by Crystal Design Electronic Supplementary Information ... · Achieving Very Bright Mechanoluminescence from Purely Organic Luminophores with Aggregation-Induced Emission by Crystal

Electronic Supplementary Information

Achieving Very Bright Mechanoluminescence from Purely Organic Luminophores with Aggregation-Induced Emission by Crystal Design

Bingjia Xu,a,b Wenlang Li,a Jiajun He,a Sikai Wu,a Qiangzhong Zhu,b Zhiyong Yang,*a Yuan-Chun Wu,c Yi Zhang,*a Chongjun Jin,b Po-Yen Lu,c Zhenguo Chi,*a Siwei Liu,a Jiarui Xua and Martin R. Bryced

a PCFM Lab, GD HPPC Lab, Guangdong Engineering Technology Research Center for High-performance

Organic and Polymer Photoelectric Functional Films, State Key Laboratory of Optoelectronic Material and

Technologies, School of Chemistry and Chemical Engineering, Sun Yet-sen University, Guangzhou 510275,

China.

E-mail: [email protected]; [email protected]; [email protected]; Tel: +86 20

84112712.b State Key Laboratory of Optoelectronic Material and Technologies, School of Physics and Engineering,

Sun Yat-sen University, Guangzhou 510275, China.c Shenzhen China Star Optoelectronics Technology Co., Ltd, Guangdong, China.d Department of Chemistry, Durham University, Durham DH1 3LE, UK.

1. General experimental proceduresMaterials (2-bromoethene-1,1,2-triyl)tribenzene, 9H-fluoren-9-one, benzophenone, tetrakis(triphenyl

phosphine) palladium(0), Aliquat 336, (4-acetylphenyl)boronic acid, (4-formylphenyl)boronic acid and (3-

formylphenyl)boronic acid purchased from Alfa Aesar were used as received. The compounds 4-(1,2,2-

triphenylvinyl)benzaldehyde (p-P4A)1 and 9-(dibromomethylene)-9H-fluorene (FBr2)2, and (2,2-dibromo ethene-

1,1-diyl)dibenzene (P2Br2)2 were synthesized according to the literature methods. Ultra-pure water was used in

the experiments. All other reagents and solvents were purchased with analytical grade from Guangzhou

Jincheng Company (China) and used without further purification. The water/tetrahydrofuran mixtures with

different water fractions were prepared by slowly adding distilled water into the THF solution of the

samples under ultrasound at room temperature.

Characterization Proton and carbon NMR (1HNMR and 13CNMR) spectra were measured on a Mercury-Plus

300 spectrometer, a Bruker AVANCE 400 spectrometer or a Bruker AVANCE III spectrometer (CDCl3,

tetramethylsilane as the internal standard). The mass spectra were measured using Thermo spectrometers

(DSQ & MAT95XP-HRMS). The FT-IR spectra were obtained on a Nicolet NEXUS 670 spectrometer (KBr

pellet). The elemental analysis was performed with a Vario EL analyzer. The UV-visible absorption spectra

were determined on a Hitachi U-3900 spectrophotometer. The PL spectra were measured on an Ocean

Optics Maya Pro2000 instrument with a 365 nm Ocean Optics LLS-LED as the excitation source. Light was

introduced into the detector through an optical fiber. The ML spectra were collected from an Acton SP2750

spectrometer with a liquid-nitrogen-cooled CCD (SPEC-10, Princeton) as a power detector. ML images of p-

P4A, m-P4A and p-P4A2 were directly extracted from the supplementary movies (Videos S1, S2, S4 and S5)

captured by a digital camera (Nikon D5100) with an AF-S Nikkor 35mm f/1.8G DX camera lens. This method

is similar to the one employed in previous report.3 Herein, the movies were transcribed by the camera in

Electronic Supplementary Material (ESI) for Chemical Science.This journal is © The Royal Society of Chemistry 2016

an automatic mode with a capturing speed of 29 frames per second. The image of the capital letters “AITL”

was captured by the Nikon D5100 digital camera in a manual mode. The corresponding parameters were

set up as follows: aperture value f/2, exposure time 26 s, ISO 1600 and exposure compensation +0.3. The

thermal behaviors were determined by DSC at heating and cooling rates of 10 °C/min under N2 atmosphere

using a NETZSCH thermal analyzer (DSC 204F1). Wide-angle XRD measurements were performed at 293 K

using a Bruker X-ray diffractometer (D8 ADVANCE, Germany) with an X-ray source of Cu Kα (λ= 0.15406 nm)

at 40 kV and 40 mA at a scan rate of 4° (2θ)/min. The fluorescence quantum yields of solid powders were

measured in air on an integrating sphere (HAMAMATSU C11347) with a 330 nm UV light as the excitation

source. The quantum chemistry calculations were performed at the B3LYP/6-31G (d, p) level of theory

using the DFT method in the Gaussian 09 software.

The single crystals of all the target compounds were isolated from the mixtures of ethanol and CH2Cl2

through the method of solvent evaporation. X-ray diffraction data for the single crystals were collected

from a Bruker Smart 1000 CCD with Cu-K radiation ( =1.54178 Å) at 150(10) K. All the structures were

solved using direct methods following the difference Fourier syntheses. All non-hydrogen atoms were

anisotropically refined through least-squares on F2 using the SHELXTL program suite. The anisotropic

thermal parameters were assigned to all non-hydrogen atoms. The hydrogen atoms attached to carbon

were placed in idealized positions and refined using a riding model to the atom from which they were

attached. The pictures of the structures were produced using Diamond 3.2. CCDC 1468361, 1468362,

1468363, 1468364, and 1468365 contain the supplementary crystallographic data of m-P4A, p-FP2A, p-P4A,

p-P4A2, p-P4Ac for this paper, respectively.

References1 X. Q. Zhang, Z. G. Chi, H. Y. Li, B. J. Xu, X. F. Li, W. Zhou, S. W. Liu, Y. Zhang and J. R. Xu., Chem.-Asian J. 2011,

6, 808.

2 P. M. Donovan and L. T. Scott., J. Am. Chem. Soc., 2003, 126, 3108.

3 S. M. Jeong, S. Song, S. Lee, and N. Y. Ha., Adv. Mater., 2013, 25, 6194.

2. Synthesis

O

Br

Pd(PPh3)4 , K2CO3 (2 M.aq.)

BHO

HO

Aliquat 336, Toluene, 80 oC, 16 h

O

CH3

CH3

p-P4Ac

O


BHO

HO


O

H

H

p-P4A

Pd(PPh3)4 , K3PO4

BHO

HO

1,4-Dioxane, 80 oC, 16 h

OH

m-P4A

O H

O


BHO

HO


O

H

p-FP2A

Br Br BHO

HOH

FBr2

O


BHO

HO


O

H HBr Br

O

H

p-P4A2P2Br2

Scheme 1. Synthetic routes of the target compounds.

Synthesis of 4-(1,2,2-triphenylvinyl)benzaldehyde (p-P4A) [1] (2-bromoethene-1,1,2-triyl)tribenzene (1.00 g, 2.98

mmol) and (4-formylphenyl)boronic acid (0.49 g, 3.28 mmol) were dissolved in toluene (30 mL), and then 2 M

aqueous K2CO3 solution (4.5 mL) and Aliquat 336 (5 drops) were added. The mixture was stirred for 40 min under

an argon atmosphere at room temperature. Then the Pd(PPh3)4 catalyst was added, and the reaction mixture

was stirred at 80 ˚C for 16 h. After cooling to room temperature, the product was concentrated and purified by

silica gel column chromatography with dichloromethane/n-hexane (v/v=1:3). Compound p-P4A was obtained as a

yellow crystalline solid in 97% yield (1.04 g). 1H NMR (300 MHz, CDCl3) δ (ppm): 9.90-9.87 (s, 1 H); 7.64-7.57 (d,

J=8.4 Hz, 2 H); 7.22-7.16 (d, J=8.1 Hz, 2 H); 7.15-7.05 (m, 9 H); 7.05-6.96 (m, 6 H). EI-MS, m/z: [M]+ 360; calcd for

C27H20O 360. HRMS, m/z: [M]+ 360.1511; calcd for C27H20O 360.1514. Anal. Calc. for C27H20O: C 89.97%, H 5.59%;

found: C 89.91%, H 5.63%.

Synthesis of 1-(4-(1,2,2-triphenylvinyl)phenyl)ethanone (p-P4Ac) (2-bromoethene-1,1,2-triyl) tribenzene (1.00g,

2.98 mmol) and (4-acetylphenyl)boronic acid (0.54 g, 3.28 mmol) were dissolved in toluene (30 mL), and then 2

M aqueous K2CO3 solution (4.5 mL) and Aliquat 336 (5 drops) were added. The mixture was stirred for 40 min

under an argon atmosphere at room temperature. Then the Pd(PPh3)4 catalyst was added and the reaction

mixture was stirred at 80 ˚C for 16 h. After cooling to room temperature, the product was concentrated and

purified by silica gel column chromatography with dichloromethane/n-hexane (v/v=1:3). p-P4Ac was obtained as

a white crystalline solid in 94% yield (1.05 g). 1H NMR (300 MHz, CDCl3) δ (ppm): 7.72-7.64 (d, J=8.1 Hz, 2 H); 7.16-

7.06 (m, 11 H); 7.05-6.95 (m, 6 H); 2.57-2.50 (s, 3 H). 13C NMR (100 MHz, CDCl3) δ (ppm): 191.79, 146.66, 144.20,

143.55, 143.50, 141.69, 140.19, 137.29, 135.09, 132.00, 131.35, 131.31, 130.34, 130.18, 128.02, 127.81, 127.76,

127.66, 127.34, 126.64, 126.59, 126.55, 126.50. FT-IR (KBr) υ (cm-1): 3056, 3022, 1675, 1600, 1490, 1441, 1263,

763, 699. EI-MS, m/z: [M]+ 374; calcd for C28H22O 374. HRMS, m/z: [M]+ 374.1662; calcd for C28H22O 374.1671.

Anal. Calc. for C28H22O: C 89.81%, H 5.92%; found: C 89.84%, H 5.96%.

Synthesis of 4-((9H-fluoren-9-ylidene)(phenyl)methyl)benzaldehyde (p-FP2A) FBr2 (1.00g, 2.97mmol),

benzeneboronic acid (0.40g, 3.27mmol) and (4-formylphenyl)boronic acid (0.49g, 3.27mmol) were dissolved in

toluene (30 mL), and then 2 M aqueous K2CO3 solution (4 mL) and Aliquat 336 (5 drops) were added. The mixture

was stirred for 40 min under an argon atmosphere at room temperature. Then the Pd(PPh3)4 catalyst was added

and the reaction mixture was stirred at 80 ˚C for 16 h. After cooling to room temperature, the product was

concentrated and purified by silica gel column chromatography with dichloromethane/n-hexane (v/v=1:2). p-

FP2A was obtained as a pale yellow crystalline solid in 46% yield (0.49 g). 1H NMR (300 MHz, CDCl3) δ (ppm):

10.13-10.00 (s, 1 H); 7.98-7.88 (d, J=8.0 Hz, 2 H); 7.73-7.65 (d, J=7.5 Hz, 2 H); 7.61-7.54 (d, J=8.3 Hz, 2 H); 7.46-

7.40 (m, 3 H); 7.39-7.34 (m, 2 H); 7.29-7.21 (t, 2 H); 6.96-6.89 (m, 2 H); 6.64-6.58 (d, J=8.0 Hz, 2 H). 13C NMR (100

MHz, CDCl3) δ (ppm): 191.76, 149.22, 143.31, 142.12, 140.83, 140.67, 138.35, 138.08, 135.80, 135.31, 130.51,

130.18, 129.65, 129.06, 128.55, 128.18, 126.64, 126.56, 125.05, 124.84, 119.48, 119.36. FT-IR (KBr) υ (cm-1): 3052,

2841, 1700, 1598, 1437, 737, 698. EI-MS, m/z: [M]+ 358; calcd for C27H18O 358. HRMS, m/z: [M]+ 358.1354; calcd

for C27H18O 358.1358. Anal. Calc. for C27H18O: C 90.47%, H 5.06%; found: C 90.42%, H 5.09%.

Synthesis of 3-(1,2,2-triphenylvinyl)benzaldehyde (m-P4A) (2-bromoethene-1,1,2-triyl)tribenzene (1.23 g, 3.67

mmol) and (3-formylphenyl)boronic acid (0.50 g, 3.33 mmol) were dissolved in 1,4-dioxane (30 mL), and then

potassium phosphate (1.72g, 8.10 mmol) were added. The mixture was stirred for 40 min under an argon

atmosphere at room temperature. Then the Pd(PPh3)4 catalyst was added and the reaction mixture was stirred at

80 ˚C for 16 h. After cooling to room temperature, the product was concentrated and purified by silica gel column

chromatography with dichloromethane/n-hexane (v/v=1:4). m-P4A was obtained as a white crystalline solid in 72%

yield (0.70 g). 1H NMR (300 MHz, CDCl3) δ (ppm): 9.81-9.76 (s, 1 H); 7.63-7.59 (dd, 1 H); 7.54-7.49 (s, 1 H); 7.33-

7.21 (m, 2 H); 7.15-7.07 (m, 9 H), 7.06-6.99 (m, 6 H). 13C NMR (100 MHz, CDCl3) δ (ppm): 192.20, 144.83, 143.10,

143.03, 142.86, 142.43, 139.45, 137.28, 136.12, 133.05, 131.26, 131.23, 131.15, 128.37, 127.90, 127.87, 127.72,

127.22, 126.82, 126.74. FT-IR (KBr) υ (cm-1): 3051, 2716, 2795, 1702, 1586, 1437, 755, 700. EI-MS, m/z: [M]+ 360;

calcd for C27H20O 360. HRMS, m/z: [M]+ 360.1508; calcd for C27H20O 360.1514. Anal. Calc. for C27H20O: C 89.97%,

H 5.59%; found: C 89.93%, H 5.61%.

Synthesis of 4,4'-(2,2-diphenylethene-1,1-diyl)dibenzaldehyde (p-P4A2) P2Br2 (1.00g, 2.97mmol) and (4-

formylphenyl)boronic acid (0.98 g, 6.51 mmol) were dissolved in toluene (30 mL), and then 2 M aqueous K2CO3

solution (8 mL) and Aliquat 336 (5 drops) were added. The mixture was stirred for 40 min under an argon

atmosphere at room temperature. Then the Pd(PPh3)4 catalyst was added and the reaction mixture was stirred at

80 ˚C for 16 h. After cooling to room temperature, the product was concentrated and purified by silica gel column

chromatography with dichloromethane/n-hexane (v/v=2:1). p-P4A2 was obtained as a yellow crystalline solid in

83% yield (1.09 g). 1H NMR (500 MHz, CDCl3) δ (ppm): 9.93-9.90 (s, 2 H); 7.66-7.63 (d, J=8.3 Hz, 4 H); 7.19-7.11 (m,

10 H); 7.04-6.99 (dd, J=7.9, 1.5 Hz, 4 H). 13C NMR (125 MHz, CDCl3) δ (ppm): 191.75, 149.62, 145.08, 142.37,

138.52, 134.59, 131.39, 131.21, 129.37, 128.03, 127.53.. FT-IR (KBr) υ (cm-1): 3058, 2800, 2744, 1694, 1597, 1564,

1208, 1166, 700. EI-MS, m/z: [M]+ 388; calcd for C28H20O2 388. HRMS, m/z: [M]+ 388.1454; calcd for C28H20O2

388.1463. Anal. Calc. for C28H20O2: C 86.57%, H 5.19%; found: C 86.52%, H 5.23%.

3. Figures and Tables

S

N NS

O O

SFPC

a

S

O

P4TA

b

TMPE

c

O O

O O

Fig. S1 Molecular structures of previously reported AIE-ML luminophores.

50 100 150 200

m-P4A

p-P4A2

Wavelength (nm)

End

o 180 oC

136 oC

(a)

0 10 20 30 40

Nor

mal

ized

Inte

nsity

2 (Deg)

p-P4A2-SC

p-P4A2-P

m-P4A-SC

m-P4A-P

(b)

Fig. S2 DSC curves (a) and XRD patterns (b) of m-P4A and p-P4A2. m-P4A-P, powder of m-P4A; m-P4A-SC,

single crystal of m-P4A; p-P4A2-P, powder of p-P4A2; p-P4A2-SC, single crystal of p-P4A2.

Fig. S3 Molecular packing and intermolecular interactions of p-P4A (a), m-P4A (b) and p-P4A2 (c) in their

single crystal structures

Fig. S4 The HOMO (lower images), LUMO (upper images), oscillator strengths (f) and dipolar moments of

the molecules in their single crystal structures. p-P4A-BSC1 and p-P4A-BSC2 are the two conformations of p-

P4A.

Table S1. Computed vertical transitions and their oscillator strengths.

Conformation Oscillator Strength (f) Transition Coefficients

0.3722 HOMO→LUMO 0.70088

0.0020 HOMO-2→LUMO 0.56951

HOMO-2→LUMO+1 0.16973

HOMO-1→LUMO -0.34159

0.1340 HOMO-3→LUMO 0.14718


HOMO→LUMO+1 0.66590

0.0233 HOMO-3→LUMO 0.15269

HOMO-2→LUMO 0.32352



p-P4A-BSC1 a


0.0004 HOMO-1→LUMO 0.67912

HOMO-1→LUMO+1 -0.14246

0.3270 HOMO→LUMO 0.69801

0.0939 HOMO-2→LUMO 0.49176


0.1160 HOMO-3→LUMO 0.36658


p-P4A-BSC2 a

HOMO→LUMO+1 -0.39175

0.0152 HOMO→LUMO 0.69946

0.0007 HOMO-4→LUMO 0.67992

HOMO-4→LUMO+1 0.10950

0.3357 HOMO→LUMO+1 0.70038

0.0157 HOMO-2→LUMO -0.11298


HOMO-1→LUMO+1 -0.14060

m-P4A

HOMO-1→LUMO+2 -0.25398

0.3146 HOMO→LUMO 0.68955

HOMO→LUMO+1 -0.13006

0.2413 HOMO→LUMO 0.12768


0.0000 HOMO-3→LUMO -0.12430


HOMO-2→LUMO+1 0.34096

HOMO-2→LUMO+3 0.14894


HOMO-1→LUMO+1 -0.14811

0.0020 HOMO-4→LUMO -0.37880

p-P4A2

HOMO-4→LUMO+1 0.51392


HOMO-3→LUMO+1 -0.17444a p-P4A-BSC1 and p-P4A-BSC2 are the two conformations of p-P4A.

350 400 450 500 550 600 6500

100

200

300

400

500

0 20 40 60 80 1000

100

200

300

400

500

PL In

tens

ity (a

.u.)

Water Fraction (%)

PL In

tens

ity (a

.u.)

Wavelength (nm)

0 20 40 60 80 90 95

Water Fraction (%)(a)

300 400 500 600 700 8000.0

0.5

1.0

1.5

PL In

tens

ity (a

.u.)

Wavelength (nm)

0 20 40 60 80 90 95

Water Fraction (%)

(b)

Fig. S5 PL (a) and UV-visible (b) spectra of p-P4A2 in the mixtures of THF/water with different water

contents. The inset of (a) are the changes of peak intensities (upper) of the PL spectra and the fluorescence

images (lower) of p-P4A2 in pure THF and in the mixtures of THF/water with 95% water fraction. The PL

spectra were recorded under the excitation of 365 nm UV light.

300 400 500 6000

25

50

75

0 20 40 60 80 100

0

20

40

60

80

PL In

tens

ity (a

.u.)

Water Fraction (%)

0 20 40 60 80 90 95

Water Fraction (%)

Inte

nsity

(a.u

.)

Wavelength (nm)

(a)

300 400 500 600 700 8000.0

0.5

1.0

1.5

PL In

tens

ity (a

.u.)

Wavelength (nm)

0 20 40 60 80 90 95

Water Fraction (%)

(b)

Fig. S6 PL (a) and UV-visible (b) spectra of m-P4A in the mixtures of THF/water with different water

contents. The inset of (a) are the changes of peak intensities (upper) of the PL spectra and the fluorescence

images (lower) of m-P4A in pure THF and in the mixtures of THF/water with 95% water fraction. The PL

spectra were recorded under the excitation of 365 nm UV light.

Table S2 Effective diameter and polydispersity of the compounds in THF/water mixtures.a

Compound Effective Diameter (nm) Polydispersityp-P4A 326.36 0.161p-P4A2 395.68 0.176m-P4A 339.06 0.179

a In THF/water mixtures with 95% water content.

280 300 320 3400

10

20

30

40

Num

ber P

erce

ntag

e (%

)

Diameter (nm)

p-P4A

(a)

250 300 350 400 450 500 550 6000

10

20

30

40

50(b)

Num

ber P

erce

ntag

e (%

)

Diameter (nm)

p-P4A2

250 300 350 400 4500

10

20

30

40(c)

Num

ber P

erce

ntag

e (%

)

Diameter (nm)

m-P4A

Fig. S7 The particle diameter distributions of the compounds in THF/water mixtures with 95% water

content.

0 10 20 30 40

f

e

d

b

c

Nor

mal

ized

Inte

nsity

2 (Deg)

a

Fig. S8 XRD patterns of the original and ground samples of the compounds. a, Original sample of p-P4A; b, ground sample of p-P4A; c, original sample of m-P4A; d, ground sample of m-P4A; e, original sample of p-P4A2; f, ground sample of p-P4A2.

4. Structural Information

4.04.55.05.56.06.57.07.58.08.59.09.510.010.511.0δ (ppm)

6.01

9.02

2.03

1.98

0.97

Fig. S9 1H NMR spectrum of p-P4A in CDCl3

Instrument:DSQ(Thermo)Ionization Method:EID:\DSQ\DATA-LR\14\090403 9/4/2014 3:46:47 PM P4A

090403 #49 RT: 1.27 AV: 1 NL: 2.73E5T: + c Full ms [45.00-800.00]

50 100 150 200 250 300 350 400 450m/z

0

5

10

15

20

25

30

35

40

45

50

55

60

65

70

75

80

85

90

95

100

Rel

ativ

e A

bund

ance

253

126

149 360239

57 165

69 11328291

95 176 226138 269215 289 315

202 331345

Fig. S10 EI-MS of p-P4A

Instrument:MAT 95XP(Thermo)D:\DATA-HR\15\032401-p-p4a-c1 3/24/2015 3:30:19 PM p-P4A

032401-p-p4a-c1 #22 RT: 0.95 AV: 1 NL: 3.68E4T: + c EI Full ms [ 353.50-364.50]

359.5 359.6 359.7 359.8 359.9 360.0 360.1 360.2 360.3 360.4 360.5 360.6 360.7 360.8m/z

0

5

10

15

20

25

30

35

40

45

50

55

60

65

70

75

80

85

90

95

100

Rel

ativ

e A

bund

ance

360.1511

Fig. S11 HRMS of p-P4A

2.02.53.03.54.04.55.05.56.06.57.07.5δ (ppm)

3.02

6.00

10.9

9

1.98

Fig. S12 1H NMR spectrum of p-P4Ac in CDCl3

0102030405060708090100110120130140150160170180190200δ (ppm)

26.5

0

126.

7612

6.91

127.

7112

7.78

127.

8713

1.26

134.

99

139.

89

149.

02

197.

69

Fig. S13 13C NMR spectrum of p-P4Ac in CDCl3

Instrument:DSQ(Thermo)Ionization Method:EID:\DSQ\DATA-LR\14\090404 9/4/2014 3:52:34 PM P4Ac


50 100 150 200 250 300 350 400 450m/z

0

5

10

15

20

25

30

35

40

45

50

55

60

65

70

75

80

85

90

95

100

Rel

ativ

e A

bund

ance

253

374

149

12657

69165

23981

113 31514191 359331179289226105

302202263

341

Fig. S14 EI-MS of p-P4Ac

Instrument:MAT 95XP(Thermo)D:\DATA-HR\15\032405-p4ac-c1 3/24/2015 4:48:43 PM P4Ac

032405-p4ac-c1 #15 RT: 0.56 AV: 1 NL: 3.24E4T: + c EI Full ms [ 372.50-393.70]

373.4 373.5 373.6 373.7 373.8 373.9 374.0 374.1 374.2 374.3 374.4 374.5 374.6 374.7 374.8m/z

0

5

10

15

20

25

30

35

40

45

50

55

60

65

70

75

80

85

90

95

100

Rel

ativ

e A

bund

ance

374.1662

Fig. S15 HRMS of p-P4Ac

4000 3500 3000 2500 2000 1500 1000 500

0

20

40

60

80

100

Tran

smitt

ance

(%)

Wavenumber (cm-1)

3056 3022

1675

1600

14901441

1268

763

699

Fig. S16 FT-IR spectrum of p-P4Ac

4.55.05.56.06.57.07.58.08.59.09.510.010.511.0δ (ppm)

2.01

2.02

0.99

1.06

2.01

3.00

2.00

2.02

2.01

1.00

Fig. S17 1H NMR spectrum of p-FP2A in CDCl3

100105110115120125130135140145150155160165170175180185190195200205δ (ppm)

119.

3611

9.48

124.

8412

5.05

126.

5612

6.64

128.

18

129.

0613

5.31

135.

8013

8.08

140.

6714

0.83

142.

1214

3.31

149.

22

191.

76

Fig. S18 13C NMR spectrum of p-FP2A in CDCl3

Instrument:DSQ(Thermo)Ionization Method:EID:\DSQ\DATA-LR\14\042804 4/28/2014 3:33:34 PM W2A


50 100 150 200 250 300 350 400 450m/z

0

5

10

15

20

25

30

35

40

45

50

55

60

65

70

75

80

85

90

95

100R

elat

ive

Abu

ndan

ce358

253

329

163150

313

143 300281179 224125 34326320077 23711210051

Fig. S19 EI-MS of p-FP2A

Instrument:MAT 95XP(Thermo)D:\DATA-HR\15\032404-fp2a-c1 3/24/2015 4:15:01 PM FP2A

032404-fp2a-c1 #18 RT: 0.46 AV: 1 NL: 4.42E4T: + c EI Full ms [ 353.50-364.50]

357.5 357.6 357.7 357.8 357.9 358.0 358.1 358.2 358.3 358.4 358.5 358.6 358.7 358.8 358.9 359.0m/z

0

5

10

15

20

25

30

35

40

45

50

55

60

65

70

75

80

85

90

95

100

Rel

ativ

e A

bund

ance

358.1354

Fig. S20 HRMS of p-FP2A

4000 3500 3000 2500 2000 1500 1000 500

0

20

40

60

80

100Tr

ansm

ittan

ce (%

)

Wavenumber (cm-1)

3052

2841

1700

15981437

737

698

Fig. S21 FT-IR spectrum of p-FP2A

5.86.26.67.07.47.88.28.69.09.49.810.210.611.0f1 (ppm)

6.02

9.01

0.22

1.80

1.02

1.00

0.94

Fig. S22 1H NMR spectrum of m-P4A in CDCl3

0102030405060708090100110120130140150160170180190200210f1 (ppm)

126.

7412

6.82

127.

2212

7.72

127.

8712

7.90

128.

3713

1.15

131.

2313

1.26

133.

0513

6.12

137.

2813

9.45

142.

4314

2.86

143.

0314

3.10

144.

83

192.

20

Fig. S23 13C NMR spectrum of m-P4A in CDCl3

Instrument:DSQ(Thermo)Ionization Method:EID:\DSQ\DATA-LR\14\042402 4/24/2014 5:32:52 PM m-P4A


50 100 150 200 250 300 350 400 450m/z

0

5

10

15

20

25

30

35

40

45

50

55

60

65

70

75

80

85

90

95

100

Rel

ativ

e A

bund

ance

360105

182

253

16777

152

27312657

2399169 28197 265 331141 31583

Fig. S24 EI-MS of m-P4A

Instrument:MAT 95XP(Thermo)D:\DATA-HR\15\032402-m-p4a-c1 3/24/2015 3:37:29 PM m-P4A

032402-m-p4a-c1 #22 RT: 0.63 AV: 1 NL: 2.60E4T: + c EI Full ms [ 353.50-364.50]

359.5 359.6 359.7 359.8 359.9 360.0 360.1 360.2 360.3 360.4 360.5 360.6 360.7 360.8 360.9m/z

0

5

10

15

20

25

30

35

40

45

50

55

60

65

70

75

80

85

90

95

100R

elat

ive

Abu

ndan

ce360.1508

Fig. S25 HRMS of m-P4A

4000 3500 3000 2500 2000 1500 1000 500

0

20

40

60

80

100

Tran

smitt

ance

(%)

Wavenumber (cm-1)

3051 2716

2795

1702

1586

1487

700

755

Fig. S26 FT-IR spectrum of m-P4A

4.04.55.05.56.06.57.07.58.08.59.09.510.010.511.0f1 (ppm)

4.01

10.0

5

4.00

2.00

CH2Cl2

Fig. S27 1H NMR spectrum of p-P4A2 in CDCl3

60708090100110120130140150160170180190200210f1 (ppm)

127.

5312

8.03

129.

3713

1.21

131.

9313

4.59

138.

5214

2.37

145.

08

149.

62

191.

75

Fig. S28 13C NMR spectrum of p-P4A2 in CDCl3

Instrument:DSQ(Thermo)Ionization Method:EID:\DSQ\DATA-LR\14\052302 5/23/2014 3:50:14 PM P4A2


50 100 150 200 250 300 350 400 450m/z

0

5

10

15

20

25

30

35

40

45

50

55

60

65

70

75

80

85

90

95

100R

elat

ive

Abu

ndan

ce388

253

389

252

254239126 315145 156 390331289176 359282119 22621577 19491

Fig. S29 EI-MS of p-P4A2

Instrument:MAT 95XP(Thermo)D:\DATA-HR\15\032406-p4a2-c1 3/24/2015 4:51:02 PM P4A2

032406-p4a2-c1 #15 RT: 0.37 AV: 1 NL: 9.81E4T: + c EI Full ms [ 379.50-393.70]

387.4 387.5 387.6 387.7 387.8 387.9 388.0 388.1 388.2 388.3 388.4 388.5 388.6 388.7 388.8 388.9m/z

0

5

10

15

20

25

30

35

40

45

50

55

60

65

70

75

80

85

90

95

100

Rel

ativ

e A

bund

ance

388.1454

Fig. S30 HRMS of p-P4A2

4000 3500 3000 2500 2000 1500 1000 500

20

40

60

80

100

Tran

smitt

ance

(%)

Wavenumber (cm-1)

3058

2800 2744

1694

1597

1208

1166

700

1564

Fig. S31 FT-IR spectrum of p-P4A2

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