Supporting Information

Highly Efficient Aggregation-Induced Red-

Emissive Organic Thermally Activated Delayed
Fluorescence Materials with Prolonged
Fluorescence Lifetime for Time-Resolved
Luminescence Bioimaging
Sujie Qi,‡,a Sangin Kim,‡,c Van-Nghia Nguyen,*,a,b Youngmee Kim,a Guangle Niu,d Gyoungmi Kim,a Sung-
Jin Kim,a Sungnam Park*,c and Juyoung Yoon*,a

a
Department of Chemistry and Nanoscience, Ewha Womans University, Seoul 03760,

Republic of Korea

b
Institute of Research and Development, Duy Tan University, Da Nang 550000, Vietnam

c
Department of Chemistry, Korea University, Seoul, 02841, Republic of Korea

d
Center of Bio and Micro/Nano Functional Materials, State Key Laboratory of Crystal

Materials, Shandong University, Jinan 250100, China

Corresponding Author

*E-mail: nguyenvannghia8@duytan.edu.vn; spark8@korea.ac.kr; jyoon@ewha.ac.kr.

Table of contents

1. Synthetic route….…………...……………….………….…….….…………….…….S1

2. NMR spectra and HRMS……....………………………….……………….…...……S2

3. Crystallographic data……………………………….………………….…....……….S9

4. Optical properties and biological studies …………………………………….…....S15

1. Synthetic route

Scheme S1. The synthetic routes to PXZ-NI, PTZ-NI, and Lyso-PXZ-NI.

S1
2. NMR spectra and HR-MS

Figure S1. 1H NMR spectrum (300 MHz, CDCl3) of compound 1.

Figure S2. 13C NMR spectrum (75 MHz, CDCl3) of compound 1.

S2
Figure S3. 1H NMR spectrum (300 MHz, CDCl3) of compound 2.

Figure S4. 13C NMR spectrum (75 MHz, CDCl3) of compound 2.

S3
Figure S5. 1H NMR spectrum (300 MHz, CDCl3) of PXZ-NI.

Figure S6. 13C NMR spectrum (75 MHz, CDCl3) of PXZ-NI.

S4
Figure S7. HRMS spectrum of PXZ-NI.

Figure S8. 1H NMR spectrum (300 MHz, CDCl3) of PTZ-NI.

S5
Figure S9. 13C NMR spectrum (75 MHz, CDCl3) of PTZ-NI.

Figure S10 HRMS spectrum of PTZ-NI.

S6
Figure S11. 1H NMR spectrum (300 MHz, CDCl3) of Lyso-PXZ-NI.

Figure S12. 13C NMR spectrum (75 MHz, CDCl3) of Lyso-PXZ-NI.

S7
Figure S13. HRMS spectrum of Lyso-PXZ-NI.

S8
3. Crystallographic data

Figure S14. ORTEP drawing of PXZ-NI and PTZ-NI.

Figure S15. The dihedra angles between the PXZ or PTZ plane (red) and NI (purple) plane in

the X-ray crystal structures of PXZ-NI and PTZ-NI.

S9
Figure S16. Molecular packing in the crystal structures of PXZ-NI and PTZ-NI.

S10
Table S1. Crystal data and structure refinement for PXZ-NI.
__________________________________________________________________________
Empirical formula C28 H22 N2 O3
Formula weight 434.47
Temperature 223(2) K
Wavelength 0.71073 Å
Crystal system Triclinic
Space group P -1
Unit cell dimensions a = 8.9858(3) Å = 88.868(2)°
b = 10.2915(4) Å = 84.867(2)°
c = 11.4789(4) Å  = 86.801(2)°
Volume 1055.52(7) Å3
Z 2
Density (calculated) 1.367 Mg/m3
Absorption coefficient 0.090 mm-1
F(000) 456
Crystal size 0.150 x 0.140 x 0.050 mm3
Theta range for data collection 1.781 to 28.532°.
Index ranges -12<=h<=12, -13<=k<=13, -15<=l<=15
Reflections collected 35559
Independent reflections 5329 [R(int) = 0.0366]
Completeness to theta = 25.242° 99.9 %
Absorption correction Multi-scan
Refinement method Full-matrix least-squares on F2
Data / restraints / parameters 5329 / 0 / 299
Goodness-of-fit on F2 1.023
Final R indices [I>2sigma(I)] R1 = 0.0440, wR2 = 0.1021
R indices (all data) R1 = 0.0750, wR2 = 0.1190
Largest diff. peak and hole 0.207 and -0.204 e.Å-3

S11
Table S2. Selected bond lengths [Å], angles [°] and torsional angles for PXZ-NI.
_____________________________________________________
Lengths
C(1)-O(1) 1.3876(16)
C(6)-N(1) 1.4094(16)
C(7)-N(1) 1.4057(17)
C(12)-O(1) 1.3850(16)
C(13)-C(14) 1.363(2)
C(13)-C(22) 1.4233(19)
C(13)-N(1) 1.4343(17)
Angles
C(14)-C(13)-C(22) 121.15(12)
C(14)-C(13)-N(1) 119.82(13)
C(22)-C(13)-N(1) 119.01(12)
C(7)-N(1)-C(6) 118.90(11)
C(7)-N(1)-C(13) 119.03(11)
C(6)-N(1)-C(13) 120.08(11)
Torsion angles
C(22)-C(13)-N(1)-C(7) -75.87(2)
C(14)-C(13)-N(1)-C(6) -93.55(2)
C(7)-N(1)-C(13)-C(14) 102.63(2)
C(22)-C(13)-N(1)-C(6) 87.96(2)
_____________________________________________________

S12
Table S3. Crystal data and structure refinement for PTZ-NI.
___________________________________________________________________________
Empirical formula C28 H22 N2 O2S
Formula weight 450.53
Temperature 298(2) K
Wavelength 0.71073 Å
Crystal system Triclinic
Space group P -1
Unit cell dimensions a = 9.1053(5) Å = 67.115(3)°
b = 11.2519(6) Å = 72.274(3)°
c = 12.1419(7) Å  = 83.772(3)°
Volume 1091.57(11) Å3
Z 2
Density (calculated) 1.371 Mg/m3
Absorption coefficient 0.178 mm-1
F(000) 472
Crystal size 0.240 x 0.200 x 0.190 mm3
Theta range for data collection 2.160 to 28.378°.
Index ranges -12<=h<=12, -15<=k<=14, -16<=l<=16
Reflections collected 26438
Independent reflections 5412 [R(int) = 0.0333]
Completeness to theta = 25.242° 99.9 %
Absorption correction Multi-scan
Refinement method Full-matrix least-squares on F2
Data / restraints / parameters 5412 / 0 / 299
Goodness-of-fit on F2 1.111
Final R indices [I>2sigma(I)] R1 = 0.0458, wR2 = 0.1411
R indices (all data) R1 = 0.0724, wR2 = 0.1702
Largest diff. peak and hole 0.329 and -0.393 e.Å-3

S13
Table S4. Selected bond lengths [Å], angles [°] and torsional angles for PTZ-NI.
_____________________________________________________
Lengths
C(13)-C(12) 1.421(2)
C(12)-C(11) 1.373(3)
C(12)-N(2) 1.437(2)
C(28)-N(2) 1.425(3)
C(17)-N(2) 1.418(3)
S(1)-C(23) 1.758(2)
C(22)-S(1) 1.757(2)
Angles
C(23)-S(1)-C(22) 98.79(9)
C(11)-C(12)-N(2) 121.18(2)
C(13)-C(12)-N(2) 118.23(1)
C(17)-N(2)-C(12) 119.49(1)
C(28)-N(2)-C(17) 120.79(1)
C(28)-N(2)-C(12) 116.49(1)
Torsion angles
C(13)-C(12)-N(2)- C(17) -116.86(2)
C(13)-C(12)-N(2)- C(28) 83.09(2)
C(11)-C(12)-N(2)- C(17) 65.09(2)
C(11)-C(12)-N(2)- C(28) -94.95(2)
____________________________________________________________

S14
4. Optical properties and biological studies

Figure S17. UV-Vis absorption and normalized absorption spectra of (a) PXZ-NI, (b) PTZ-

NI, and (c) Lyso-PXZ-NI (50 μM) in hexane, toluene, THF, ACN, and DMSO.

Figure S18. Fluorescence spectra of (a) PXZ-NI, (b) PTZ-NI, and (c) Lyso-PXZ-NI (50 μM)

in hexane, toluene, THF, ACN, and DMSO, λex = 470 nm.

S15
Table S5. Photophysical properties of compounds.

Compounds λabs[nm]a ε[104 M-1cm-1]b λem[nm] ΦF[%]c

PXZ-NI 330 1.86 578 4.8

PTZ-NI 331 1.70 584 2.7

Lyso-PXZ-NI 330 1.99 584 3.7

a
Maximal UV-vis absorption wavelength in hexane. bMolar extinction coefficient at the

absorption maxima. cFluorescence quantum yield (ΦF) of compounds in hexane that were

measured with Rhodamine 6G used as a standard (ΦF = 95% in ethanol).

Figure S19. TRPL signals of (a) PXZ-NI, (b) PTZ-NI, and (c) Lyso-PXZ-NI (30 μM) in water

(10% DMSO) under aerated and Ar atmosphere at room temperature.

Figure S20. Size distribution of (a) PXZ-NI, (b) PTZ-NI, and (c) Lyso-PXZ-NI in water. The

concentration is 20 μM in water containing 1% DMSO.

S16
Figure S21. Cytotoxicity of different concentrations of (a) PXZ-NI, (b) PTZ-NI, and (c) Lyso-

PXZ-NI to HeLa cells by MTT assay.

Figure S22. Confocal FL images of HeLa cells incubated with PXZ-NI, PXZ-NI, and Lyso-

PXZ-NI (20 μM) for different times (0, 30, 60, 90 and 120 min).

S17
Figure S23. Normalized fluorescence intensities of PXZ-NI, PTZ-NI, Lyso-PXZ and LTG in

HeLa cells were measured by continuous irradiation with a 473 nm laser (50% power) on the

confocal microscope.

Figure S24. The time-gated luminescence images of Hela cells incubated with Lyso-PXZ-NI

with the delay time (0, 50, 100, and 200 ns). Scale bar = 30 μm.

S18