
0.96
0.96
1.05
1.04
0.89
1.10
abun
danc
e0
1.0
2.0
X : parts per Million : Proton
10.9 10.7 10.5 10.3 10.1 9.9 9.7 9.5 9.3 9.1 8.9 8.7 8.5 8.3 8.1 7.9 7.7 7.5
10.
730
9.
083
8.
724
8.
667
8.
281
8.
276
8.
141
7.
976
7.
971
7.
591
7.
569
7.
566
7.
560
7.
538
9.66
9.24
2.01
0.94 0.96
0.961.
051.
04
0.89 1.
10
400 MHz 1H NMR spectrum of 6a in CDCl3
(tho
usan
dths
)0
10.0
20.0
30.0
40.0
50.0
60.0
70.0
X : parts per Million : Carbon13
150.0 140.0 130.0 120.0 110.0 100.0 90.0 80.0 70.0 60.0 50.0 40.0 30.0 20.0 10.0 0
154
.699
152
.703
142
.976
142
.317
138
.508
136
.331
133
.267
125
.085
124
.436
123
.109
122
.699
120
.389
116
.465
115
.940
115
.148
114
.928
110
.814
77.
000
34.
843
34.
824
32.
065
100 MHz 13C NMR spectrum of 6a in CDCl3
S14
abun
danc
e0
2.0
4.0
6.0
8.0
10.0
12.0
X : parts per Million : Proton
9.0 8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 0
9.
060
8.
433
8.
430
8.
146
8.
142
7.
911
7.
890
7.
779
7.
775
7.
693
7.
688
7.
672
7.
668
7.
260
1.
507
1.
499
19.0
717
.63
2.03
2.03
2.01
2.00
2.00
1.98
abun
danc
e0
0.2
0.4
0.6
0.8
1.0
1.2
X : parts per Million : Proton
9.2 9.1 9.0 8.9 8.8 8.7 8.6 8.5 8.4 8.3 8.2 8.1 8.0 7.9 7.8 7.7 7.6
9.
060
8.
433
8.
430
8.
146
8.
142
7.
911
7.
890
7.
779
7.
775
7.
693
7.
688
7.
672
7.
668
36.2
1
2.03
2.03
2.01
2.00
2.00
1.98
400 MHz 1H NMR spectrum of 2a in CDCl3
(tho
usan
dths
)0
10.0
20.0
30.0
X : parts per Million : Carbon13
170.0 160.0 150.0 140.0 130.0 120.0 110.0 100.0 90.0 80.0 70.0 60.0 50.0 40.0 30.0 20.0 10.0 0
170
.021
144
.369
143
.052
142
.384
141
.811
139
.644
130
.460
126
.327
126
.193
125
.515
124
.074
119
.615
117
.057
113
.868
113
.687
107
.720
77.
000
35.
082
34.
910
32.
008
31.
912
100 MHz 13C NMR spectrum of 2a in CDCl3
S15
abun
danc
e0
2.0
4.0
6.0
8.0
10.0
12.0
X : parts per Million : Proton
9.0 8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 0
9.
188
8.
640
8.
439
8.
435
8.
139
8.
135
7.
902
7.
881
7.
833
7.
829
7.
674
7.
668
7.
652
7.
647
7.
260
1.
530
1.
485
9.17
8.91
1.86
1.01
1.01
1.01
1.00
1.00
0.99
abun
danc
e0
0.2
0.4
0.6
0.8
1.0
1.2
X : parts per Million : Proton
9.3 9.2 9.1 9.0 8.9 8.8 8.7 8.6 8.5 8.4 8.3 8.2 8.1 8.0 7.9 7.8 7.7 7.6
9.
188
8.
640
8.
439
8.
435
8.
139
8.
135
7.
902
7.
881
7.
833
7.
829
7.
674
7.
668
7.
652
7.
647
9.17
8.91
1.86
1.01
1.01
1.01
1.00
1.00
0.99
400 MHz 1H NMR spectrum of 7 in CDCl3
(tho
usan
dths
)0
10.0
20.0
30.0
40.0
X : parts per Million : Carbon13
170.0 160.0 150.0 140.0 130.0 120.0 110.0 100.0 90.0 80.0 70.0 60.0 50.0 40.0 30.0 20.0 10.0 0
169
.515
157
.028
151
.892
144
.092
142
.689
139
.462
135
.377
128
.150
125
.744
125
.391
124
.016
119
.444
116
.942
116
.580
113
.964
113
.630
107
.950
77.
000
35.
062
34.
862
31.
988
31.
969
100 MHz 13C NMR spectrum of 7 in CDCl3
S16
abun
danc
e0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
1.6
1.8
X : parts per Million : Carbon13
150.0 140.0 130.0 120.0 110.0 100.0 90.0 80.0 70.0 60.0 50.0 40.0 30.0 20.0 10.0
138
.336
136
.579
136
.379
136
.293
133
.954
133
.229
129
.229
128
.188
128
.131
128
.083
121
.305
120
.045
111
.024
104
.016
77.
000
20.
962
20.
867
abun
danc
e0
2.0
4.0
6.0
8.0
X : parts per Million : Proton
8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 0
8.
309
7.
759
7.
757
7.
718
7.
577
7.
557
7.
373
7.
370
7.
260
7.
252
7.
249
6.
984
6.
975
2.
359
2.
355
2.
056
2.
047
6.06
5.77
3.01
2.94
2.03
1.94
1.13
1.04
1.00
0.95
0.92
0.91
400 MHz 1H NMR spectrum of 3b in CDCl3
abun
danc
e0
1.0
2.0
X : parts per Million : Proton
8.3 8.2 8.1 8.0 7.9 7.8 7.7 7.6 7.5 7.4 7.3 7.2 7.1 7.0 6.9
8.
309
7.
759
7.
757
7.
718
7.
577
7.
557
7.
373
7.
370
7.
260
7.
252
7.
249
7.
231
7.
228
6.
984
6.
975
6.06
5.77
3.01
2.94
2.03
1.94
1.13
1.04
1.00
0.95
0.92
0.91
100 MHz 13C NMR spectrum of 3b in CDCl3
S17
abun
danc
e0
1.0
2.0
3.0
X : parts per Million : Proton
11.0 10.0 9.0 8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 0
11.
069
8.
762
7.
966
7.
860
7.
794
7.
792
7.
724
7.
703
7.
312
7.
308
7.
287
7.
260
7.
058
7.
003
2.
407
2.
372
2.
142
2.
089
13.2
313
.48
6.87
6.79
4.10
4.08
2.17
2.02
1.98
1.97
2.02
2.00
2.01
abun
danc
e0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
X : parts per Million : Proton
8.9 8.8 8.7 8.6 8.5 8.4 8.3 8.2 8.1 8.0 7.9 7.8 7.7 7.6 7.5 7.4 7.3 7.2 7.1 7.0 6.9
8.
762
7.
966
7.
860
7.
794
7.
792
7.
724
7.
703
7.
312
7.
308
7.
291
7.
287
7.
260
7.
058
7.
003
13.2
313
.48
6.87
6.79
4.10
4.08
2.17
2.02
1.98
1.97 2.02
2.00
2.01
400 MHz 1H NMR spectrum of 5b in CDCl3
(tho
usan
dths
)0
10.0
20.0
30.0
40.0
50.0
60.07
0.0
X : parts per Million : Carbon13
170.0 160.0 150.0 140.0 130.0 120.0 110.0 100.0 90.0 80.0 70.0 60.0 50.0 40.0 30.0 20.0 10.0 0
168
.846
152
.226
139
.042
136
.742
136
.618
136
.427
133
.009
132
.169
128
.293
128
.102
126
.880
125
.171
122
.947
121
.114
114
.966
111
.348
77.
000
21.
096
21.
029
20.
991
100 MHz 13C NMR spectrum of 5b in CDCl3
S18
abun
danc
e0
1.0
2.0
3.0
4.0
5.0
X : parts per Million : Proton
11.0 10.0 9.0 8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 0
11.
045
9.
086
8.
789
8.
672
7.
962
7.
851
7.
774
7.
719
7.
699
7.
306
7.
304
7.
285
7.
282
7.
260
7.
048
7.
000
2.
397
2.
369
2.
126
2.
081
6.53
6.23
3.25
3.09
2.15
2.07
1.03
1.00
1.00
0.99
1.00
0.97
0.96 1.12
0.83
abun
danc
e0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
1.6
X : parts per Million : Proton
9.2 9.1 9.0 8.9 8.8 8.7 8.6 8.5 8.4 8.3 8.2 8.1 8.0 7.9 7.8 7.7 7.6 7.5 7.4 7.3 7.2 7.1 7.0 6.9
9.
086
8.
789
8.
672
7.
962
7.
851
7.
774
7.
719
7.
699
7.
306
7.
304
7.
285
7.
282
7.
260
7.
048
7.
000
6.53
6.23
3.25
3.09
2.15
2.07
1.03
1.00
1.00
0.99
1.00
0.97
0.96 1.
12
0.83
400 MHz 1H NMR spectrum of 6b in CDCl3
abun
danc
e0
0.02
0.04
0.06
0.08
0.1
X : parts per Million : Carbon13
170.0 160.0 150.0 140.0 130.0 120.0 110.0 100.0 90.0 80.0 70.0 60.0 50.0 40.0 30.0 20.0 10.0 0
168
.760
152
.111
136
.780
136
.637
136
.446
133
.181
132
.007
128
.236
128
.188
128
.045
126
.775
122
.813
121
.009
115
.673
114
.938
111
.358
77.
000
21.
134
21.
086
21.
039
100 MHz 13C NMR spectrum of 6b in CDCl3
S19
abun
danc
e0
2.0
4.0
6.0
8.0
10.0
12.0
X : parts per Million : Proton
9.0 8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 0
9.
168
8.
119
8.
117
8.
052
8.
031
7.
855
7.
733
7.
731
7.
405
7.
401
7.
385
7.
380
7.
260
7.
054
7.
001
2.
399
2.
370
2.
114
2.
086
12.4
212
.28
6.29
6.27
4.50
4.48
2.21
2.10
2.00
2.00
1.97
1.95
abun
danc
e0
0.1
0.2
0.3
0.4
0.5
X : parts per Million : Proton
8.2 8.1 8.0 7.9 7.8 7.7 7.6 7.5 7.4 7.3 7.2 7.1 7.0 6.9 6.8
8.
119
8.
117
8.
052
8.
031
7.
855
7.
733
7.
731
7.
405
7.
401
7.
385
7.
380
7.
260
7.
054
7.
001
48.1
5
12.4
212
.28
6.29
6.27
4.50
4.48
2.21
2.10
2.00
2.00
1.97
1.95
400 MHz 1H NMR spectrum of 2b in CDCl3
abun
danc
e0
0.1
0.2
0.3
X : parts per Million : Carbon13
170.0 160.0 150.0 140.0 130.0 120.0 110.0 100.0 90.0 80.0 70.0 60.0 50.0 40.0 30.0 20.0 10.0 0
170
.116
137
.448
136
.541
134
.441
132
.875
129
.983
129
.362
128
.455
128
.121
124
.064
121
.630
114
.231
114
.126
108
.637
77.
000
21.
058
20.
981
100 MHz 13C NMR spectrum of 2b in CDCl3
S20
abun
danc
e0
2.0
4.0
6.0
8.0
10.0
12.0
14.0
X : parts per Million : Proton
11.0 10.0 9.0 8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 0
10.
989
8.
739
8.
456
8.
453
8.
348
8.
194
8.
190
7.
769
7.
738
7.
611
7.
606
7.
562
7.
559
7.
545
7.
542
7.
468
7.
464
7.
260
1.
491
1.
443
39.7
337
.70
4.18
4.12
2.05
2.05
2.04
2.04
2.00
1.95
2.00
2.01
1.85
abun
danc
e0
0.2
0.4
0.6
0.8
1.0
1.2
X : parts per Million : Proton
8.8 8.7 8.6 8.5 8.4 8.3 8.2 8.1 8.0 7.9 7.8 7.7 7.6 7.5 7.4
8.
739
8.
456
8.
453
8.
348
8.
194
8.
190
7.
794
7.
790
7.
773
7.
769
7.
738
7.
716
7.
611
7.
606
7.
562
7.
559
7.
542
7.
468
7.
464
7.
459
39.7
3
37.7
0
4.18
4.12
2.05
2.05
2.04
2.04
2.00
1.95 2.00
2.01
1.85
400 MHz 1H NMR spectrum of 5c in CDCl3
abun
danc
e0
0.02
0.04
0.06
0.08
0.1
0.12
X : parts per Million : Carbon13
170.0 160.0 150.0 140.0 130.0 120.0 110.0 100.0 90.0 80.0 70.0 60.0 50.0 40.0 30.0 20.0 10.0 0
168
.732
152
.150
151
.481
151
.138
141
.534
141
.162
137
.267
135
.138
126
.661
125
.486
123
.338
122
.155
121
.973
121
.305
120
.818
119
.253
114
.852
111
.472
77.
000
35.
139
35.
043
31.
712
31.
654
100 MHz 13C NMR spectrum of 5c in CDCl3
S21
abun
danc
e0
1.0
2.0
3.0
4.0
5.0
X : parts per Million : Proton
11.0 10.0 9.0 8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 0
11.
022
9.
096
8.
788
8.
694
8.
465
8.
371
8.
173
7.
793
7.
771
7.
742
7.
721
7.
589
7.
585
7.
559
7.
520
7.
517
7.
460
7.
456
7.
260
1.
462
1.
435
20.4
919
.58
2.16
2.11
1.24
1.03
1.02
1.02
1.00
0.96
0.96
0.93
0.83
0.94
1.01
abun
danc
e0
0.1
0.2
0.3
0.4
0.5
X : parts per Million : Proton
9.2 9.1 9.0 8.9 8.8 8.7 8.6 8.5 8.4 8.3 8.2 8.1 8.0 7.9 7.8 7.7 7.6 7.5 7.4
9.
096
8.
788
8.
694
8.
465
8.
371
8.
173
7.
793
7.
771
7.
742
7.
721
7.
589
7.
585
7.
559
7.
520
7.
517
7.
460
7.
456
20.4
9
19.5
8
2.16
2.11
1.24
1.03
1.02
1.02
1.00
0.96
0.96
0.93
0.83 0.
94 1.01
400 MHz 1H NMR spectrum of 6c in CDCl3
abun
danc
e0
0.1
0.2
0.3
0.4
X : parts per Million : Carbon13
180.0 170.0 160.0 150.0 140.0 130.0 120.0 110.0 100.0 90.0 80.0 70.0 60.0 50.0 40.0 30.0 20.0 10.0 0
168
.904
154
.269
152
.102
151
.376
151
.109
141
.553
140
.923
134
.384
132
.818
126
.556
125
.257
121
.945
121
.926
121
.171
119
.186
115
.539
114
.766
111
.319
77.
000
35.
062
35.
024
31.
683
100 MHz 13C NMR spectrum of 6c in CDCl3
S22
abun
danc
e0
2.0
4.0
6.0
8.0
10.0
12.0
14.0
X : parts per Million : Proton
9.0 8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 0
9.
165
8.
608
8.
606
8.
379
8.
376
8.
071
8.
069
8.
054
7.
578
7.
575
7.
553
7.
485
7.
481
7.
477
7.
260
1.
478
1.
444
39.6
238
.22
10.0
8
3.94
2.05
2.00
1.98
1.96
1.90
abun
danc
e0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
1.6
X : parts per Million : Proton
8.7 8.6 8.5 8.4 8.3 8.2 8.1 8.0 7.9 7.8 7.7 7.6 7.5 7.4
8.
608
8.
606
8.
379
8.
376
8.
071
8.
069
8.
054
7.
884
7.
880
7.
863
7.
859
7.
578
7.
575
7.
553
7.
485
7.
481
7.
477
39.6
238
.22
10.0
8
3.94
2.05
2.00
1.98
1.96
1.90
400 MHz 1H NMR spectrum of 2c in CDCl3
(tho
usan
dths
)0
10.0
20.0
30.0
X : parts per Million : Carbon13
180.0 170.0 160.0 150.0 140.0 130.0 120.0 110.0 100.0 90.0 80.0 70.0 60.0 50.0 40.0 30.0 20.0 10.0 0
170
.059
151
.730
151
.195
141
.362
140
.283
136
.455
135
.300
130
.689
127
.739
124
.704
122
.642
122
.040
121
.773
121
.019
119
.940
114
.355
108
.561
77.
000
35.
139
35.
062
31.
654
100 MHz 13C NMR spectrum of 2c in CDCl3
S23
abun
danc
e0
1.0
2.0
3.0
4.0
5.0
6.0
X : parts per Million : Proton
11.0 10.0 9.0 8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 0
11.
068
10.
762
8.
738
8.
679
8.
154
8.
000
7.
995
7.
968
7.
792
7.
789
7.
576
7.
573
7.
566
7.
260
7.
061
7.
010
2.
410
2.
378
2.
146
2.
097
1.
564
1.
494
13.6
19.
89
6.36
5.70
3.32
2.99
2.42
2.09
1.96
1.06
1.01
1.01
1.00
0.99
0.97
0.96
0.95
0.93
0.92
0.91
0.86
abun
danc
e0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
X : parts per Million : Proton
8.8 8.7 8.6 8.5 8.4 8.3 8.2 8.1 8.0 7.9 7.8 7.7 7.6 7.5 7.4 7.3 7.2 7.1 7.0 6.9
8.
738
8.
679
8.
288
8.
285
8.
154
8.
000
7.
995
7.
968
7.
865
7.
792
7.
789
7.
739
7.
718
7.
598
7.
576
7.
573
7.
566
7.
545
7.
318
7.
315
7.
298
7.
294
7.
260
7.
061
7.
010
13.6
1
9.89
6.36
5.70
3.322.
99
2.42
2.09
1.96
1.06
1.01
1.01
1.00
0.99
0.97
0.96
0.95
0.93
0.92
0.91
0.86
400 MHz 1H NMR spectrum of 5d in CDCl3
(tho
usan
dths
)0
10.0
20.0
30.0
X : parts per Million : Carbon13
170.0 160.0 150.0 140.0 130.0 120.0 110.0 100.0 90.0 80.0 70.0 60.0 50.0 40.0 30.0 20.0 10.0 0
169
.190
168
.560
152
.150
151
.959
136
.780
136
.656
136
.455
128
.236
128
.169
128
.054
126
.766
124
.369
122
.861
116
.389
114
.833
114
.775
111
.358
110
.766
77.
000
34.
786
32.
036
21.
153
21.
058
100 MHz 13C NMR spectrum of 5d in CDCl3
S24
abun
danc
e0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
1.6
1.8
X : parts per Million : Proton
9.0 8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 0
9.
144
9.
116
8.
483
8.
479
8.
154
8.
150
8.
113
8.
111
7.
869
7.
866
7.
858
7.
719
7.
716
7.
686
7.
260
7.
050
7.
005
2.
397
2.
371
2.
111
2.
089
1.
554
1.
489
47.5
49.
69
6.48
5.90
3.14
2.93
2.96
2.33
1.96
1.09
1.07
1.04
1.04
1.00
1.00
1.00
0.95
0.93
abun
danc
e0
0.1
0.2
0.3
0.4
0.5
X : parts per Million : Proton
9.1 9.0 8.9 8.8 8.7 8.6 8.5 8.4 8.3 8.2 8.1 8.0 7.9 7.8 7.7 7.6 7.5 7.4 7.3 7.2 7.1 7.0 6.9
9.
144
9.
116
8.
483
8.
479
8.
154
8.
150
8.
113
8.
111
8.
064
8.
045
7.
869
7.
866
7.
858
7.
719
7.
716
7.
686
7.
682
7.
660
7.
408
7.
404
7.
387
7.
384
7.
260
7.
050
7.
005
47.5
49.
69
6.48
5.90
3.14
2.932.96
2.33
1.96
1.09
1.07
1.04
1.04
1.00
1.00
1.00
0.95
0.93
400 MHz 1H NMR spectrum of 2d in CDCl3
(tho
usan
dths
)0
2.0
4.0
6.0
8.0
10.0
12.0
14.0
X : parts per Million : Carbon13
170.0 160.0 150.0 140.0 130.0 120.0 110.0 100.0 90.0 80.0 70.0 60.0 50.0 40.0 30.0 20.0 10.0 0
170
.116
169
.877
136
.579
129
.248
128
.379
128
.074
125
.534
123
.978
123
.911
121
.563
119
.663
117
.076
113
.954
113
.525
108
.599
107
.606
77.
000
35.
091
34.
862
31.
941
31.
903
21.
106
21.
039
100 MHz 13C NMR spectrum of 2d in CDCl3
S25
abun
danc
e0
1.0
2.0
3.0
4.0
5.0
6.0
X : parts per Million : Proton
11.0 10.0 9.0 8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 0
10.
935
10.
580
8.
654
8.
604
8.
399
8.
233
8.
187
8.
183
8.
005
8.
000
7.
629
7.
625
7.
562
7.
558
7.
542
7.
517
7.
468
7.
260
1.
494
1.
451
34.8
119
.81
5.95
1.20
1.06
1.05
1.03
1.01
1.00
1.21
0.98
0.96
1.05
0.95
0.90
0.90
0.89
abun
danc
e0
0.2
0.4
0.6
0.8
1.0
X : parts per Million : Proton
8.7 8.6 8.5 8.4 8.3 8.2 8.1 8.0 7.9 7.8 7.7 7.6 7.5
8.
654
8.
604
8.
402
8.
399
8.
237
8.
233
8.
203
8.
187
8.
183
8.
052
8.
048
8.
005
8.
000
7.
732
7.
727
7.
711
7.
707
7.
629
7.
625
7.
607
7.
562
7.
558
7.
546
7.
542
7.
517
7.
468
34.8
1
19.8
1
5.95
1.20
1.06
1.05
1.03
1.01
1.00 1.21
0.98
0.96 1.05
0.95
0.90
0.90
0.89
400 MHz 1H NMR spectrum of 5e in CDCl3
abun
danc
e0
0.02
0.04
0.06
0.08
0.1
0.12
X : parts per Million : Carbon13
170.0 160.0 150.0 140.0 130.0 120.0 110.0 100.0 90.0 80.0 70.0 60.0 50.0 40.0 30.0 20.0 10.0 0
168
.846
168
.235
151
.940
151
.396
151
.023
141
.524
141
.009
137
.057
132
.713
126
.584
122
.804
122
.575
122
.260
122
.021
121
.248
115
.415
114
.393
110
.785
110
.728
77.
000
35.
129
35.
024
34.
776
34.
604
32.
132
31.
912
31.
683
31.
664
100 MHz 13C NMR spectrum of 5e in CDCl3
S26
abun
danc
e0
1.0
2.0
3.0
4.0
5.0
6.0
7.0
X : parts per Million : Proton
9.0 8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 0
9.
125
9.
104
8.
584
8.
467
8.
464
8.
347
8.
132
8.
062
8.
058
7.
867
7.
864
7.
576
7.
572
7.
543
7.
478
7.
260
1.
561
1.
485
1.
473
1.
444
18.9
718
.56
9.05
8.96
3.22
3.13
2.21
1.05
1.05
1.01
1.00
1.00
0.99
0.99
0.99
0.98
0.97
abun
danc
e0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
X : parts per Million : Proton
8.7 8.6 8.5 8.4 8.3 8.2 8.1 8.0 7.9 7.8 7.7 7.6 7.5 7.4
8.
584
8.
467
8.
464
8.
351
8.
347
8.
136
8.
132
8.
062
8.
058
8.
046
8.
025
7.
876
7.
867
7.
864
7.
856
7.
848
7.
843
7.
675
7.
670
7.
653
7.
648
7.
576
7.
572
7.
543
7.
478
18.9
718
.56
9.05
8.96
3.22
3.13
2.21
1.05
1.05
1.01
1.00
1.00
0.99
0.99
0.99
0.98
0.97
400 MHz 1H NMR spectrum of 2e in CDCl3
(tho
usan
dths
)0
10.0
20.0
30.0
40.0
50.0
60.07
0.0
X : parts per Million : Carbon13
170.0 160.0 150.0 140.0 130.0 120.0 110.0 100.0 90.0 80.0 70.0 60.0 50.0 40.0 30.0 20.0 10.0 0
170
.317
170
.078
151
.768
151
.271
143
.023
141
.534
140
.398
135
.319
127
.653
125
.420
122
.050
121
.744
119
.902
113
.687
108
.713
107
.816
77.
000
35.
167
35.
101
34.
871
31.
998
31.
969
31.
702
100 MHz 13C NMR spectrum of 2e in CDCl3
S27
abun
danc
e0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
1.6
X : parts per Million : Proton
11.0 10.0 9.0 8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 0
11.
067
8.
769
8.
760
8.
470
8.
191
8.
188
7.
974
7.
801
7.
798
7.
748
7.
726
7.
604
7.
599
7.
569
7.
565
7.
463
7.
260
7.
061
7.
006
2.
410
2.
374
2.
146
2.
092
1.
478
1.
440
18.8
518
.67
6.37
5.92
3.39
3.28
2.32
2.24
2.21
2.12
2.10
2.10
1.91
1.17
1.05
1.02
1.02
1.01
1.01
1.00
1.00
0.94
1.11
abun
danc
e0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
X : parts per Million : Proton
8.9 8.8 8.7 8.6 8.5 8.4 8.3 8.2 8.1 8.0 7.9 7.8 7.7 7.6 7.5 7.4 7.3 7.2 7.1 7.0 6.9
8.
769
8.
760
8.
473
8.
470
8.
383
8.
191
8.
188
7.
974
7.
971
7.
864
7.
801
7.
798
7.
748
7.
604
7.
599
7.
569
7.
565
7.
533
7.
463
7.
318
7.
314
7.
298
7.
293
7.
260
7.
061
7.
006
18.8
518
.67
6.37
5.92
3.39
3.28
2.32
2.24
2.21
2.12
2.10
2.10
1.91
1.17
1.05
1.02
1.02
1.01
1.01
1.00
1.00
0.94 1.11
400 MHz 1H NMR spectrum of 5f in CDCl3
(tho
usan
dths
)0
10.0
20.0
30.0
40.0
X : parts per Million : Carbon13
180.0 170.0 160.0 150.0 140.0 130.0 120.0 110.0 100.0 90.0 80.0 70.0 60.0 50.0 40.0 30.0 20.0 10.0 0
168
.932
168
.846
152
.236
151
.481
151
.205
136
.799
136
.742
136
.608
133
.372
128
.331
122
.136
122
.021
114
.976
111
.539
111
.377
77.
000
35.
129
35.
072
31.
683
31.
664
21.
086
21.
029
20.
972
100 MHz 13C NMR spectrum of 5f in CDCl3
S28
abun
danc
e0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
1.6
X : parts per Million : Proton
9.0 8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 0
9.
182
9.
175
8.
622
8.
619
8.
369
8.
078
8.
074
8.
046
7.
859
7.
856
7.
734
7.
731
7.
568
7.
564
7.
544
7.
260
7.
056
7.
003
2.
402
2.
371
2.
115
2.
088
1.
468
1.
436
18.7
118
.32
6.13
5.96
5.72
3.03
3.00
2.99
2.39
2.08
2.02
1.10
1.09
1.09
1.03
1.00
0.94
0.94
0.82
abun
danc
e0
0.03
0.06
0.09
0.12
0.15
0.18
X : parts per Million : Proton
9.3 9.2 9.1 9.0 8.9 8.8 8.7 8.6 8.5 8.4 8.3 8.2 8.1 8.0 7.9 7.8 7.7 7.6 7.5 7.4 7.3 7.2 7.1 7.0 6.9
9.
182
9.
175
8.
622
8.
619
8.
373
8.
369
8.
120
8.
078
8.
074
8.
066
8.
046
7.
877
7.
859
7.
856
7.
734
7.
731
7.
568
7.
564
7.
544
7.
475
7.
471
7.
408
7.
260
7.
056
7.
003
18.7
118
.32
6.13
5.96
3.03
3.00
2.99
2.98
2.39
2.23
2.08
2.02
1.10
1.09
1.09
1.03
1.00
0.94
0.94
0.82
400 MHz 1H NMR spectrum of 2f in CDCl3
abun
danc
e0
0.02
0.04
0.06
0.08
0.1
0.12
0.14
X : parts per Million : Carbon13
170.0 160.0 150.0 140.0 130.0 120.0 110.0 100.0 90.0 80.0 70.0 60.0 50.0 40.0 30.0 20.0 10.0 0
169
.992
151
.663
151
.119
141
.267
140
.159
136
.570
128
.379
128
.064
127
.768
122
.050
121
.735
114
.298
108
.580
108
.475
77.
000
35.
110
35.
024
31.
616
21.
096
21.
029
100 MHz 13C NMR spectrum of 2f in CDCl3
S29
abun
danc
e0
1.0
2.0
3.0
4.0
5.0
X : parts per Million : Proton
8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 0
8.
401
8.
399
8.
371
8.
151
7.
858
7.
746
7.
741
7.
725
7.
721
7.
621
7.
600
7.
260
4.04
2.00
1.97
1.962.05
0.82
abun
danc
e0
1.0
2.0
3.0
4.0
5.0
X : parts per Million : Proton
8.5 8.4 8.3 8.2 8.1 8.0 7.9 7.8 7.7 7.6 7.5
8.
401
8.
399
8.
371
8.
151
7.
858
7.
746
7.
741
7.
725
7.
721
7.
621
7.
600
4.04
2.00
1.97
1.962.05
0.82
400 MHz 1H NMR spectrum of 3,6-bis[3,5-bis(trifluoromethyl)phenyl]carbazole in CDCl3
(tho
usan
dths
)0
10.0
20.0
30.0
40.0
50.0
60.0
X : parts per Million : Carbon13
150.0 140.0 130.0 120.0 110.0 100.0 90.0 80.0 70.0 60.0 50.0 40.0 30.0 20.0 10.0 0
144
.131
140
.465
132
.226
130
.727
127
.291
125
.964
124
.236
119
.444
111
.749
77.
000
100 MHz 13C NMR spectrum of 3,6-bis[3,5-bis(trifluoromethyl)phenyl]carbazole in CDCl3
S30
abun
danc
e0
1.0
2.0
3.0
4.0
5.0
6.0
7.0
8.0
X : parts per Million : Proton
9.0 8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 0
8.
510
8.
376
8.
371
8.
329
8.
326
8.
144
8.
120
7.
884
7.
880
7.
875
7.
790
7.
770
7.
765
7.
688
7.
667
7.
260
3.02
2.06
2.00
1.02
1.01
1.01
0.99
0.80
abun
danc
e0
1.0
2.0
X : parts per Million : Proton
8.6 8.5 8.4 8.3 8.2 8.1 8.0 7.9 7.8 7.7 7.6
8.
510
8.
376
8.
371
8.
329
8.
326
8.
144
8.
120
7.
884
7.
880
7.
875
7.
790
7.
786
7.
770
7.
765
7.
688
7.
667
3.02
2.06
2.00
1.02
1.01
1.01
0.99
0.80
400 MHz 1H NMR spectrum of 3d in CDCl3
(tho
usan
dths
)0
10.0
20.0
30.0
40.0
X : parts per Million : Carbon13
150.0 140.0 130.0 120.0 110.0 100.0 90.0 80.0 70.0 60.0 50.0 40.0 30.0 20.0 10.0 0
143
.806
142
.918
140
.016
139
.071
132
.150
127
.911
127
.358
126
.680
119
.949
118
.527
112
.217
105
.267
77.
000
100 MHz 13C NMR spectrum of 3d in CDCl3
S31
abun
danc
e0
1.0
2.0
3.0
4.0
X : parts per Million : Proton
9.0 8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 0
9.
176
9.
167
8.
209
8.
182
8.
147
8.
144
8.
135
7.
718
7.
716
7.
417
7.
414
7.
396
7.
392
7.
260
7.
063
7.
011
2.
409
2.
378
2.
120
2.
095
6.57
6.41
3.33
3.19
3.16
3.02
2.45
2.41
2.23
2.20
1.05
1.02
1.00
0.98
0.95
0.94
0.91 1.07
abun
danc
e0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
X : parts per Million : Proton
9.2 9.1 9.0 8.9 8.8 8.7 8.6 8.5 8.4 8.3 8.2 8.1 8.0 7.9 7.8 7.7 7.6 7.5 7.4
9.
176
9.
167
8.
646
8.
643
8.
463
8.
459
8.
209
8.
182
8.
147
8.
144
8.
135
8.
116
8.
045
8.
024
7.
973
7.
920
7.
916
7.
895
7.
864
7.
718
7.
716
7.
417
7.
414
7.
396
7.
392
6.57
6.41
3.33
3.19
3.16
3.02
2.45
2.41
2.23
2.20
1.05
1.02
1.00
0.98
0.95
0.94
0.91 1.
07
400 MHz 1H NMR spectrum of 2g in CDCl3
S32
[E] Fluorescence Lifetime
(a)
(b)
(c)
(d)
(f)
S33
Fig. S1 Fluorescence decay analyses of (a) 7, (b) 2a, (c) 2b, (d) 2c, (e) 2d, (f) 2e, (g) 2f and (f)
2g in CH2Cl2 (left) and in the solid state (right).
(e)
(f)
(g)
(h)
S34
[F] X-ray Crystal Structures
Single crystals of 2a and 7 were obtained by the vapor diffusion method (chlorobenzene/EtOH
for 2a and CH2Cl2/MeOH for 7). X-ray data at 93 K were taken on a Rigaku-Raxis-RAPID imaging
plate system with Cu-Kα radiation (λ = 1.54187 Å), and structures were processed and refined by
CrystalStructure and Yadokari. All non-hydrogen atoms were refined anisotropically and the
hydrogen atoms were calculated in ideal positions.
Fig. S2 Crystal structures of (a) 2a and (b) 7. Hydrogen atoms and solvent molecules are
omitted for clarity. The thermal ellipsoids are drawn at the 50% probability level. Selected bond
distances (Å) are shown. Mean plane deviations (MPV) are calculated for the atoms excluding the
peripheral substituents.
Crystallographic data for 2a: formula: C48H46N4S2B2F4·3(C6H5Cl), Mw = 1078.28, Tricrinic, space group P–1 (2), a = 8.2634(10), b = 12.174(2), c = 15.232(3) Å, = 88.77(3), = 79.422(18), = 76.323(18), V = 1463.2(4) Å3, Z = 1, calcd = 1.337, T = –180 °C, 18884 measured reflection, 5066 unique reflections (Rint = 0.0426), R1 = 0.0487, wR2 = 0.1387 (all data), GOF = 1.004Crystallographic data for 7: formula: 2(C28H26N3S2BF2)·0.615(CCl2), Mw = 1085.71, Tricrinic, space group P–1 (2), a = 9.6199(15), b = 11.2244(19), c = 24.169(4) Å, = 88.899(15), = 85.634(13), = 83.446(12), V = 2585.0(7) Å3, Z = 2, calcd = 1.395, T = –180 °C, 32248 measured reflection, 8710 unique reflections (Rint = 0.0258), R1 = 0.0520, wR2 = 0.1517 (all data), GOF = 1.024.
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