electronic supplementary information red fluorescence in ... · s1 electronic supplementary...

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



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




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


(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




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


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



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


mg, 48.0 mol), HP(t-Bu)3BF4 (29.2 mg, 101 mol), and Cs2CO3




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



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


mg, 51.6 mol), HP(t-Bu)3BF4 (28.6 mg, 98.6 mol), and Cs2CO3




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


(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


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


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


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


(tho

usan

dths

)0

10.0

20.0

30.0

40.0

50.0

60.0

70.0


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

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


S14

abun

danc

e0

2.0

4.0

6.0

8.0

10.0

12.0


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


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


(tho

usan

dths

)0

10.0

20.0

30.0


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

.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


S15

abun

danc

e0

2.0

4.0

6.0

8.0

10.0

12.0


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


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


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


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


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


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


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


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


(tho

usan

dths

)0

10.0

20.0

30.0

40.0

50.0

60.07

0.0


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

.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


S18

abun

danc

e0

1.0

2.0

3.0

4.0

5.0


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


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


abun

danc

e0

0.02

0.04

0.06

0.08

0.1


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


S19

abun

danc

e0

2.0

4.0

6.0

8.0

10.0

12.0


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


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


abun

danc

e0

0.1

0.2

0.3


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


S20

abun

danc

e0

2.0

4.0

6.0

8.0

10.0

12.0

14.0


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


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


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


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


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


abun

danc

e0

0.1

0.2

0.3

0.4


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


S22

abun

danc

e0

2.0

4.0

6.0

8.0

10.0

12.0

14.0


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


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


(tho

usan

dths

)0

10.0

20.0

30.0


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


S23

abun

danc

e0

1.0

2.0

3.0

4.0

5.0

6.0


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


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


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


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


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


(tho

usan

dths

)0

2.0

4.0

6.0

8.0

10.0

12.0

14.0


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

.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


S25

abun

danc

e0

1.0

2.0

3.0

4.0

5.0

6.0


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


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


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


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


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


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


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


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


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


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


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


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


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


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


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


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


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


(tho

usan

dths

)0

10.0

20.0

30.0

40.0


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

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


S31

abun

danc

e0

1.0

2.0

3.0

4.0


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


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.

electronic supplementary information red fluorescence in ... · s1 electronic supplementary...

Documents