1

Supporting Information

Fluoranthene Derivatives as Blue Fluorescent Materials for Non-doped Organic Light-Emitting

Diodes Shiv Kumar1, Deepak Kumar1, Yogesh Patil2, Satish Patil1*

1Solid Sate and Structural Chemistry Unit (SSCU), Indian Institute of Science, Bangalore 560012, India

2Inorganic and Physical Chemistry (IPC), Indian Institute of Science, Bangalore 560012, India

Corresponding Author*Prof. Satish Patil

Solid State and Structural Chemistry Unit

Indian Institute of Science, Bangalore 560012 INDIA

E-mail: satish@sscu.iisc.ernet.in

Phone: +91 80 2293-2651

Electronic Supplementary Material (ESI) for Journal of Materials Chemistry C.This journal is © The Royal Society of Chemistry 2015

2

Table of contents1. Synthetic procedures of precursor materials and fluoranthene

derivatives2. 1H & 13C NMR spectra of fluoranthene derivatives3. Mass spectra fluoranthene derivatives4. ORTEP diagram5. Selective crystallographic details6. Summary of torsion angles7. Simulated UV-visible spectra8. Assignment of selective key electronic transitions in absorption

spectra9. CIE 1931 chromaticity plot

3

1. Synthesis of precursor materials

7,9-diphenyl-8H-cyclopenta[a]acenaphthylen-8-one (DPC)

OO

O O

KOHethanol

reflux, 15 min

DPC

Procedure

A two-necked 250 mL round bottom flask was equipped with a reflux condenser and

rubber septum and charged with acenenapthenequinone (5.00 g, 27.5 mmol) and

diphenylacetone (5.75 g, 27.5 mmol). Ethanol (70 mL) was added and the mixture

brought to reflux, at which point ethanolic potassium hydroxide (2.5 mL) was added drop

by drop. The reaction immediately became violent and a black precipitate formed. After

15 minutes the reaction vessel was capped and cooled to 0 °C. Pure DPC (9.10 g, 93%

yield) was then collected by filtration as a deep purple crystalline solid. 1H NMR (400

MHz, CDCl3, ppm): δ 8.01 (d, J= 7 Hz, 2H), 7.9 (d, J= 8.2 Hz, 2H), 7.8 (d, J= 7.3 Hz,

4H), 7.6 (t, J=7.4, 2H), 7.5 (t, J= 7.6, 4H), 7.4 (t, J= 7.4, 2H).13C NMR (101 MHz,

CDCl3): δ 204.51, 193.38, 128.96, 128.75, 128.52, 121.06, 89.97, 65.11, 52.96, 40.14,

39.93, 39.72, 39.51, 39.30, 39.09, 38.88, 0.39.

1-(Hexyloxy)-4-iodobenzene (P1)

OH

I OC6H13

I

C6H13Br

K2CO3DMF

reflux, 12h(80 %) P1

4

Procedure

A mixture of 4-Iodophenol (5.0 g, 22.7 mmol) and anhydrous potassium carbonate (6.28

g, 45.5 mmol) was taken in N,N-dimethylforamide (20 mL). To the above reaction

mixture 1-bromohexane (5.63 g, 34.1 mmol) was added. Reaction mixture was reflux for

16h. Reaction mixture was poured into 150 mL water and extracted with

dichloromethane. The organic layer was washed with distilled water. The organic layer

was dried over anhydrous sodium sulphate, filtered and subjected to rotary evaporation.

Product was further purified using column chromatography with 2% ethyl acetate/hexane

as eluent. Colourless liquid was obtained (90% yield). 1H NMR (400 MHz, CDCl3, ppm):

δ 7.52 (d, 2H, J= 8.8 Hz), 6.66 (d, 2H, J= 9.2 Hz), 3.90 (t, 2H, J= 6.4 Hz), 1.79-1.75 (m,

2H), 1.47-1.43 (m, 2H), 1.35-1.31 (m, 4H), 0.90 (t, 3H, J= 4.32 Hz). 13C NMR (100

MHz, CDCl3, ppm): δ 159.01, 138.12, 116.93, 82.36, 77.32, 77.00, 76.68, 68.11, 31.53,

29.09, 25.65, 22.56, 13.99.

((4-(hexyloxy)phenyl)ethynyl)trimethylsilane (P2)

OC6H13

I

OC6H13

SiMe3

H SiMe3

CuI

PdCl2(PPh3)2

Et3N

4h, 90 oC(99 %)

P1

P2

Procedure

A reaction mixture of compound P1 (2.0 g, 6.5 mmol), trimethylsilyacetylene (0.7 g, 7.0

mmol), bis(triphenylphosphinepalladium(II))dichloride (4% mol) and copper iodide (10%

mol) was taken in triethylamine (20 mL). In above reaction mixture was stirred at room

temperature for 15 min and then refluxed for 4h under argon atmosphere. Reaction mixture

was cooled to room temperature and subjected to solvent evaporation under reduced pressure.

Residue was directly adsorbed over silica gel and purified using column chromatography

5

with 2% ethylacetate/hexane as eluent. Colourless liquid was obtained. 1H NMR (400 MHz,

CDCl3, ppm): δ 7.38 (d, 2H, J= 8.8 Hz), 6.79 (d, 2H, J= 8.8 Hz), 3.93 (t, 2H, J= 6.8 Hz),

1.78-1.72 (m, 2H), 1.46-1.42 (m, 2H), 1.34-1.31 (m, 4H), 0.90 (t, 3H, J= 4.32 Hz), 0.23 (s,

9H). 13C NMR (100 MHz, CDCl3, ppm): δ 159.36, 133.42, 115.01, 114.34, 105.34, 92.24,

77.32, 77.00, 76.68, 68.04, 31.56, 29.14, 25.67, 22.57, 13.99, 0.06.

Synthesis of 1-ethynyl-4-(hexyloxy)benzene (P3)

OC6H13

SiMe3

OC6H13

H

K2CO3

MeOH3h, r.t.(95 %)

P2 P3

Procedure

Compound P2 (1.7 g, 6.2 mmol) was treated with anhydrous potassium carbonate (85 mg, 0.6

mmol) in methanol (20 mL) at room temperature for 3 h under argon atmosphere. Solvent

was evaporated and residue was extracted with dichloromethane/water mixture. Organic layer

dried over anhydrous sodium sulphate, filtered and subjected to rotary evaporation. Product

was further purified using column chromatography with 2% ethylacetate/hexane as eluent.

Colourless liquid was obtained(95% yield).1H NMR (400 MHz, CDCl3, ppm): δ 7.4 (d, 2H,

J= 8.8 Hz), 6.82 (d, 2H, J= 8.8 Hz), 3.94 (t, 2H, J= 6.8 Hz), 2.98 (s, 1H), 1.80-1.73 (m, 2H),

1.53-1.43 (m, 2H), 1.35-1.31 (m, 4H), 0.91 (t, 3H, J= 4.32 Hz). 13C NMR (100 MHz, CDCl3,

ppm): δ 159.56, 133.55, 114.47, 113.89, 83.78, 77.32, 77.00, 76.68, 75.61, 68.08, 31.55,

29.12, 25.67, 22.57, 13.99.

1,2-bis(4-(hexyloxy)phenyl)ethyne (P4)

6

OC6H13

HOC6H13

OC6H13

OC6H13I

PdCl2(PPh3)2

Et3N

4h, 90 oC(87 %)

CuI

P4P3

Procedure

A mixture of compound P1 (1.9 g, 6.2 mmol), 3 (1.2 g, 5.9 mmol),

bis(triphenylphosphinepalladium(II))dichloride (4% mol) and copper iodide (10% mol) was

taken in triethylamine (10 mL). In above reaction mixture was stirred at room temperature for

15 min, and then refluxed for 4 h under argon atmosphere. Reaction mixture was cooled to

room temperature and solvent was evaporated and residue directly adsorbed over silica gel

and purified using column chromatography with 2% ethylacetate/hexane as eluent.

Crystalline white flakes were obtained(87% yield).1H NMR (400 MHz, CDCl3, ppm): δ 7.42

(d, 4H, J= 8.8 Hz), 6.82 (d, 4H, J= 8.8 Hz), 3.95 (t, 4H, J= 6.8 Hz), 1.80-1.73 (m, 4H), 1.53-

1.43 (m, 4H), 1.35-1.31 (m, 8H), 0.91 (t, 6H, J= 4.32 Hz). 13C NMR (100 MHz, CDCl3,

ppm): δ 138.17, 132.85, 115.55, 114.54, 87.98, 68.10, 31.60, 29.71, 29.20, 25.72,

22.61.Anal.Calcd for C26H34O2: C, 82.49; H, 9.05; O, 8.45. Found: C, 82.31; H, 8.91.

4-((trimethylsilyl)ethynyl)benzonitrile (P5)

CN

Br

CN

SiMe3

H SiMe3

CuI

Pd(PPh3)4

Et3N

4h, 90 oC(99 %) P5

7

Procedure

A reaction mixture of 4-bromobenzonitrile (1.82 g, 10mmol), trimethylsilyacetylene (0.98 g,

11.0 mmol), tetrakis(triphenylphosphinepalladium(0)) (4% mol) and copper iodide (10%

mol) was taken in triethylamine (20 mL). In above reaction mixture was stirred at room

temperature for 15 min and then refluxed for 4h under argon atmosphere. Reaction mixture

was cooled to room temperature and subjected to solvent evaporation under reduced pressure.

Residue was directly adsorbed over silica gel and purified using column chromatography

with 2% ethylacetate/hexane as eluent.White solid powder was obtained (yield 85 %). 1H

NMR (400 MHz, CDCl3, ppm): δ 7.59 (d, J = 8.3 Hz, 2H), 7.53 (d, J = 8.1 Hz, 2H), 0.26 (s,

9H). 13C NMR (100 MHz, CDCl3, ppm): δ 132.43, 131.90, 128.01, 118.39, 111.79, 102.97,

99.55, 29.68, -0.30.

4-ethynylbenzonitrile (P6)

CN

SiMe3

CN

H

MeOH3h, r.t.(95 %)

P5 P6

K2CO3

Procedure

Compound P5 (1.7 g, 6.2 mmol) was treated with anhydrous potassium carbonate (85 mg, 0.6

mmol) in methanol (20 mL) at room temperature for 3 h under argon atmosphere. Solvent

was evaporated and residue was extracted with dichloromethane/water mixture. Organic layer

dried over anhydrous sodium sulphate, filtered and subjected to rotary evaporation. Product

was further purified using column chromatography with 2% ethylacetate/hexane as eluent.

Colourless liquid was obtained (95% yield). 1H NMR (400 MHz, CDCl3, ppm): δ 7.62 (d, J =

8.2 Hz, 2H), 7.57 (d, J = 8.3 Hz, 2H), 3.30 (s, 1H). 13C NMR (100 MHz, CDCl3, ppm): δ

132.65, 132.00, 126.98, 118.21, 112.33, 81.84, 81.51, 29.67.

8

Synthesis of fluoranthene derivatives8-(4-cyanophenyl)-7,10-dipenylfluoranthene (CN-TPF)

O

Diels-Alderreaction

diphenyl ether220 oC, 24h

CN

CN

DPCCN-TPF

Procedure

The compound DPC (1 mmol) and P6 (1 mmol) were dissolved in diphenyl ether (5 mL) and

kept in a sealed Teflon tube at 220 oC. After 24 h, reaction mixture was cooled down to room

temperature; diphenyl ether was stripped under vacuum. Residue was diluted with hexane to

precipitate the crude product. The resulting yellow solid was purified via column

chromatography using 4:1 hexane/chloroform as eluent to afford green crystalline solid (yield

66%).1H NMR (400 MHz, CDCl3, ppm): δ 7.76 (t, J = 8.7 Hz, 2H), 7.69 (d, J = 7.3 Hz, 2H),

7.60 – 7.51 (m, 3H), 7.46 (d, J = 8.1 Hz, 2H), 7.39 (dd, J = 13.4, 5.5 Hz, 4H), 7.35 – 7.26 (m,

7H), 6.72 (d, J = 7.1 Hz, 1H).13C NMR (100 MHz, CDCl3, ppm): δ 146.03, 140.35, 138.69,

138.55, 138.42, 138.18, 136.71, 136.14, 135.89, 135.50, 133.12, 131.37, 130.61, 130.20,

129.73, 129.03, 128.74, 128.04, 127.76, 127.68, 127.62, 127.06, 126.97, 123.54, 123.33,

118.95, 110.11. ESI-MS: 455.27 (M+). Elemental Analysis: (C35H21N) Calc. (%): C, 92.28;

H, 4.65; N, 3.07; Found (%): C, 92.23; H, 4.67; N, 3.10.

7,8,10-triphenylfluoranthene (TPF)

9

O

Diels-Alderreaction

diphenyl ether220 oC, 24h

DPCH-TPF

Procedure

Same as above. Green crystalline solid (yield 66%).1H NMR (400 MHz, CDCl3, ppm): δ 7.72

(dd, J = 10.1, 7.3 Hz, 4H), 7.53 (dt, J = 20.3, 7.0 Hz, 3H), 7.36 (d, J = 11.0 Hz, 6H), 7.30 (dd,

J = 16.1, 9.0 Hz, 3H), 7.23 (d, J = 7.1 Hz, 2H), 7.17 (q, J = 6.4 Hz, 3H), 6.69 (d, J = 7.1 Hz,

1H).13C NMR (100 MHz, CDCl3, ppm): δ 141.01, 140.79, 139.33, 138.22, 137.92, 136.62,

136.18, 135.92, 135.71, 133.14, 131.14, 130.33, 129.96, 129.72, 129.13, 128.62, 128.45,

127.80, 127.62, 127.53, 127.27, 126.63, 126.33, 123.34, 122.91. ESI-MS: 431.73 (M++H).

Elemental Analysis: (C34H22) Calc. (%): C, 94.85; H, 5.15; Found (%): C, 94.18; H, 5.82

7,10-diphenyl-8-(p-tolyl)fluoranthene (CH3-TPF)

O

Diels-Alderreaction

diphenyl ether220 oC, 24h

CH3

CH3

DPCCH3-TPF

Procedure

Same as above. Greenish-Yellow crystalline powder (yield 65 %). 1H NMR (400 MHz,

CDCl3, ppm): δ 7.73 – 7.67 (m, 4H), 7.57 – 7.48 (m, 3H), 7.40 – 7.36 (m, 5H), 7.34 (d, J =

8.0 Hz, 2H), 7.32 (s, 1H), 7.28 (d, J = 7.1 Hz, 2H), 7.24 (d, J = 8.1 Hz, 1H), 7.13 – 7.09 (m,

2H), 6.97 (d, J = 7.9 Hz, 2H), 6.65 (d, J = 7.1 Hz, 1H), 2.26 (s, 3H).13C NMR (101 MHz,

CDCl3, ppm): δ 140.85, 140.68, 139.51, 138.26, 138.02, 137.90, 136.68, 136.17, 135.97,

10

135.91, 135.51, 133.13, 131.22, 130.32, 129.80, 129.70, 129.13, 128.61, 128.47, 128.30,

127.76, 127.60, 127.51, 127.22, 126.56, 123.31, 122.83, 21.07. ESI-MS: 445.73 (M++H).

Elemental Analysis: (C35H24) Calc. (%): C, 94.56; H, 5.44; Found (%): C, 94.49; H, 5.51.

8-(4-(hexyloxy)phenyl)-7,10-diphenylfluoranthene (asym-TPF)

O

Diels-Alderreaction

diphenyl ether220 oC, 24h

OC6H13

OC6H13

DPCasym-TPF

ProcedureSame as above. Green crystalline powder was obtained (yield 70 %). 1H NMR (400 MHz,

CDCl3, ppm): δ 7.70 (t, J = 7.4 Hz, 12H), 7.52 (ddd, J = 14.4, 8.4, 4.5 Hz, 11H), 7.46 – 7.21

(m, 26H), 7.12 (d, J = 8.7 Hz, 6H), 6.68 (dd, J = 15.5, 7.9 Hz, 9H), 3.87 (t, J = 6.6 Hz, 6H),

1.79 – 1.67 (m, 6H), 1.41 (dd, J = 13.7, 6.2 Hz, 7H), 1.37 – 1.25 (m, 10H), 0.89 (t, J = 6.4

Hz, 7H).13C NMR (101 MHz, CDCl3, ppm): δ 157.74, 140.88, 140.42, 139.56, 138.26,

137.90, 136.71, 136.19, 136.00, 135.34, 133.17, 133.13, 131.16, 130.96, 130.33, 129.70,

129.13, 128.60, 128.51, 127.75, 127.60, 127.50, 127.21, 126.56, 126.51, 123.29, 122.77,

113.62, 67.86, 31.60, 29.26, 25.72, 22.58, 14.01. ESI-MS: 531.60 (M++H). Elemental

Analysis: (C40H34O) Calc. (%): C, 90.53; H, 6.46; O, 3.01; Found (%): C, 90.06; H, 6.52.

8,9-bis(4-(hexyloxy)phenyl)-7,10-diphenylfluoranthene (sym-TPF)

11

Procedure

Same as above. Greenish-yellow crystalline powder was obtained (yield 60 %). 1H NMR

(400 MHz, CDCl3, ppm): δ 7.68 (d, J = 8.2 Hz, 2H), 7.35 – 7.23 (m, 12H), 6.77 (d, J = 8.5

Hz, 4H), 6.56 (d, J = 7.1 Hz, 2H), 6.43 (d, J = 8.5 Hz, 4H), 3.74 (t, J = 6.7 Hz, 4H), 1.71 –

1.59 (m, 4H), 1.32 (ddd, J = 15.9, 13.4, 7.7 Hz, 16H), 0.88 (t, J = 6.7 Hz, 6H).13C NMR (100

MHz, CDCl3, ppm): δ 156.60, 140.66, 140.17, 137.53, 136.64, 136.34, 133.26, 132.25,

130.09, 129.60, 128.16, 127.58, 126.74, 126.34, 123.04, 112.86, 67.68, 31.62, 29.68, 29.22,

25.67, 22.55, 14.00. ESI-MS = 707.93 (M++H). Elemental Analysis: (C52H50O2) Calc. (%): C,

88.34; H, 7.13; O, 4.53; Found (%): C, 88.19; H, 7.57.

12

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.5f1 (ppm)

CN-M-1

1.00

7.08

4.12

2.04

3.00

2.03

2.06

-0.0

003

1.54

90

6.70

896.

7267

7.25

047.

2817

7.28

827.

3073

7.32

787.

3395

7.34

497.

3660

7.38

497.

4047

7.41

337.

4473

7.46

757.

5237

7.54

157.

5494

7.56

827.

5849

7.67

617.

6944

7.73

447.

7562

7.77

77

1H NMR (400 MHz, CDCl3) δ7.76 (t, J= 8.7 Hz, 2H), 7.69 (d,J= 7.3 Hz, 2H), 7.60 – 7.51 (m, 3H), 7.46 (d,J= 8.1 Hz, 2H), 7.39 (dd,J= 13.4, 5.5 Hz, 4H), 7.35 – 7.26 (m, 7H), 6.72 (d,J= 7.1 Hz, 1H).

N

Figure S1 1H NMR spectra of CN-TPF

102030405060708090100110120130140150160f1 (ppm)

CN-M-1

76.6

877

.00

77.3

2

110.

11

118.

95

123.

3312

3.54

126.

9712

7.06

127.

6212

7.68

127.

7612

8.04

128.

7412

9.03

129.

7313

0.20

130.

6113

1.37

133.

1213

5.50

135.

8913

6.14

136.

7113

8.18

138.

4213

8.55

138.

6914

0.35

146.

03

13C NMR (100 MHz, CDCl3) δ146.03, 140.35, 138.69, 138.55, 138.42, 138.18, 136.71, 136.14, 135.89, 135.50, 133.12, 131.37, 130.61, 130.20, 129.73, 129.03, 128.74, 128.04, 127.76, 127.68, 127.62, 127.06, 126.97,

123.54, 123.33, 118.95, 110.11, 77.32, 77.00, 76.68.

N

Figure S2 13C NMR spectra of CN-TPF.

13

-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.0f1 (ppm)

M-1

1.00

3.33

2.00

3.20

6.18

3.22

4.14

0.00

01

0.83

480.

8606

0.87

940.

8945

1.25

55

1.53

09

6.67

786.

6955

7.14

137.

1581

7.17

717.

1922

7.21

677.

2343

7.24

867.

2684

7.28

697.

3046

7.33

137.

3485

7.37

607.

4863

7.50

377.

5213

7.53

717.

5559

7.57

337.

7019

7.71

797.

7250

7.74

54

1H NMR (400 MHz, CDCl3) δ7.72 (dd, J= 10.1, 7.3 Hz, 4H), 7.53 (dt,J= 20.3, 7.0 Hz, 3H), 7.36 (d,J= 11.0 Hz, 6H), 7.30 (dd,J= 16.1, 9.0 Hz, 3H), 7.23 (d,J= 7.1 Hz, 2H), 7.17 (q,J= 6.4 Hz, 3H), 6.69 (d,J=

7.1 Hz, 1H).

Figure S3 1H NMR spectra of TPF.

5101520253035404550556065707580859095100105110115120125130135140145f1 (ppm)

M-1

14.1

0

22.6

8

29.3

529

.69

30.0

331

.92

76.6

877

.00

77.3

2

122.

9112

3.34

126.

3312

6.63

127.

2712

7.53

127.

6212

7.80

128.

4512

8.62

129.

1312

9.72

129.

9613

0.33

131.

1413

3.14

135.

7113

5.92

136.

1813

6.62

137.

9213

8.22

139.

3314

0.79

141.

01

13C NMR (100 MHz, CDCl3) δ141.01, 140.79, 139.33, 138.22, 137.92, 136.62, 136.18, 135.92, 135.71, 133.14, 131.14, 130.33, 129.96, 129.72, 129.13, 128.62, 128.45, 127.80, 127.62, 127.53, 127.27, 126.63, 126.33,

123.34, 122.91, 77.32, 77.00, 76.68, 31.92, 30.03, 29.69, 29.35, 22.68, 14.10.

Figure S4 13C NMR spectra of TPF.

14

-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.5f1 (ppm)

CH3-M-1

3.00

1.02

2.14

2.08

0.78

2.26

1.00

1.81

4.54

3.00

3.74

0.00

0

1.49

5

2.26

2

6.64

36.

661

6.96

46.

984

7.10

07.

105

7.11

67.

120

7.23

27.

252

7.27

27.

290

7.31

67.

332

7.35

27.

366

7.37

07.

376

7.38

37.

388

7.39

37.

491

7.50

57.

509

7.51

37.

525

7.52

87.

539

7.54

37.

561

7.68

57.

689

7.69

37.

705

7.70

97.

724

CH3

1H NMR (400 MHz, CDCl3) δ7.73 – 7.67 (m, 4H), 7.57 – 7.48 (m, 3H), 7.40 – 7.36 (m, 5H), 7.34 (d,J= 8.0 Hz, 2H), 7.32 (s, 1H), 7.28 (d,J= 7.1 Hz, 2H), 7.24 (d,J= 8.1 Hz, 1H), 7.13 – 7.09 (m, 2H), 6.97 (d,J=

7.9 Hz, 2H), 6.65 (d,J= 7.1 Hz, 1H), 2.26 (s, 3H).

Figure S5 1H NMR spectra of CH3-TPF.

0102030405060708090100110120130140f1 (ppm)

CH3-M-1

21.0

7

76.6

877

.00

77.3

2

122.

8312

3.31

126.

5612

7.22

127.

5112

7.60

127.

7612

8.30

128.

4712

8.61

129.

1312

9.70

129.

8013

0.32

131.

2213

3.13

135.

5113

5.91

135.

9713

6.17

136.

6813

7.90

138.

0213

8.26

139.

5114

0.68

140.

85

CH3

13C NMR (101 MHz, CDCl3) δ140.85, 140.68, 139.51, 138.26, 138.02, 137.90, 136.68, 136.17, 135.97, 135.91, 135.51, 133.13, 131.22, 130.32, 129.80, 129.70, 129.13, 128.61, 128.47, 128.30, 127.76, 127.60, 127.51,

127.22, 126.56, 123.31, 122.83, 77.32, 77.00, 76.68, 21.07.

Figure S6 13C NMR spectra of CH3-TPF.

15

-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.0f1 (ppm)

M-7

2.46

3.44

2.40

2.02

2.15

2.99

2.00

8.91

3.75

4.18

0.00

0

0.87

80.

894

0.91

0

1.31

31.

322

1.33

11.

384

1.40

11.

420

1.43

41.

509

1.69

01.

706

1.72

61.

743

1.76

03.85

23.

868

3.88

5

6.64

76.

665

6.68

46.

706

7.10

67.

128

7.23

87.

252

7.27

27.

282

7.29

07.

306

7.33

17.

351

7.36

17.

373

7.38

67.

418

7.47

57.

494

7.50

07.

511

7.52

77.

546

7.55

87.

563

7.68

67.

704

7.72

3

1H NMR (400 MHz, CDCl3) δ7.70 (t, J= 7.4 Hz, 12H), 7.52 (ddd,J= 14.4, 8.4, 4.5 Hz, 11H), 7.46 – 7.21 (m, 26H), 7.12 (d,J= 8.7 Hz, 6H), 6.68 (dd,J= 15.5, 7.9 Hz, 9H), 3.87 (t,J= 6.6 Hz, 6H), 1.79 – 1.67 (m,

6H), 1.41 (dd,J= 13.7, 6.2 Hz, 7H), 1.37 – 1.25 (m, 10H), 0.89 (t,J= 6.4 Hz, 7H).

O

CH3

Figure S7 1H NMR spectra of asym-TPF.

0102030405060708090100110120130140150160170f1 (ppm)

M-7

14.0

1

22.5

825

.72

29.2

631

.60

67.8

6

76.6

877

.00

77.3

2

113.

62

122.

7712

3.29

126.

5112

6.56

127.

2112

7.50

127.

6012

7.75

128.

5112

8.60

129.

1312

9.70

130.

3313

0.96

131.

1613

3.13

133.

1713

6.00

136.

1913

6.71

137.

9013

9.56

140.

4214

0.88

157.

74

O

CH3

13C NMR (101 MHz, CDCl3) δ157.74, 140.88, 140.42, 139.56, 138.26, 137.90, 136.71, 136.19, 136.00, 135.34, 133.17, 133.13, 131.16, 130.96, 130.33, 129.70, 129.13, 128.60, 128.51, 127.75, 127.60, 127.50, 127.21,

126.56, 126.51, 123.29, 122.77, 113.62, 77.32, 77.00, 76.68, 67.86, 31.60, 29.26, 25.72, 22.58, 14.01.

Figure S8 13C NMR spectra of asym-TPF.

16

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.0f1 (ppm)

M-3

6.54

16.4

0

4.04

3.95

3.96

1.99

3.99

12.6

2

2.00

-0.0

001

0.86

400.

8813

0.89

75

1.25

381.

2771

1.28

611.

2934

1.32

801.

3438

1.36

301.

3784

1.52

001.

6294

1.64

841.

6659

3.72

203.

7387

3.75

53

6.41

946.

4407

6.55

176.

5694

6.76

376.

7850

7.24

567.

2641

7.27

197.

2832

7.29

347.

3053

7.31

907.

6673

7.68

77

O O

CH3 CH3

1H NMR (400 MHz, CDCl3) δ7.68 (d, J= 8.2 Hz, 2H), 7.35 – 7.23 (m, 12H), 6.77 (d,J= 8.5 Hz, 4H), 6.56 (d,J= 7.1 Hz, 2H), 6.43 (d,J= 8.5 Hz, 4H), 3.74 (t,J= 6.7 Hz, 4H), 1.71 – 1.59 (m, 4H), 1.32 (ddd,J=

15.9, 13.4, 7.7 Hz, 16H), 0.88 (t,J= 6.7 Hz, 6H).

Figure S9 1H NMR spectra of sym-TPF.

102030405060708090100110120130140150160170f1 (ppm)

M-3

14.0

0

22.5

525

.67

29.2

229

.68

31.6

2

67.6

8

76.6

877

.00

77.3

2

112.

86123.

0412

6.34

126.

7412

7.58

128.

1612

9.60

130.

0913

2.25

133.

2613

6.34

136.

6413

7.53

140.

1714

0.66

156.

60

O

CH3

O

CH3

13C NMR (100 MHz, CDCl3) δ156.60, 140.66, 140.17, 137.53, 136.64, 136.34, 133.26, 132.25, 130.09, 129.60, 128.16, 127.58, 126.74, 126.34, 123.04, 112.86, 77.32, 77.00, 76.68, 67.68, 31.62, 29.68, 29.22, 25.67,

22.55, 14.00.

Figure S10 13C NMR spectra of sym-TPF.

17

Figure S11 Mass spectra of CN-TPF.

Figure S12 Mass spectra of TPF.

18

Figure S13 Mass spectra of CH3-TPF.

Figure S14 Mass spectra of asym-TPF.

19

Figure S15 Mass spectra of sym-TPF.

20

Figure S16 Supramolecular packing diagram of fluoranthene derivatives.

21

Table S1. Selective Crystallographic details of fluoranthene derivatives.

Molecule CN-TPF TPF CH3-TPF asym-TPF sym-TPF

Formula C35H21N C34H22 C35H24 C40H34O C56H63O4.5

Formula weight 455.53 430.52 444.54 530.67 808.06

Crystal system Monoclinic Monoclinic Monoclinic Triclinic Monoclinic

Temperature 298K 110K 110K 110K 298K

Space group P21/c P21/c P21/c P-1 P21/c

a (Å) 13.735(2) 10.417(1) 10.717(5) 10.661(1) 12.522(2)

b (Å) 17.809(2) 24.645(1) 21.264(5) 12.346(1) 24.786(6)

c (Å) 10.840(1) 8.672(1) 11.420(5) 13.545(1) 15.897(2)

α(°) 90 90 90 65.98(1) 90

β(°) 112.05(1) 92.51(1) 113.40(1) 69.79(1) 108.86(1)

γ(°) 90 90 90 64.80(1) 90

Volume (Å3) 2457.5(5) 2224.3(2) 2388.3(16) 1443.2(1) 4669.0(1)

Z 4 4 4 2 4

Density (g cm-3) 1.231 1.286 1.236 1.223 1.115

μ (mm-1) 0.071 0.073 0.070 0.071 0.071

F (000) 952 904 936 564 1740

Reflections

collected

55107 18570 19714 23110 94880

Unique

reflections

4315 4331 4596 5603 8196

L.S.

parameters

325 307 318 422 489

Rint 0.0585 0.0422 0.0573 0.0399 0.1411

R1[I > 2σ(I)] 0.0600 0.0406 0.0878 0.0435 0.1392

wR2[I > 2σ(I)] 0.1688 0.0945 0.1669 0.1067 0.3497

∆ρmin, max (e Å-3) -0.219/0.292 -0.211/0.193 -0.280/0.248 -0.193/0.247 -0.464/0.636

GOOF 1.100 1.009 1.116 1.070 1.226

CCDC No. 1402234 965009 965006 965010 1402235

22

Table S2 Summary of torsional angles.

Compounds

Torsion angle

about C13-

C23(°)

Torsion angle

about C16-

C17(°)

Torsion angle

about C15-C29(°)

Torsion angle

about C14-

C35(°)

CN-TPF 54.3(4) -75.2(3) -49.4(4) -

TPF 128.4(1) -61.6(2) -51.4(2) -

CH3-TPF 83.4(5) -67.5(5) -53.9(5) -

asym-TPF -56.1(2) 65.2(2) 62.6(2) -

sym-TPF 68.2(7) -101.2(6) -118.4(5) 62.5(7)

Figure S17 Cyclic voltammograms of fluoranthene derivatives in acetonitrile. Fc/Fc+ couple was used as an internal reference and Bu4NF6 was used as supporting electrolyte with scan rate of 50 mV s-1.

23

Figure S18 Simulated UV-visible absorption spectra of fluoranthene derivatives at TD-DFT/M062X/3-21G level of theory.

Table S3. Selected UV-visible key transitions of fluoranthene derivatives at the TD-DFT/M062X/3-21G level of theory in gaseous phase.

TD-DFT/M062X/3-21GCompound Expt.

(nm) λ (nm) λ (eV) fKey transitions

CN-TPF

376329302243

358285279241

3.464.334.435.13

0.310.100.630.18

H-1→L, H→LH-4→L, H-2→L

H-2→L+1, H→L+1H-1→L+1, H→L+2

TPF

375329295243

362287279

3.424.304.43

0.250.120.38

H-1→L, H→L, H→L+1H-5→L, H-4→L, H-2→L

H-5→L, H-3→L, H-1→L, H→L+1

CH3-TPF

375329298243

498415325312279259

2.482.983.813.964.434.78

0.070.170.320.130.070.05

H-1→L, H→LH-1→L, H→L, H→L+1

H-5→L, H-4→L, H-3→L, H-1→L, H→L+1H-5→L, H-4→L, H-3→L, H-1→L+1, H→L+1

H→L+2, H→L+4H-2→L+1, H-1→L+2, H→L+4, H→L+6, H→L+7

asym -TPF

377329300243

427356280227

2.903.484.425.44

0.100.280.620.22

H-1→L, H→LH-1→L, H→L, H→L+1

H-3→L, H→L+1H-4→L, H→L+2, H→L+5, H→L+6

sym-TPF

376329300243

360309283211

3.444.014.375.85

0.400.080.570.46

H-1→L, H→L+2H-6→L, H-2→L, H→L

H-3→L, H→L+1H-1→L+3, H-1→L+6

24

Figure S19 CIE 1931 chromaticity plot.

Figure S20 Luminescence efficiency-luminance (LE-L) characteristic plot.