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Electronic Supporting Information

The Unusual Aggregation-Induced Emission of Coplanar

Organoboron Isomers and Their Lipid Droplets-Specific Applications

Jen-Shyang Ni, Haixiang Liu, Junkai Liu, Meijuan Jiang, Zheng Zhao, Yuncong Chen, Ryan

T. K. Kwok, Jacky W. Y. Lam, Qian Peng* and Ben Zhong Tang*

HKUST-Shenzhen Research Institute, No. 9 Yuexing 1st RD, South Area, Hi-tech Park,

Nanshan, Shenzhen 518057, China

Department of Chemistry, Hong Kong Branch of Chinese National Engineering Research

Center for Tissue Restoration and Reconstruction, Institute for Advanced Study, Division of

Life Science and Division of Biomedical Engineering, Hong Kong University of Science and

Technology, Clear Water Bay, Kowloon, Hong Kong

Key Laboratory of Organic Solids, Institute of Chemistry, Chinese Academy of Sciences,

Beijing 100190, China

SCUT-HKUST Joint Research Laboratory, State Key Laboratory of Luminescent Materials and

Devices, South China University of Technology, Guangzhou 510640, China

Electronic Supplementary Material (ESI) for Materials Chemistry Frontiers.This journal is © the Partner Organisations 2018

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Scheme S1. Structures of near-coplanar AIEgens.

Scheme S2. Lipid droplets targeting probes based on organoboron materials.

3

Figure S1. 1H NMR spectrum of POABP in CDCl3.

Figure S2. 13C NMR spectrum of POABP in CDCl3.

9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 ppm

7.4

94

7.5

13

7.5

32

7.5

94

7.5

99

7.6

11

7.6

31

7.6

61

7.6

79

7.6

97

7.9

04

8.1

99

8.2

17

8.4

41

8.4

60

2.0

9

3.0

6

1.0

8

1.0

7

2.0

0

2.0

7

180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm

126.9

02

128.7

79

128.9

56

129.0

95

129.3

70

133.7

54

134.4

36

134.8

37

150.8

96

173.0

73

4

Figure S3. 1H NMR spectrum of DMA-POABP in THF-d8.

Figure S4. 13C NMR spectrum of DMA-POABP in THF-d8.

9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 ppm

3.1

55

6.8

65

6.8

88

7.4

76

7.4

94

7.5

13

7.5

52

7.5

65

7.5

70

7.5

77

7.5

89

7.8

63

8.1

35

8.1

39

8.1

57

8.4

31

8.4

47

6.0

9

2.0

5

2.0

5

1.0

3

1.0

4

2.0

0

2.0

0

180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm

40.2

19

40.5

36

112.5

28

112.8

77

117.9

84

128.4

73

129.2

68

129.4

08

129.6

56

133.5

79

138.1

42

151.2

50

155.6

26

170.6

47

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Figure S5. 1H NMR spectrum of POABP-DMA in THF-d8.

Figure S6. 13C NMR spectrum of POABP-DMA in THF-d8.

9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 ppm

3.0

89

6.7

82

6.8

04

7.5

77

7.5

82

7.5

98

7.6

17

7.6

25

7.6

35

7.6

41

8.0

24

8.0

47

8.5

82

8.5

86

8.6

03

6.0

8

2.0

3

3.0

0

2.9

7

2.0

0

180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm

40

.26

9

11

2.1

98

11

4.2

91

13

0.0

54

13

1.4

28

13

1.7

60

13

4.6

83

13

5.0

41

14

8.6

78

15

5.3

51

17

4.3

36

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Figure S7. High-resolution mass spectrum of POABP.

Figure S8. High-resolution mass spectrum of DMA-POABP.

njs-js01, mw=272; NH3

m/z60 80 100 120 140 160 180 200 220 240 260 280 300 320 340 360 380 400 420 440 460 480

%

0

100

tan170908_6 86 (1.434) Cm (84:86-1:48) TOF MS CI+ 3.62e4273.0999

253.0965195.0537 225.1028 290.1305

njs-js03, mw=315; NH3

m/z60 80 100 120 140 160 180 200 220 240 260 280 300 320 340 360 380 400 420 440 460 480 500 520 540

%

0

100

tan170908_8 97 (1.617) Cm (97-1:61) TOF MS CI+ 459316.1354

296.1278

147.0895

222.0763166.0857 250.1341 335.2045

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Figure S9. High-resolution mass spectrum of POABP-DMA.

250 310 370 430 490 550

UV_POABP

PL_POABP

Inte

nsit

y (

au

)

Wavelength (nm)

Figure S10. Normalized UV-vis and PL spectra of POABP in THF (10 μM).

njs-js05, mw=315; NH3

m/z160 180 200 220 240 260 280 300 320 340 360 380 400 420 440 460

%

0

100

tan170908_10 76 (1.267) Cm (74:78-1:58) TOF MS CI+ 413315.1364

296.1367

250.1199220.8157 355.0925

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400 500 600 700 800

POABP

DMA-POABP

POABP-DMA

PL

in

ten

sit

y (

au

)

Wavelength (nm)

Figure S11. Normalized PL spectra of POABP, DMA-POABP and POABP-DMA in the solid

state.

Figure S12. Molecular dipole moments of S0 and S1 states of (A) DMA-POABP and (B)

POABP-DMA calculated with TD-DFT based on the solvation of THF. μ and μ* denoted the

dipole moment of geometries in the ground and excited states, respectively, and Δμ denoted

the difference of the dipole moments between the ground and excited states.

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Figure S13. The speculation of conjugation mode of DMA-POABP and POABP-DMA.

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Figure S14. (A and B) PL spectra of (A) DMA-POABP and (B) POABP-DMA in the different

solvents and (bottom) the fluorescent photos of their solutions taken under 365 nm UV

irradiation from a hand-held UV lamp.

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Figure S15. (A) UV-vis spectra and (B) the color changing under UV irradiation of 365 nm

wavelength in THF and THF/water mixtures with the different water fractions (fw) of DMA-

POABP.

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Figure S16. (A) UV-vis spectra and (B) the color changing under UV irradiation of 365 nm

wavelength in THF and THF/water mixtures with the different water fractions (fw) of POABP-

DMA.

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Figure S17. The packing structure of single crystals of DMA-POABP.

Figure S18. The packing structure of single crystals of POABP-DMA.

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Figure S19. Single crystals of organoboron compounds reported previously and their bond

lengths and dihedral angles.

Figure S20. The molecular electrostatic potential of POABP, DMA-POABP and POABP-

DMA in S0 state.

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Figure S21. Setup of our QM/MM model for a cluster of DMA-POABP molecules cut from

the crystal structure with the central one as QM region and the surrounding 37 molecules as

MM region.

Figure S22. Setup of our QM/MM model for a cluster of POABP-DMA molecules cut from

the crystal structure with the central one as QM region and the surrounding 41 molecules as

MM region.

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Figure S23. The potential energy surfaces of S1 state at different dihedral angles of (A and B)

POABP, (C, D and E) DMA-POABP and (F, G and H) POABP-DMA, calculated with TD-

DFT as the level of PBE0/6-31G* based on solvation of THF.

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Figure S24. Monitoring the E/Z isomerization of DMA-POABP by 1H NMR spectroscopy by

irradiating its pure Z form in THF-d8 (40 mM) with a blue LED lamp for 5 and 10 min. Solvent

peak was marked with asterisk.

Figure S25. Monitoring the E/Z isomerization of POABP-DMA by 1H NMR spectroscopy by

irradiating its pure Z form in THF-d8 (40 mM) with a blue LED lamp for 5 and 10 min. Solvent

peak was marked with asterisk.

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Figure S26. The proposal rotation of the double bond in the excited state of DMA-POABP and

POABP-DMA according to the variations of bond lengths in S0 and S1 states (Table S8).

Figure S27. A proposed model for the excited-state of E/Z isomerization of (A) DMA-POABP

and (B) POABP-DMA. ΔE* denoted the energy barrier from Z to E-form, and ΔECI denoted

the energy gap of the de-excitation pathway through the conical intersection between the S0

and SZ→E states.

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Table S1. Calculation data of DMA-POABP and POABP-DMA in S0 state.a)

Luminogen Excited states Configurations E (eV) λ (nm) fos

POABP S01 H → L (99%) 3.65 339.87 0.97

S02 H‒2 → L (93%), H → L+2 (4%) 4.31 287.34 0.03

DMA-POABP S01 H → L (99%) 3.18 390.39 1.12

S02 H‒1 → L (70%), H → L+1 (28%) 4.30 288.42 0.15

POABP-DMA S01 H → L (99%) 2.95 420.64 0.89

S02 H‒1 → L (87%), H → L+1 (12%) 4.03 307.54 0.42

a) Calculated with TD-DFT at the level of PBE0/6-31G* based on solvation of THF, in which

the vertical excitation as linear response solvation was used. S01 and S02 denoted the first and

second vertical transition from the S0 state to the S1 and S2, respectively, and fos denoted

oscillator strength between the ground and excited states.

Table S2. Photophysical parameters of DMA-POABP and POABP-DMA in various solvents.

Solvent

DMA-POABP POABP-DMA

λabs

(nm)

λem

(nm)

Δλ

(nm)

ṽ

(cm-1)

λabs

(nm)

λem

(nm)

Δλ

(nm)

ṽ

(cm-1)

Acetonitrile 422 482 60 2950 417 602 185 7370

Dibutylether 420 459 39 2023 407 496 89 4409

DMSO 433 493 60 2811 425 618 193 7348

Ethyl acetate 418 469 51 2601 407 554 147 6519

Ethanol 411 473 62 3189 414 564 150 6424

Hexane 415 457 42 2215 416 484 68 3377

Isopropanol 411 471 60 3099 411 552 141 6215

Triethylamine 419 463 44 2268 414 495 81 3953

Table S3. Molecular dipole moments of organoboron compounds in S0 and S1 states.

Luminogen State X (Debye) Y (Debye) Z (Debye) Total (Debye)

POABP S0 2.7057 -6.3690 0.0001 6.9199

S1 1.3520 -7.2337 0.0001 7.3590

DMA-POABP S0 -10.2878 -7.6370 -0.0002 12.8126

S1 -15.7137 -8.2403 -0.0091 17.7433

POABP-DMA S0 -4.3747 -8.2008 0.0004 9.2947

S1 -17.9997 -8.9299 -0.0145 20.0931

a) Calculated with TD-DFT as the level of PBE0/6-31G* based on solvation of THF, in which

the vertical excitation as linear response solvation was used.

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Table S4. Crystal data and structure refinement for DMA-POABP and POABP-DMA.

Empirical formula DMA-POABP POABP-DMA

Formula weight 315.13 315.13

Temperature/K 297.0 220.01(10)

Crystal system monoclinic triclinic

Space group P21/n P-1

a /Å 9.4912(16) 7.4604(4)

b /Å 17.4789(16) 9.2599(4)

c /Å 10.2389(12) 11.5405(6)

α /° 90 86.303(4)

β /° 110.403(15) 81.372(4)

γ /° 90 72.383(4)

Volume /Å3 1592.0(4) 751.10(7)

Z 4 2

ρcalc /gcm-3 1.315 1.393

μ /mm-1 0.099 0.881

F(000) 656.0 328.0

Crystal size /mm3 0.60 × 0.48 × 0.30 0.45 × 0.4 × 0.4

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Table S5. Dihedral angles and bond lengths of single crystals of DMA-POABP and POABP-

DMA.

DMA-POABP POABP-DMA

θAP: C2-N1-C3-C4 (°) 2.09 θAP: C18-N3-C14-C15 (°) 6.75

θPD: C5-C6-C9-H9 (°) 0.81 θPD: C7-C2-C1-N1 (°) 0.43

θZE: H9-C9-N3-B1 (°) 2.27 θZE: H1-C1-N1-B1 (°) 0.46

θPB: N2-C10-C11-C16 (°) 1.23 θPB: C12-C11-C10-O1 (°) 2.88

H7…N2 (Å) 2.332 H7-N2 (Å) 2.359

N3→B1 (Å) 1.566 N1→B1 (Å) 1.587

N3−N2 (Å) 1.398 N1−N2 (Å) 1.389

N2=C10 (Å) 1.292 N2=C10 (Å) 1.310

C10−O1 (Å) 1.325 C10−O1 (Å) 1.331

O1−B1 (Å) 1.473 O1−B1 (Å) 1.461

B1−F1 (Å) 1.362 B1−F1 (Å) 1.362

Table S6. Calculated data of organoboron compounds in S1 state.a)

Luminogen Excited state Configurations E (eV) λ (nm) fos

POABP S10 H → L (~100%) 2.96 418.37 1.14

DMA-POABP S10 H → L (99%) 2.71 458.36 1.29

POABP-DMA S10 H → L (99%) 2.56 485.06 0.90

a) Calculated with TD-DFT at the level of PBE0/6-31G* based on solvation of THF, in which

the vertical excitation as linear response solvation was used. S10 denoted the first vertical

radiation from the S1 state to the S0 state, and fos denoted oscillator strength between the ground

and excited states.

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Table S7. Calculated data of DMA-POABP and POABP-DMA in S1 state.a)

Luminogen Excited state Configurations E (eV) λ (nm) fos

DMA-POABP S10 H → L (99%) 3.08 402.69 0.80

POABP-DMA S10 H → L (~100%) 2.32 535.42 0.56

a) Calculated with TD-DFT at the level of PBE0/6-31G* based on solvation of THF, in which

vertical excitation as state-specific solvation was used. S10 denoted the first vertical radiation

from the S1 state to the S0 state, and fos denoted oscillator strength between the ground and

excited states.

Table S8. Dihedral angles and bond lengths of DMA-POABP and POABP-DMA in S0 and S1

states. a)

Luminogen

DMA-POABP POABP-DMA

State S0 S1 S0 S1

θAP: C11-N3-C1-C2 (°) 0.004 -0.376 0.038 0.004

θPD: C3-C4-C5-H1 (°) -0.005 -0.108 0.030 -0.207

θPB: C8-C7-C6-O1 (°) -0.014 0.021 -0.119 -0.009

θZE: H1-C5-N1-B1 (°) 0.002 -0.010 -0.001 -0.212

C4−C5 (Å) 1.427 1.418 (↓0.009) 1.447 1.410 (↓0.036)

C5=N1 (Å) 1.302 1.344 (↑0.042) 1.295 1.345 (↑0.050)

N1−N2 (Å) 1.375 1.323 (↓0.052) 1.364 1.371 (↑0.007)

N2=C6 (Å) 1.309 1.353 (↑0.044) 1.321 1.305 (↓0.016)

C6−O1 (Å) 1.317 1.321 (↑0.004) 1.318 1.323 (↑0.005)

O1−B1 (Å) 1.487 1.480 (↓0.007) 1.481 1.494 (↑0.013)

N1→B1 (Å) 1.587 1.586 (↓0.001) 1.598 1.561 (↓0.037)

C6−C7 (Å) 1.462 1.423 (↓0.039) 1.444 1.460 (↑0.016)

H2…N2 (Å) 2.292 2.262 (↓0.030) 2.271 2.314 (↑0.043)

a) Calculated with TD-DFT at the level of PBE0/6-31G* based on solvation of THF.

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Table S9. Dihedral angles and bond lengths of DMA-POABP and POABP-DMA in S0 and S1

states.a)

Luminogen

DMA-POABP POABP-DMA

State S0 S1 S0 S1

θAP: C11-N3-C1-C2 (°) -2.03 -10.80 6.06 1.16

θPD: C3-C4-C5-H1 (°) 1.48 3.81 1.05 1.03

θPB: C8-C7-C6-O1 (°) -2.01 -1.10 -2.27 -3.64

θZE: H1-C5-N1-B1 (°) 2.16 1.76 1.22 1.84

C4−C5 (Å) 1.427 1.449 (↑0.022) 1.445 1.408 (↓0.037)

C5=N1 (Å) 1.304 1.317 (↑0.013) 1.294 1.337 (↑0.043)

N1−N2 (Å) 1.374 1.331 (↓0.043) 1.365 1.407 (↑0.042)

N2=C6 (Å) 1.307 1.357 (↑0.050) 1.320 1.280 (↓0.040)

C6−O1 (Å) 1.316 1.322 (↑0.006) 1.320 1.319 (↓0.001)

O1−B1 (Å) 1.492 1.474 (↓0.018) 1.475 1.507 (↑0.032)

N1→B1 (Å) 1.589 1.602 (↑0.013) 1.596 1.550 (↓0.046)

C6−C7 (Å) 1.461 1.418 (↓0.043) 1.444 1.496 (↑0.052)

H2…N2 (Å) 2.264 2.212 (↓0.052) 2.280 2.334 (↑0.054)

a) Calculated with TD-DFT at the level of PBE0/6-31G*, in which high-level QM/MM

method in ONIOM methodology in solid was used.