A facile strategy for realizing room temperature phosphorescence and

A facile strategy for realizing room temperature phosphorescence and single molecule white light emission Wang et al.

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A facile strategy for realizing room temperature phosphorescence and single molecule white light emission Jianguo Wang1,3, Xinggui Gu1,2,*, Huili Ma4, Qian Peng5, Xiaobo Huang6, Xiaoyan Zheng1, Simon H. P. Sung1, Guogang Shan1, Zhigang Shuai4, Jacky W. Y. Lam1 & Ben Zhong Tang1,7,8,*

1Department

of Chemistry, Hong Kong Branch of Chinese National Engineering, Research Center for Tissue Restoration and Reconstruction, Institute of Molecular Functional Materials, State Key Laboratory of Molecular Nanoscience, Division of Life Science and Biomedical Engineering, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, Hong Kong, China. 2Beijing Advanced Innovation Center for Soft Matter Science and Engineering, Beijing University of Chemical Technology, Beijing 100029, China. 3Key Laboratory of Organo-Pharmaceutical Chemistry, Gannan Normal University, Ganzhou 341000, China. 4Key Laboratory of Organic Optoelectronics and Molecular Engineering, Department of Chemistry, Tsinghua University, Beijing 100084, China. 5Key Laboratory of Organic Solids, Beijing National Laboratory for Molecular Science, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China. 6College of Chemistry and Materials Engineering, Wenzhou University, Wenzhou 325035, China. 7NSFC Center for Luminescence from Molecular Aggregates, SCUT-HKUST Joint Research Institute, State Key Laboratory of Luminescent Materials and Devices, South China University of Technology, Guangzhou 510640, China. 8HKUST-Shenzhen Research Institute, No. 9 Yuexing 1st RD, South Area, Hi-tech Park, Nanshan, Shenzhen 518057, China. *

Correspondence and requests for materials should be addressed to X.G. (email: [email protected]) or to B.Z.T. (email: [email protected])

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Supplementary Figure 1 Synthesis route of TPO-I, TPO-Br, TPO-Cl, and TPO-F.

Supplementary Figure 2 1H NMR spectrum of TPO-I in CD3OD.

Supplementary Figure 3 13C NMR spectrum of TPO-I in CD3OD.

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wjg-3MOACTPO; MW=506; DHB tan161115_24 16 (0.533) Cn (Cen,4, 90.00, Ar); Sb (15,10.00 ); Sm (SG, 2x3.00); Cm (6:22)

TOF LD+ 965

374.1533

%

100

375.1580

105.0136

309.5110

327.1017

376.1714

192.9643

0 100

120

140

160

180

200

220

240

260

280

300

320

340

360

380

400

408.1257

420

440

460

480

500

520

540

560

580

Supplementary Figure 4 HRMS spectrum of TPO-I.

Supplementary Figure 5 1H NMR spectrum of TPO-Br in CD3OD.

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m/z 600

Supplementary Figure 6 13C NMR spectrum of TPO-Br in CD3OD. wjg-TPO-ClO4; MW=374; DHB tan161130_5 5 (0.165) Cn (Cen,4, 90.00, Ar); Sb (15,10.00 ); Sm (SG, 2x3.00); Cm (2:8)

TOF LD+ 1.66e3

374.1557

%

100

375.1605

449.2014

376.1733 450.1975 137.0328

0 100

154.0412 180.0540

m/z 120

140

160

180

200

220

240

260

280

300

320

340

360

380

400

420

440

460

480

500

520

540

Supplementary Figure 7 HRMS spectrum of TPO-Br.

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560

580

600

Supplementary Figure 8 1H NMR spectrum of TPO-Cl in CD3OD.

Supplementary Figure 9 13C NMR spectrum of TPO-Cl in CD3OD.

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wjg-TPO-Cl; MW=374; DHB tan161209_12 12 (0.399) Cn (Cen,4, 90.00, Ar); Sb (15,10.00 ); Sm (SG, 2x3.00); Cm (9:12)

TOF LD+ 594

374.1579

%

100

375.1598

449.1934

136.9805

0 100

153.9838 176.9836

273.0332

376.1693

450.1864

372.1159 377.1974

451.1778

m/z 120

140

160

180

200

220

240

260

280

300

320

340

360

380

400

420

440

460

480

500

520

540

560

580

600

Supplementary Figure 10 HRMS spectrum of TPO-Cl.

Supplementary Figure 11 1H NMR spectrum of TPO-F in CD3OD.

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Supplementary Figure 12 13C NMR spectrum of TPO-F in CD3OD.

wjg-TPO-F, MW=374; NH3 tan171206_1 100 (1.667) Cm (98:105-2:49)

TOF MS CI+ 37.5

374.1530

100

392.1556

%

346.1573

334.8573

358.0822 364.9931

0 320

325

330

335

340

345

350

355

360

365

370

375

380

385

390

395

400

405

410

415

Supplementary Figure 13 HRMS spectrum of TPO-F.

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420

m/z 425

1.2

b

TPO-I TPO-Br TPO-Cl TPO-F TPO-P

0.9

Normalized PL intensity (au)

Normalized absorption (au)

a

0.6

0.3

0.0 240

280

320

360

400

1.0

TPO-I TPO-Br TPO-Cl TPO-F TPO-P

0.8 0.6 0.4 0.2 0.0 360

430

Wavelength (nm)

500

570

640

Wavelength (nm)

Supplementary Figure 14 a UV-vis and b Photoluminescence (PL) spectra of TPO-I, TPO-Br, TPOCl, TPO-F and TPO-P (10 μM) in EtOH solution.

Normalized absorption (au)

1.2 TPO-I TPO-Br TPO-Cl TPO-F TPO-P

0.9

0.6

0.3

0.0 240

280

320

360

400

Wavelength (nm)

Supplementary Figure 15 UV-vis spectra of TPO-I, TPO-Br, TPO-Cl, TPO-F and TPO-P (10 μM) in DCM solution.

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Supplementary Figure 16 Time-resolved PL decay of a TPO-I, b TPO-Br, c TPO-Cl, and d TPO-F at maximum emission wavelength in EtOH solution.

Supplementary Figure 17 The delayed (50 µs) PL spectra of powder of a TPO-I and b TPO-Br.

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a

b 88 μs

1.65 ms

48 μs

0.0

RT 77 K

Intensity (au)

Intensity (au)

RT 77 K

0.2

706 μs

0.4

0.6

0.8

1.0

2

0

Time (ms)

6

4

8

10

Time (ms)

Supplementary Figure 18 Time-resolved PL decay of powders of a TPO-I at 559 nm and b TPO-Br at 549 nm under different temperature.

Intensity (au)

TPO-I TPO-Br

0

2

4

6

Time (ms)

Supplementary Figure 19 Time-resolved PL decay of TPO-I (@ 559 nm) and TPO-Br (@ 549 nm) in powder in vacuum.

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a

b 1.0

Normalized PL intensity


1.0 in MeOH in THF

0.8 0.6 0.4 0.2 0.0 380

460

540

620

in MeOH in THF

0.8 0.6 0.4 0.2 0.0 380

700

460

540

620

700

Wavelength (nm)

Wavelength (nm)

Supplementary Figure 20 PL spectra of a TPO-I and b TPO-Br in different solvents (THF and MeOH) with different dielectric constants at room temperature. The dielectric constants of THF and MeOH are 7.58 and 32.7, respectively. Their emission peaks are at about 450 nm.

a In THF

Intensity (au)

Intensity (au)

In MeOH

0

10

20

30

40

0

50

10

Time (ns)

b

20

30

40

50

Time (ns)

In THF

Intensity (au)

Intensity (au)

In MeOH

0

10

20

30

40

50

Time (ns)

0

10

20

30

40

50

Time (ns)

Supplementary Figure 21 Time-resolved PL decay of a TPO-I (@ 450 nm) and b TPO-Br (@ 450 nm) in different solvents at the room temperature (λex = 375 nm) under air.

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1.5


1.2

110-5 77 K 110-3 77 K 110-5 300 K 110-3 300 K

b

110-4 77 K 110-2 77 K 110-4 300 K 110-2 300 K


a

0.9 0.6 0.3 0.0 380

460

540

620

110-5 77 K 110-4 77 K 110-3 77 K 110-2 77 K 110-5 300 K 110-4 300 K 110-3 300 K 110-2 300 K

1.0

0.5

0.0

700

424 477 530 583 636 689

Wavelength (nm)

Wavelength (nm)

Supplementary Figure 22 PL spectra of a TPO-I and b TPO-Br with different concentrations at 300 K and 77 K.

a -3

-2

110 mol/L

110 mol/L

20

30

40

10

b

20

30

40

50

-2

40

30

50

40

10

20

30

10

40

20

30

-4

50

50

-5

110 mol/L

300 K 77 K

Time (ns)

40

Time (ns)

Intensity (au) 0

0

50

110 mol/L

300 K 77 K

Intensity (au) 30

20

Time (ns) -3

Intensity (au)

20

Time (ns)

10

110 mol/L

300 K 77 K

10

0

Time (ns)

110 mol/L

0

Intensity (au)

Intensity (au) 0

50

Time (ns)

300 K 77 K

Intensity (au)

10

300 K 77 K

300 K 77 K

Intensity (au)

Intensity (au) 0

-5

110 mol/L

-4

110 mol/L

300 K 77 K

300 K 77 K

0

10

20

30

Time (ns)

40

50

0

10

20

30

40

50

Time (ns)

Supplementary Figure 23 Time-resolved PL decay of a TPO-I (@ 447 nm) and b TPO-Br (@ 444 nm) with the different concentrations in MeOH at 300 K and 77 K (λex = 375 nm) under air.

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a

b

-2

1 10 mol/L -3 1 10 mol/L -4 1 10 mol/L -5 1 10 mol/L

-2

0.0

Intensity (au)

Intensity (au)

1 10 mol/L -3 1 10 mol/L

0.5

1.0

1.5

2.0

0.0

0.5

1.0

1.5

2.0

Time (ms)

Time (ms)

Supplementary Figure 24 Time-resolved PL decay of a TPO-I (@ 559 nm) and b TPO-Br (@ 549 nm) with the different concentrations in MeOH at 77 K (λex = 350 nm) under air.

PL Intensity (au)

298 K 348 K 398 K 448 K 498 K

400

490

580

670

760

850

Wavelength (nm)

Supplementary Figure 25 PL spectra of TPO-I powder at different temperature.

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a

24

b

18

I573 /I448

PL Intensity (au)

298 K 348 K 398 K 448 K 498 K

12

6

0 400

500

600

700

800

300

350

Wavelength (nm)

400

450

500

Time (s)

Supplementary Figure 26 a PL spectra and b phosphorescence (@ 573 nm)/fluorescence (@ 448 nm) intensity ratio of TPO-Br powder at different temperature.

a

b

5

7

9

11

13

298 K 348 K 398 K 448 K 498 K

Intensity (au)

Intensity (au)

298 K 348 K 398 K 448 K 498 K

15

5

6

Time (ns)

8

9

10

Time (ns)

c

d

0.2

0.3

0.4

0.5

298 K 348 K 398 K 448 K 498 K

Intensity (au)

298 K 348 K 398 K 448 K 498 K

Intensity (au) 0.1

7

0.6

Time (ms)

0

1

2

3

4

5

Time (ms)

Supplementary Figure 27 Time-resolved PL decay of powders of TPO-I a @ 450 nm, c @ 559 nm and TPO-Br b @ 434 nm, d @ 549 nm at different temperature under air.

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Powder Microcrystal


1.0 0.8 0.6 0.4 0.2 0.0 400

450

500

550

600

650

Wavelength (nm)

Supplementary Figure 28 PL spectra of powder and microcrystal of TPO-Br.

a 15

72

I549 /I434

PL intensity

10

b 96 0s 5s 10 s 15 s 20 s 25 s

48

5 24

0 380

0 460

540

620

700

0

5

10

15

20

25

Grinding time (s)

Wavelength (nm)

Supplementary Figure 29 a PL spectra and b the intensity ratio between phosphorescence (@ 549 nm) and fluorescence (@ 434 nm) for TPO-Br microcrystals under grinding for different time.

25 s 20 s

Intensity (au)

15 s 10 s 5s

0s 3

12

21

30

2 (degree)

Supplementary Figure 30 XRD patterns of TPO-Br microcrystals under grinding for different time.

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Nomalized PL intensity (au)

0s 5s 15 s 30 s 60 s 120 s 180 s 240 s 300 s 360 s 420 s 480 s

380

460

540

620

700

Wavelength (nm)

Supplementary Figure 31 PL spectra of TPO-I powder under grinding for different time.

Intensity (au)

8 min

0 min

3

12

21

30

2 (degree)

Supplementary Figure 32 XRD patterns of TPO-I powder before and after grinding for 8 min.

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b

a 3.447 Å 3.980 Å

3.316 Å

d

c 3.069 Å

3.494 Å

Supplementary Figure 33 a and c Short contacts, hydrogen bonding, anion-π+ interactions and b and d intermolecular stacking of TPO-I (top) and TPO-Br (bottom), respectively.

Supplementary Figure 34 QM/MM model taking TPO-Br as an example: one central QM molecule for the higher layer and the remain MM molecules for the lower layer.

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a

b 0.00 eV

S1

I: 2.51% T1

I: 2.44% T2

I: 2.34% T3

100%

I: 2.42%

100%

S0

T 2,3 T1

100%

1.26 eV

1.29 eV

0.03 eV

100%

S1 (f = 0.000)

ξ(S1,T3) = 1163.04 cm -1 ξ(S1,T2) = 1105.89 cm -1 ξ(S1,T1) = 305.71 cm -1 ξ(S0,T1) = 316.03 cm -1 I: 97.4%

I: 97.3%

I: 94.7%

I: 96.3%

Supplementary Figure 35 The calculated energy level diagram, spin-orbit couplings (ξ) between singlet and triplet states, and the oscillator strengths (f) of the S1 state of a TPO-I in crystal based on the optimized ground-state geometries using ONIOM method. The natural transition orbitals (NTOs) (hole ones at the bottom and electron ones on the top) and the corresponding proportions for b TPOI.

380

b

440

500

560

Wavelength (nm)

620

680 380

c 5 mg/mL 10 mg/mL 15 mg/mL

440

500

100 L 50 L 20 L 15 L 10 L

PL intensity (au)

50 L 100 L

PL intensity (au)

PL intensity (au)

a

560

Wavelength (nm)

620

680 380

440

500

560

620

680

Wavelength (nm)

Supplementary Figure 36 PL spectra of TPO-Br films which were made to take a 10 mg/mL TPOBr in MeOH solution with different volume on quartz plate, b 50 µL TPO-Br in MeOH solution with different concentration on quartz plate and c 5 mg/mL TPO-Br in MeOH solution with different volume on quartz plate.

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Supplementary Figure 37 XRD patterns of film and powder of TPO-Br.

Supplementary Figure 38 a PL spectra and b CIE 1931 coordinates and c CIE value of films of TPO-Br were monitored at room temperature (22 oC) during one month. Excitation wavelength: 347 nm.

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a

1.3

0d 2d 4d 6d 8d 10 d 12 d 14 d 16 d 18 d 20 d

1.0

0.7

b

c

0.4

0.1 380

440

500

560

620

680

Wavelength (nm)


d

1.3

0d 2d 4d 6d 8d 10 d 12 d 14 d 16 d 18 d 20 d

1.0

0.7

e

f

0.4

0.1 380

440

500

560

620

680

Wavelength (nm)


g

1.6

0d 2d 4d 6d 8d 10 d 12 d 14 d 16 d 18 d 20 d

1.3

1.0

0.7

h

i

0.4

0.1 380

440

500

560

620

680

Wavelength (nm)

Time (day)

CIE x

CIE y

0

0.31

0.33

2

0.29

0.34

4

0.29

0.33

6

0.29

0.34

8

0.29

0.34

10

0.29

0.34

12

0.29

0.34

14

0.29

0.34

16

0.29

0.33

18

0.30

0.35

20

0.30

0.35

Time (day)

CIE x

CIE y

0

0.31

0.33

2

0.30

0.33

4

0.30

0.32

6

0.30

0.33

8

0.30

0.33

10

0.29

0.33

12

0.30

0.33

14

0.30

0.33

16

0.28

0.33

18

0.29

0.33

20

0.29

0.32

Time (day)

CIE x

CIE y

0

0.30

0.32

2

0.29

0.32

4

0.32

0.34

6

0.32

0.37

8

0.31

0.36

10

0.30

0.36

12

0.30

0.36

14

0.30

0.35

16

0.30

0.36

18

0.32

0.37

20

0.32

0.38

Supplementary Figure 39 PL spectra (a, d and g), CIE 1931 coordinates (b, e and h) and CIE value (c, f and i) of films of TPO-Br were monitored at (a, b and c) -20 oC, (d, e and f) 40 oC and (g, h and i) 70 oC during 20 days.

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Supplementary Figure 40 PL spectra of TPO-I film.

a

b

100

100

Average: 250 nm 80

Cell viability (%)

Intensity

80

60

40

20

0 10

c

60

40

20

0

100

1000

10000

Bright-field

25

50

100

200

400

Concentration (ug/mL)

Size (nm)

Luminescence

Merged

Supplementary Figure 41 a DLS analysis of DSPE-PEG-encapsulated TPO-Br NPs. b Cell viabilities of HeLa cells in the presence of different concentrations of TPO-Br NPs. Error bars are defined as s.d. c Bright-field, luminescent and merged images of HeLa cells stained with TPO-Br NPs (1 mg/mL) based on laser scanning confocal microscope (LSCM). Excitation wavelength: 405 nm, emission was acquired in the range from 500 to 720 nm. Scale bar: 50 µm.

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20180601130815 1ÈÕ 13:08:16 pen V12.5, f1, 17s 1204N5847, Andor,iKon

Right

Left

a

TPE-CN

Blank

TPO-Br

b

Bright field

Fluorescence

Image Min = 5.73e+05 Max = 6.2665e+08 radiant efficiency

Image Min = -24948 Max = 47622 p/sec/cm^2/sr

Phosphorescence

60 6

Image Min = 5.73e+05 Max = 6.2665e+08 radiant efficiency

40000 40000

Image Min = -24948 Max = 47622 p/sec/cm^2/sr

60

40000

50

6

30000

40 4

30

30000 30000 25000

20

30 3

Color Bar Min = 22070 Max = 41176

Color Bar Min = 1.8248e+07 Max = 6.2665e+07

25000 25000

20 2

User: NX Click # BKG20180601124328 Group: DING DAN 2018Äê6ÔÂ1ÈÕ 12:43:28 Experiment: Time drive Em filter=Open Comment1: #4 1 h Bin:8/4, FOV12.5, f1, 17s Comment2: Camera: IS1204N5847, Andor,iKonsuccess

Click # BKG20180601124445 2018Äê6ÔÂ1ÈÕ 12:44:46 Level=High, Em=Cy5.5, Ex=430 Bin:8/4, FOV12.5, f2, 2s Camera: IS1204N5847, Andor,iKon

x10

40

6

Click # BKG20180601124445 2018Äê6ÔÂ1ÈÕ 12:44:46 Bin:M (2), FOV12.5, f8, 0.2s Filter: Open Camera: IS1204N5847, Andor,iKon

35000

35000 35000

x10

User: NX Group: DING DAN Experiment: Time drive

User: NX Group: DING DAN Experiment: Time drive Comment1: #4 1 h Comment2: success

50 5

Radiance

(107

bkg sub flat-fielded cosmic


Color Bar

User: NX Radiance Group: DING p/s/cm2/sr) MinDAN = 1.8248e+07 Experiment: Time drive Max = 6.2665e+07 Comment1: #4 1 h Comment2: success

NX Color Bar Group: DING DAN (p/s/cm2/sr)User:

Min = 22070

Experiment: Time drive Max Comment1: #4= 141176 h Comment2: success

Supplementary Figure 42 In vivo phosphorescent imaging. a Luminescent photos of the aqueous solutions of DSPE-PEG-encapsulated TPE-CN NPs and TPO-Br NPs (Left: fluorescence; Right: bkg sub flat-fielded cosmic




phosphorescence). Blank is the DSPE-PEG solution. b Luminescent imaging in living mice after subcutaneous injection of TPE-CN NPs (fluorescence) and TPO-Br NPs (Phosphorescence).


τ2 (ns) / A2 (%) τ (ns) a a

447 0.46 / 96.43 2.61 / 3.57 0.83

444 0.40 / 100 / 0.40

TPO-Cl

443 0.39 / 100 / 0.39

TPO-F

TPO-P

438 0.36 / 100 / 0.36

444 0.86 / 100 / 0.86

τ = average fluorescence lifetime at 434 nm calculated by τ = ΣAiτi2/ΣAiτi, where Ai is the pre-exponential factor for

lifetime τi.

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40000

τ1 (ns) / A1 (%)

TPO-Br

35000

λem (nm)

TPO-I

30000

K; λex = 375 nm) under air.

Color Bar Min = 30000 Max = 50000

Supplementary Table 1 Fluorescence lifetime data of AIEgens in EtOH at room temperature (298

Supplementary Table 2 Fluorescence lifetime data of AIEgens in powder at room temperature (298 K; λex = 375 nm) under air and in vacuum. TPO-Br

λem (nm) τ1 (ns) / A1 (%)

τ2 (ns) / A2 (%) τ (ns) a a

TPO-Cl

TPO-F

TPO-P

under air

in vacuum

under air

in vacuum

under air

in vacuum

under air

in vacuum

434 0.75 / 91.75 5.30 / 8.25 2.52

434 0.05 / 92.63 2.14 / 7.37 1.64

435 0.83 / 82.62 2.69 / 17.38 1.60

435 0.95 / 86.04 2.81 / 3.96 1.55

420 0.80 / 100

420 0.74 / 83.00 2.37 / 17.00 1.39

422 1.02 / 100

422 0.49 / 81.51 1.28 / 18.49 0.78

τ = average fluorescence lifetime at 434 nm calculated by τ =

/ 0.80 ΣAiτi2/ΣAiτi,

/ 1.02

where Ai is the pre-exponential factor for

lifetime τi.

Supplementary Table 3 Phosphorescence lifetime data of AIEgens in powder at 77 K under air (λex = 350 nm). λem (nm) τ1 (µs) / A1 (%)

τ (µs) a a

TPO-I

TPO-Br

559 88.16 / 100 88.16

549 1646.75 / 100 1646.75

τ = average phosphorescence lifetime calculated by τ = ΣAiτi2/ΣAiτi, where Ai is the pre-exponential factor for lifetime

τi.

Supplementary Table 4 Phosphorescence lifetime data of AIEgens in powder at room temperature (298 K; λex = 350 nm) under air and in vacuum. TPO-I λem (nm) τ1 (µs) / A1 (%)

τ2 (µs) / A2 (%) τ3 (µs) / A3 (%) τ (µs) a a

TPO-Br

under air

in vacuum

under air

in vacuum

559 66.09 / 41.30 27.66 / 58.70 / 48.74

559 9.42 / 2.24 54.65 / 77.76 / 52.52

549 204.00 / 20.14 743.12 / 76.25 5.79 / 3.61 706.42

549 92.31 / 1.94 388.80 / 4.74 858.40 / 63.32 763.16


τi.

S24

Supplementary Table 5 Fluorescence lifetime data of TPO-I in different solvents with different dielectric constants at room temperature (λex = 375 nm, λem = 450 nm) under air. τ1 (ns) / (%) τ2 (ns) / (%) τ (µs) a a

THF b

MeOH b

4.37 / 3.44 0.31 / 96.56 1.67

4.47 / 8.96 0.28 / 91.04 2.84

τ = average fluorescence lifetime calculated by τ = ΣAiτi2/ΣAiτi, where Ai is the pre-exponential factor for lifetime τi.

b

The dielectric constants of THF and MeOH are 7.58 and 32.7, respectively.

Supplementary Table 6 Fluorescence lifetime data of TPO-Br in different solvents with different dielectric constants at room temperature (λex = 375 nm, λem = 450 nm) under air. τ1 (ns) / (%) τ2 (ns) / (%) τ (ns) a a

THF

MeOH

4.98 / 0.01 0.30 / 99.99 0.30

0.37 / 94.65 6.17 / 5.35 3.18


b

The dielectric constants of THF and MeOH are 7.58 and 32.7, respectively.

Supplementary Table 7 Fluorescence lifetime data of TPO-I with different concentrations in MeOH at 300 K and 77 K (λex = 375 nm, λem = 447 nm) under air. 1×10-2 (mol/L) τ1 (ns) / (%) τ2 (ns) / (%) τ (ns) a a

1×10-3 (mol/L)

1×10-4 (mol/L)

1×10-5 (mol/L)

300 K

77 K

300 K

77 K

300 K

77 K

300 K

77 K

0.23 / 96.46 3.25 / 3.54 1.26

3.91 / 18.86 1.16 / 81.14 2.37

3.99 / 1.85 0.26 / 98.15 1.10

4.76 / 48.79 1.22/ 51.21 4.01

0.29 / 98.50 4.86 / 1.50 1.22

4.70 / 45.19 1.18 / 54.81 3.88

4.47 / 8.96 0.28 / 91.04 2.84

1.71 / 21.56 5.01 / 78.44 4.72


Supplementary Table 8 Fluorescence lifetime data of TPO-Br with different concentrations in MeOH at 300 K and 77 K (λex = 375 nm, λem = 444 nm) under air. 1×10-2 (mol/L) τ1 (ns) / (%) τ2 (ns) / (%) τ (ns) a a

1×10-3 (mol/L)

1×10-4 (mol/L)

1×10-5 (mol/L)

300 K

77 K

300 K

77 K

300 K

77 K

300 K

77 K

0.2 / 97.99 2.34/ 2.01 0.61

3.63 / 12.42 1.15 / 87.58 1.92

5.48 / 2.08 0.27 / 97.91 1.84

4.37 / 26.89 1.16/ 73.11 3.02

7.00 / 2.06 0.32 / 97.94 2.43

4.99 / 75.88 1.44 / 24.12 4.69

0.37 / 94.65 6.17 / 5.35 3.18

5.01 / 31.43 0.66 / 68.57 4.03


S25

Supplementary Table 9 Phosphorescence lifetime data of TPO-I with different concentrations in MeOH at 300 K and 77 K (λex = 350 nm, λem = 559 nm) under air. 1×10-2 (mol/L) 300 K τ1 (µs) / (%) τ2 (µs) / (%) τ3 (µs) / (%) τ (µs) b a

a

ND ND ND ND

1×10-3 (mol/L)

1×10-4 (mol/L)

1×10-5 (mol/L)

77 K

300 K

77 K

300 K

77 K

300 K

77 K

365 / 15.42 125 / 43.67 35 / 40.91 222

ND ND ND ND

256 / 12.07 57 / 16.11 6 / 71.82 199

ND ND ND ND

100 / 2.19 7 / 96.52 371 / 1.29 149

ND ND ND ND

7.5 / 100 / / 7.5

No detectable. b τ = average phosphorescence lifetime calculated by τ = ΣAiτi2/ΣAiτi, where Ai is the pre-exponential

factor for lifetime τi.

Supplementary Table 10 Phosphorescence lifetime data of TPO-Br with different concentrations in MeOH at 300 K and 77 K (λex = 350 nm, λem = 549 nm) under air. 1×10-2 (mol/L) 300 K τ1 (µs) / (%) τ2 (µs) / (%) τ (µs) b a

a

ND ND ND

1×10-3 (mol/L)

1×10-4 (mol/L)

1×10-5 (mol/L)

77 K

300 K

77 K

300 K

77 K

300 K

77 K

5.6 / 100 / 5.6

ND ND ND

ND ND ND

ND ND ND

ND ND ND

ND ND ND

ND ND ND

No detectable. b τ = average phosphorescence lifetime calculated by τ = ΣAiτi2/ΣAiτi, where Ai is the pre-exponential

factor for lifetime τi.

Supplementary Table 11 Fluorescence lifetime data of TPO-I powder at different temperature under air (λex = 375 nm, λem = 450 nm). τ1 (ns) / (%) τ2 (ns) / (%) τ (ns) a a

298 K

348 K

398 K

448 K

498 K

0.14 / 20.86 1.55 / 79.14 1.52

0.11 / 20.59 1.47 / 79.41 1.44

0.09 / 25.22 1.59 / 74.78 1.19

0.06 / 30.36 1.21 / 69.64 1.18

0.05 / 29.22 1.99 / 70.78 1.97


Supplementary Table 12 Fluorescence lifetime data of TPO-Br powder at different temperature under air (λex = 375 nm, λem = 434 nm). τ1 (ns) / (%) τ2 (ns) / (%) τ (ns) a a

298 K

348 K

398 K

448 K

498 K

0.05 / 88.28 0.90 / 11.72 0.65

0.04 / 89.58 0.80 / 10.42 0.57

0.08 / 85.31 0.59 / 14.69 0.37

0.02 / 89.88 0.62 / 10.12 0.49

0.02 / 91.83 0.60 / 8.17 0.44


S26

Supplementary Table 13 Phosphorescence lifetime data of TPO-I powder at different temperature under air (λex = 350 nm, λem = 559 nm). τ1 (µs) / (%) τ2 (µs) / (%) τ (µs) a a

298 K

348 K

398 K

448 K

498 K

30.27 / 36.38 61.03 / 63.62 54.23

27.16 / 71.82 58.13 / 28.18 41.30

7.02 / 14.81 22.10 / 85.19 21.31

/ / /

/ / /


τi.

Supplementary Table 14. Phosphorescence lifetime data of TPO-Br powder at different temperature under air (λex = 350 nm, λem = 549 nm). τ1 (µs) / (%) τ2 (µs) / (%) τ (µs) a a

298 K

348 K

398 K

448 K

498 K

269 / 35.69 715 / 64.31 637

95 / 47.80 284 / 52.20 240

31 / 38.28 83 / 61.72 73

5 / 47.65 13 / 52.35 11

3 / 50.02 12 / 49.98 10


τi.

S27

Supplementary Table 15 Crystallographic and structural refinement data of TPO-I and TPO-Br. TPO-I

TPO-Br

Empirical formula

C27H20INO

C27H20BrNO

Formula weight

501.34

454.35

Temperature (K)

293(2) K

130

Wavelength (Å)

0.71073

0.71073

Crystal system

monoclinic

monoclinic

space group

P 21/n

P 1 21/c 1

a (Å)

10.1672(10)

17.168(7)

b (Å)

18.4224(18)

10.100(4)

c (Å)

12.1232(11)

13.276(5)

α (deg)

90

90

β (deg)

99.428(3)°

109.827(6)°

90

90

Volume (Å )

2240.1(4)

2165.5(15)

Z

4

4

Density (calculated) Absorption coefficient

1.487 Mg/m3 1.447 mm-1

1.394 Mg/m3 1.916 mm-1

γ (deg) 3

F(000)

1000

928

Crystal size

0.140 x 0.100 x 0.060 mm3

Theta range for data collection

2.030 to 25.499°.

0.165 x 0.1 x 0.01 mm3 2.378 to 27.739°.

Index ranges

-9