Supporting Information

Stabilized Lamellar Liquid Crystalline Phase with Aggregation-

Induced Emission Features Based on Pyrrolopyrrole Derivatives

Shuangxiong Dai,a Zhengxu Cai,a Zhe Peng,a Zhi Wang,a Bin Tong,a* Jianbing Shi,a Shenglong

Gan,b Qiming He,c Wei Chen b,c and Yuping Dong a*

a. Beijing Key Laboratory of Construction Tailorable Advanced Functional Materials and Green

Applications, School of Material Science & Engineering, Beijing Institute of Technology, 5 South

Zhongguancun Street, Beijing, 100081, China

b. Materials Science Division, Argonne National Laboratory, 9700 Cass Avenue, Lemont, Illinois

60439, United States

c. Institute for Molecular Engineering, The University of Chicago, 5640 South Ellis Avenue,

Chicago, Illinois 60637, United States

* To whom correspondence should be addressed: Phone: +86-10-6891-7390

E-mail: tongbin@bit.edu.cn, chdongyp@bit.edu.cn

Contents

S1. Synthesis and characterization of the TPPP derivatives

S2. Absorption and emission spectra of the TPPP derivatives in solid states

S3. Absorption spectra of the TPPP derivatives in THF/water mixtures

S4. Emission spectra of the TPPP derivatives in THF/water mixtures

S5. Time-resolved PL decays spectra of the TPPP derivatives

S6. TGA test of the TPPP derivatives

S7. XRD patterns of TPPP-C6 and TPPP-C12 in the crystalline phase

S8. Mesomorphic textures of TPPP-C7 and TPPP-C8

S9. DSC curves of TPPP-C7 and TPPP-C8

S10. Single crystal data of TPPP-C6

S11. 1H NMR, 13C NMR and MALDI-MS spectra of the TPPP derivatives

S12. Reference

Electronic Supplementary Material (ESI) for Materials Chemistry Frontiers.This journal is © the Partner Organisations 2019

S1. Synthesis and characterization of TPPP derivatives

The nine TPPP derivatives were synthesized by using the known methods.1-2 The concrete steps are

listed as follows: In a 100 mL round-bottom flask equipped with a reflux condenser and magnetic

stir bar, aniline derivative (0.023 mol), benzaldehyde (2.4 g, 0.023 mol) and TsOH (0.40 g 0.0023

mol) were dissolved with 50 mL glacial acetic acid. The mixture was stirred at 90°C for 30 min.

After that time, butane-2,3-dione (0.97 g, 0.0113 mol) was slowly added. Then the reaction mixture

was stirred at 90°C for extra 3 h. The faint yellow precipitate of the obtained TPPP derivatives was

collected by filtration. Further purification was occurred by recrystallization from CHCl3 and drying

in a vacuum oven to yield a yellowish powder. (Approximate yield: 11-14%)

NH2 CHO

COOCnH2n+1

O

OTsOH, AcOH

N

N

OCnH2n+1

OCnH2n+1

O

O

90 oC, 3h

n=1,2,3,4,5,6,7,8,12

Scheme S1. The synthetic routes of the nine TPPP derivatives.

TPPP-C1: (2,5-Diphenyl-1,4-bis(4-methylbenzoat)-1,4-dihydropyrrolo[3,2-b]-pyrrole).

PE/EA (2:1), yellowish powder, yield: 13%. 1H NMR (400 MHz, CDCl3), δ: 8.03 (d, J = 8.0 Hz,

4H), 7.32 (d, J = 8.0 Hz, 4H), 7.23 (m, 10H), 6.48 (s, 2H), 3.92 (s, 6H). 13C NMR (100 MHz,

CDCl3), δ: (ppm): 166.56, 143.80, 136.07, 133.18, 131.28, 130.70, 128.44, 128.34, 127.03, 126.77,

124.42, 96.47, 52.20. MALDI-MS (m/z): calcd. for C34H26N2O4: 526.19. Found: 526.20 (M+).

TPPP-C2: (2,5-Diphenyl-1,4-bis(4-ethylbenzoat)-1,4-dihydropyrrolo[3,2-b]-pyrrole). PE/EA

(2:1), yellowish powder, yield: 14%. 1H NMR (400 MHz, CDCl3), δ: 8.04 (d, J = 8.0 Hz, 4H), 7.33

(d, J = 8.0 Hz, 4H), 7.24 (m, 10H), 6.47 (s, 2H), 4.38 (q, J = 8.0 Hz, 4H), 1.39 (t, J = 4.0 Hz, 6H).

13C NMR (100 MHz, CDCl3), δ: (ppm): 166.09, 143.72, 136.06, 133.20, 131.29, 130.65, 128.43,

128.33, 127.39, 126.74, 124.39, 96.41, 61.05, 14.36. MALDI-MS (m/z): calcd. for C36H30N2O4:

554.22. Found: 554.67 (M+).

TPPP-C3: (2,5-Diphenyl-1,4-bis(4-propylbenzoat)-1,4-dihydropyrrolo[3,2-b]-pyrrole). PE/EA

(3:1), yellowish powder, yield: 14%. 1H NMR (400 MHz, CDCl3), δ: 8.04 (d, J = 8.0 Hz, 4H), 7.32

(d, J = 8.0 Hz, 4H), 7.24 ((m, 10H), 6.47 (s, 2H), 4.28 (t, J = 8.0 Hz, 4H), 1.80 (m, 4H), 1.03 (t, J =

4.0 Hz, 6H). 13C NMR (100 MHz, CDCl3), δ: (ppm): 166.15, 143.72, 136.06, 133.20, 131.30,

130.66, 128.43, 128.33, 127.41, 126.74, 124.40, 96.43, 66.65, 22.15, 10.55. MALDI-MS (m/z):

calcd. for C38H34N2O4: 582.25. Found: 582.10 (M+).

TPPP-C4: (2,5-Diphenyl-1,4-bis(4-butylbenzoat)-1,4-dihydropyrrolo[3,2-b]-pyrrole). PE/EA

(5:1), yellowish powder, yield: 13%. 1H NMR (400 MHz, CDCl3), δ: 8.04 (d, J = 8.0 Hz, 4H), 7.33

(d, J = 8.0 Hz, 4H), 7.23 (m, 10H), 6.47 (s, 2H), 4.33 (t, J = 4.0 Hz, 4H), 1.75 (m, 4H), 1.48 (m,

4H), 0.99 (t, J = 4.0 Hz, 6H). 13C NMR (100 MHz, CDCl3), δ: (ppm): 166.16, 143.72, 136.06,

133.20, 131.30, 130.65, 128.44, 128.33, 127.41, 126.74, 124.39, 96.43, 64.94, 30.82, 19.30, 13.78.

MALDI-MS (m/z): calcd. for C40H38N2O4: 610.28. Found: 610.81 (M+).

TPPP-C5: (2,5-Diphenyl-1,4-bis(4-amylbenzoat)-1,4-dihydropyrrolo[3,2-b]-pyrrole). PE/EA

(6:1), yellowish powder, yield: 12%. 1H NMR (400 MHz, CDCl3), δ: 8.03 (d, J = 8.0 Hz, 4H), 7.28

(d, J = 8.0 Hz, 4H), 7.23 (m, 10H), 6.47 (s, 2H), 4.31 (t, J = 8.0 Hz, 4H), 1.77 (m, 4H), 1.41 (m,

8H), 0.94 (t, J = 8.0 Hz, 6H). 13C NMR (100 MHz, CDCl3), δ: (ppm): 166.15, 143.72, 136.06,

133.21, 131.31, 130.66, 128.44, 128.34, 127.43, 126.74, 124.40, 96.44, 65.25, 28.48, 28.23, 22.39,

14.00. MALDI-MS (m/z): calcd. for C42H42N2O4: 638.31. Found: 638.31 (M+).

TPPP-C6: (2,5-Diphenyl-1,4-bis(4-hexylbenzoat)-1,4-dihydropyrrolo[3,2-b]-pyrrole). PE/EA

(6:1), yellowish powder, yield: 11%. 1H NMR (400 MHz, CDCl3), δ: 8.03 (d, J = 8.0 Hz, 4H), 7.32

(d, J = 8.0 Hz, 4H), 7.24 (m, 10H), 6.47 (s, 2H), 4.31 (t, J = 8.0 Hz, 4H), 1.76 (m, 4H), 1.45 (m,

4H), 1.34 (m, 8H), 0.91 (t, J = 4.0 Hz, 6H). 13C NMR (100 MHz, CDCl3), δ: (ppm): 166.17, 143.70,

136.05, 133.20, 131.29, 130.66, 128.44, 128.33, 127.41, 126.74, 124.39, 96.44, 65.27, 31.50, 28.73,

25.76, 22.58, 14.05. MALDI-MS (m/z): calcd. for C44H46N2O4: 666.35. Found: 666.09 (M+).

TPPP-C7: (2,5-Diphenyl-1,4-bis(4-heptylbenzoat)-1,4-dihydropyrrolo[3,2-b]-pyrrole). PE/EA

(8:1), yellowish powder, yield: 11%. 1H NMR (400 MHz, CDCl3), δ: 8.03 (d, J = 8.0 Hz, 4H), 7.33

(d, J = 8.0 Hz, 4H), 7.23 (m, 10H), 6.48 (s, 2H), 4.31 (t, J = 8.0 Hz, 4H), 1.77 (t, J = 8.0 Hz, 4H),

1.35 (m, 16H), 0.90 (t, J = 8.0 Hz, 6H). 13C NMR (100 MHz, CDCl3), δ: (ppm): 166.17, 143.70,

136.05, 133.20, 131.29, 130.66, 128.44, 128.33, 127.41, 126.74, 124.39, 96.44, 65.28, 31.76, 29.00,

28.78, 26.06, 22.63, 14.10. MALDI-MS (m/z): calcd. for C46H50N2O4: 694.38. Found: 694.92 (M+).

TPPP-C8: (2,5-Diphenyl-1,4-bis(4-octylbenzoat)-1,4-dihydropyrrolo[3,2-b]-pyrrole). PE/EA

(8:1), yellowish powder, yield: 12%. 1H NMR (400 MHz, CDCl3), δ: 8.03 (d, J = 8.0 Hz, 4H), 7.32

(d, J = 8.0 Hz, 4H), 7.24 (m, 10H), 6.47 (s, 2H), 4.31 (t, J = 8.0 Hz, 4H), 1.76 (m, 4H), 1.44 (t, J =

8.0 Hz, 4H), 1.31 (m, 16H), 0.88 (t, J = 4.0 Hz, 6H). 13C NMR (100 MHz, CDCl3), δ: (ppm): 166.16,

143.70, 136.05, 133.20, 131.29, 130.66, 128.44, 128.33, 127.41, 126.74, 124.39, 96.43, 65.28,

31.82, 29.28, 29.22, 28.77, 26.08, 22.67, 14.12. MALDI-MS (m/z): calcd. for C48H54N2O4: 722.41.

Found: 722.92 (M+).

TPPP-C12: (2,5-Diphenyl-1,4-bis(4-dodecylbenzoat)-1,4-dihydropyrrolo[3,2-b]-pyrrole).

PE/EA (10:1), yellowish powder, yield: 12%. 1H NMR (400 MHz, CDCl3), δ: 8.03 (d, J = 8.0 Hz,

4H), 7.32 (d, J = 8.0 Hz, 4H), 7.24 (m, 10H), 6.47 (s, 2H), 4.31 (t, J = 8.0 Hz, 4H), 1.76 (m, 4H),

1.43 (m, 4H), 1.36 (m, 32H), 0.88 (t, J = 4.0 Hz, 6H). 13C NMR (100 MHz, CDCl3), δ: (ppm):166.16,

143.70, 136.05, 133.20, 131.29, 130.66, 128.44, 128.33, 127.41, 126.74, 124.39, 96.43, 65.28,

31.93, 29.67, 29.62, 29.56, 29.37, 29.33, 28.77, 26.08, 22.71, 14.14. MALDI-MS (m/z): calcd. for

C56H70N2O4: 834.53. Found: 834.42 (M+).

S2. Absorption and emission spectra of the TPPP derivatives in solid states

300 350 400 450 5000.0

0.2

0.4

0.6

0.8

1.0 a

Nor

mal

ized

Abs

orpt

ion

Wavelength (nm)

TPPP-C1 TPPP-C2 TPPP-C3 TPPP-C4 TPPP-C5 TPPP-C6 TPPP-C7 TPPP-C8 TPPP-C12

400 450 500 550 600 6500.0

0.2

0.4

0.6

0.8

1.0 b

Nor

mal

ized

PL

Inte

nsity

Wavelength (nm)

TPPP-C1 TPPP-C2 TPPP-C3 TPPP-C4 TPPP-C5 TPPP-C6 TPPP-C7 TPPP-C8 TPPP-C12

Fig. S1 (a) Normalized UV-vis absorption spectra of the TPPP derivatives in solid states; (b) Normalized

fluorescence spectra of the TPPP derivatives in solid states.

S3. Absorption spectra of the TPPP derivatives in THF/water mixtures

300 400 5000.0

0.2

0.4

0.6 0 10 20 30 40 50 60 70 80 90 95 99

w (vol%)

Abs

orpt

ion

Wavelength (nm)

TPPP-C1

300 400 5000.0

0.2

0.4

0.6w (vol%)

Abs

orpt

ion

Wavelength (nm)

0 10 20 30 40 50 60 70 80 90 95 99

TPPP-C2

300 400 5000.0

0.3

0.6

0.9w (vol%)

Abso

rptio

n

Wavelength (nm)

0 10 20 30 40 50 60 70 80 90 95 99

TPPP-C3

300 400 5000.0

0.2

0.4

0.6

0.8 w (vol%)

Abso

rptio

n

Wavelength (nm)

0 10 20 30 40 50 60 70 80 90 95 99

TPPP-C4

300 350 400 450 500 5500.0

0.2

0.4

0.6

0.8w (vol%)

Abso

rptio

n

Wavelength (nm)

0 10 20 30 40 50 60 70 80 90 95 99

TPPP-C5

300 400 5000.00

0.35

0.70

w (vol%)

Abso

rptio

n

Wavelength (nm)

0 10 20 30 40 50 60 70 80 90 95 99

TPPP-C6

300 400 5000.0

0.1

0.2

0.3

0.4

0.5

0.6

w (vol%)

Abs

orpt

ion

Wavelength (nm)

0 10 20 30 40 50 60 70 80 90 95 99

TPPP-C7

300 400 5000.0

0.1

0.2

0.3

0.4

0.5 w (vol%)

Abs

orpt

ion

Wavelength (nm)

0 10 20 30 40 50 60 70 80 90 95 99

TPPP-C8

300 400 5000.0

0.1

0.2

0.3

0.4

0.5

0.6w (vol%)

Abs

orpt

ion

Wavelength (nm)

0 10 20 30 40 50 60 70 80 90 95 99

TPPP-C12

Fig. S2. UV-vis absorption spectra of the nine TPPP derivatives in THF/water mixtures with different water fractions

(fw). Concentration: 1 × 10-5 M.

S4. Emission spectra of the TPPP derivatives in THF/water mixtures

400 450 500 550 600

0

200

400

600

800

1000

1200 w (%)

PL In

tens

ity (a

.u.)

Wavelength (nm)

0 10 20 30 40 50 60 70 80 90 95 99

TPPP-C1

0 20 40 60 80 100

470

480

490

500

510

520

530

Wavelength I/I0

Wav

elen

gth

(nm

)

Water fraction (vol %)

TPPP-C1

0

2

4

6

8

I/I0

400 450 500 550 600

0

1000

2000

3000

4000

5000

0 10 20 30 40 50 60 70 80 90 95 99

w (%)

PL In

tens

ity (a

.u.)

Wavelength (nm)

TPPP-C2

0 20 40 60 80 100

450

460

470

480

490

500

510

520

530

Wav

elen

gth

(nm

)

Water fraction (vol %)

0

2

4

6TPPP-C2 Wavelength

I/I0

I/I0

400 450 500 550 600

0

1000

2000

3000

4000

5000w (%)

PL In

tens

ity (a

.u.)

Wavelength (nm)

0 10 20 30 40 50 60 70 80 90 95 99

TPPP-C3

0 20 40 60 80 100

470

480

490

500

510

520

530

Wav

elen

gth

(nm

)

Water fraction (vol %)

0

2

4

6TPPP-C3 Wavelength

I/I0

I/I0

400 450 500 550 600-200

0

200

400

600

800

1000

1200

1400

1600w (%)

PL In

tens

ity (a

.u.)

Wavelength (nm)

0 10 20 30 40 50 60 70 80 90 95 99

TPPP-C4

0 20 40 60 80 100470

480

490

500

510

520

530

Wav

elen

gth

(nm

)

Water fraction (vol %)

0

2

4

6TPPP-C4

Wavelength I/I0

I/I0

400 450 500 550 600-200

0

200

400

600

800

1000

1200

1400

1600w (%)

PL In

tens

ity (a

.u.)

Wavelength (nm)

0 10 20 30 40 50 60 70 80 90 95 99

TPPP-C5

0 20 40 60 80 100

470

480

490

500

510

520

530

540

Wav

elen

gth

(nm

)

Water fraction (vol %)

0

2

4

6TPPP-C5 Wavelength

I/I0

I/I0

400 450 500 550 600

0

200

400

600

800

1000w (%)

PL In

tens

ity (a

.u.)

Wavelength (nm)

0 10 20 30 40 50 60 70 80 90 95 99

TPPP-C7

0 20 40 60 80 100440

460

480

500

520

Wav

elen

gth

(nm

)

Water fraction (vol %)

TPPP-C7

0

2

4

6

8

Wavelength I/I0

I/I0

400 450 500 550 600

0

1000

2000

3000

4000

5000

PL in

tens

ity (a

.u.)

Wavelength (nm)

0 10 20 30 40 50 60 70 80 90 95 99

w (%)TPPP-C8

0 20 40 60 80 100

470

480

490

500

510

520

530

Wav

elen

gth

(nm

)

Water fraction (vol %)

0

1

2

3

4

5

6 Wavelength I/I0

I/I0

TPPP-C8

400 450 500 550 600

0

1000

2000

3000

4000

5000

PL in

tens

ity (a

.u.)

Wavelength (nm)

0 10 20 30 40 50 60 70 80 90 95 99

w (%)TPPP-C12

0 20 40 60 80 100

470

475

480

485

490

495

500

505

510

Wav

elen

gth

(nm

)

Water fraction (vol %)

0

2

4

6TPPP-C12 Wavelength

I/I0

I/I0

Fig. S3. Fluorescence spectra of the TPPP derivatives in THF/water mixtures with different water fractions (left);

Plot of wavelength and the ratio of maximum fluorescence intensity of the TPPP derivatives vs. water fraction (right).

I0 = emission intensity in pure THF solution. Excitation wavelength: 322 nm, concentration: 1 × 10-5 M.

S5. Time-resolved PL decays spectra of the TPPP derivatives

0 10 20 30 40 501

10

100

1000

Inte

nsity

(a.u

.)

Lifetime (ns)

TPPP-C1 (THF)= 2.95 ns

0 50 100 150 2001

10

100

1000

Inte

nsity

(a.u

.)

Lifetime (ns)

TPPP-C1 (Solid) = 15.4 ns

0 10 20 30 40 501

10

100

1000

Inte

nsity

(a.u

.)

Lifetime (ns)

TPPP-C2 (THF)= 3.09 ns

0 50 100 150 2001

10

100

1000

Inte

nsity

(a.u

.)

Lifetime (ns)

TPPP-C2 (Solid) = 8.86 ns

0 10 20 30 40 501

10

100

1000

Inte

nsity

(a.u

.)

Lifetime (ns)

TPPP-C3 (THF) = 3.21 ns

0 50 100 150 2001

10

100

1000

Inte

nsity

(a.u

.)

Lifetime (ns)

TPPP-C3 (Solid)1 = 3.59 (23.07%)2 = 8.89 (76.93%)av = 7.67 ns

0 10 20 30 40 501

10

100

1000

Inte

nsity

(a.u

.)

Lifetime (ns)

TPPP-C4 (THF)= 3.24 ns

0 50 100 150 200

10

100

1000

Inte

nsity

(a.u

.)

Lifetime (ns)

TPPP-C4 (Solid)= 15.39 ns

0 10 20 30 40 501

10

100

1000

Inte

nsity

(a.u

.)

Lifetime (ns)

TPPP-C5 (THF)= 3.28 ns

0 50 100 150 200

10

100

1000

Inte

nsity

(a.u

.)

Lifetime (ns)

TPPP-C5 (Solid)= 14.09 ns

0 10 20 30 40 501

10

100

1000

Inte

nsity

(a.u

.)

lifetime (ns)

TPPP-C6 (THF) = 3.27 ns

0 50 100 150 200

10

100

1000

Inte

nsity

(a.u

.)

Lifetime (ns)

TPPP-C6 (Solid)= 3.81 ns (21.66%)= 10.8 ns (78.34%)av= 9.29 ns

0 10 20 30 40 501

10

100

1000

Inte

nsity

(a.u

.)

Lifetime (ns)

TPPP-C7 (THF)= 3.28 ns

0 20 40 60 80 100 120

10

100

1000

Inte

nsity

(a.u

.)

Lifetime (ns)

TPPP-C7 (Solid)= 1.37 ns (37.24%)= 5.93 ns (62.76%)av = 4.23 ns

0 10 20 30 40 501

10

100

1000

Inte

nsity

(a.u

.)

Lifetime (ns)

TPPP-C8 (THF)= 3.27 ns

0 50 100 150 2001

10

100

1000

Inte

nsity

(a.u

.)

Lifetime (ns)

= 10.15 nsTPPP-C8 (Solid)

0 10 20 30 40 50

10

100

1000

Inte

nsity

(a.u

.)

Lifetime (ns)

TPPP-C12 (THF)= 3.30 ns

0 50 100 150 200

10

100

1000

Inte

nsity

(a.u

.)

Lifetime (ns)

TPPP-C12 (Solid)= 2.96 ns (19.86%)= 9.71 ns (80.14%)av= 8.37 ns

Fig. S4. Time-resolved PL decays spectra of the nine TPPP derivatives measured in THF solution (1 × 10-5 M) and

solid states. All profiles were taken at room temperature.

S6. TGA test of the TPPP derivatives

100 200 300 400 500 600 700

20

30

40

50

60

70

80

90

100

Mas

s re

mai

ning

wei

ght (

%)

Temperature (oC)

TPPP-C1 TPPP-C2 TPPP-C3 TPPP-C4 TPPP-C5 TPPP-C6 TPPP-C7 TPPP-C8 TPPP-C12

Fig. S5. TGA thermograms of the TPPP derivatives measured under nitrogen at a heating rate of 10oC/min.

S7. XRD patterns of TPPP-C6 and TPPP-C12 in the crystalline phase

5 10 15 20 25 30 35

Inte

nsity

(a.u

.)

2(deg)

TPPP-C6

5 10 15 20 25 30 35

Inte

nsity

(a.u

.)

2 (deg)

TPPP-C12

Fig. S6. XRD patterns of TPPP-C6 and TPPP-C12 in the crystalline phase.

S8. Mesomorphic textures of TPPP-C7 and TPPP-C8

Fig. S7. Mesomorphic textures of TPPP-C7 and TPPP-C8 observed on cooling to 103oC and 87oC, respectively.

On heating, no LC phase was detected. On cooling, LC phase was observed from their isotropic states at a cooling

rate of 0.5oC/min. All textures were taken after application of a shearing force and the polarizer was in the crossed

position.

S9. DSC curves of TPPP-C7 and TPPP-C8

40 60 80 100 120 140 160 180

1st cooling

End

o

Hea

t Flo

w (

w/g

)

Temperature (oC)

2nd heating

Tpeak = 142.4 oC

H = 79.25 KJ mol-1

H = -77.39 KJ mol-1

Tpeak = 95.9 oC

TPPP-C7

50 100 150 200

Temperature (oC)

Hea

t Flo

w (

w/g

) E

ndo

2nd heating

1st cooling

Tpeak = 150.5 oC

H = 89.21 KJ mol-1

Tpeak = 104.6 oC

H = -87.70 KJ mol-1

TPPP-C8

Fig. S8. DSC curves of TPPP-C7 and TPPP-C8 recorded under nitrogen during the first cooling and second heating

cycles with a scan rate of 5oC/min.

S10. Single crystal data of TPPP-C6

Table S1. Single crystal data of TPPP-C6.

Identification code TPPP-C6

Empirical formula C44H46N2O4

Formula weight 666.83

Temperature/K 153.15

Crystal system triclinic

Space group P-1

a/Å 6.3304(13)

b/Å 7.2037(14)

c/Å 20.473(4)

α/° 89.41(3)

β/° 89.13(3)

γ/° 76.08(3)

Volume/Å3 906.1(3)

Z 1

ρcalcg/cm3 1.222

μ/mm‑1 0.078

F(000) 356.0

Crystal size/mm3 0.21 × 0.2 × 0.13

Radiation MoKα (λ = 0.71073)

2θ range for data collection/° 5.826 to 54.968

Index ranges -8 ≤ h ≤ 8, -9 ≤ k ≤ 9, -26 ≤ l ≤ 26

Reflections collected 12409

Independent reflections 4138 [Rint = 0.0704, Rsigma = 0.0752]

Data/restraints/parameters 4138/0/227

Goodness-of-fit on F2 1.155

Final R indexes [I>=2σ (I)] R1 = 0.0638, wR2 = 0.1427

Final R indexes [all data] R1 = 0.0715, wR2 = 0.1476

Largest diff. peak/hole / e Å-3 0.25/-0.24

S11. 1H NMR, 13C NMR and MALDI-MS spectra of the TPPP derivatives

Fig. S9. 1H NMR spectra of TPPP-C1 in CDCl3.

Fig. S10. 13C NMR spectra of TPPP-C1 in CDCl3.

400 500 600

0

20

40

60

80

100

M/Z

526.2TPPP-C1

Fig. S11. MALDI-MS spectra of TPPP-C1.

Fig. S12. 1H NMR spectra of TPPP-C2 in CDCl3.

Fig. S13. 13C NMR spectra of TPPP-C2 in CDCl3.

400 500 600 700 800 900 1000 11000

500

1000

1500

2000

Inte

nsity

(a.u

.)

M/Z

554.674

TPPP-C2

Fig. S14. MALDI-MS spectra of TPPP-C2.

Fig. S15. 1H NMR spectra of TPPP-C3 in CDCl3.

Fig. S16. 13C NMR spectra of TPPP-C3 in CDCl3.

400 500 600

0

20

40

60

80

100In

tens

ity (a

.u.)

M/Z

582.1TPPP-C3

Fig. S17. MALDI-MS spectra of TPPP-C3.

Fig. S18. 1H NMR spectra of TPPP-C4 in CDCl3.

Fig. S19. 13C NMR spectra of TPPP-C4 in CDCl3.

400 500 600 700 800 900 1000 1100 1200

0

200

400

600

Inte

nsity

(a.u

.)

M/Z

610.805TPPP-C4

Fig. S20. MALDI-MS spectra of TPPP-C4.

Fig. S21. 1H NMR spectra of TPPP-C5 in CDCl3.

Fig. S22. 13C NMR spectra of TPPP-C5 in CDCl3.

500 1000

0

1000

2000

Inte

nsity

(a.u

.)

M/Z

638.312TPPP-C5

Fig. S23. MALDI-MS spectra of TPPP-C5.

Fig. S24. 1H NMR spectra of TPPP-C6 in CDCl3.

Fig. S25. 13C NMR spectra of TPPP-C6 in CDCl3.

400 600 800 1000 1200 1400

0

2000

4000

Inte

nsity

(a.u

.)

M/Z

666.086

TPPP-C6

Fig. S26. MALDI-MS spectra of TPPP-C6.

Fig. S27. 1H NMR spectra of TPPP-C7 in CDCl3.

Fig. S28. 13C NMR spectra of TPPP-C7 in CDCl3.

500 600 700 800 900 1000 1100

0

2000

4000

6000

8000In

tens

ity (a

.u.)

M/Z

TPPP-C7

694.920

Fig. S29. MALDI-MS spectra of TPPP-C7.

Fig. S30. 1H NMR spectra of TPPP-C8 in CDCl3.

Fig. S31. 13C NMR spectra of TPPP-C8 in CDCl3.

500 600 700 800 900 1000 1100

0

2000

4000

Inte

nsity

(a.u

.)

M/Z

TPPP-C8

722.920

Fig. S32. MALDI-MS spectra of TPPP-C8.

Fig. S33. 1H NMR spectra of TPPP-C12 in CDCl3.

Fig. S34. 13C NMR spectra of TPPP-C12 in CDCl3.

400 600 800 1000

0

2000

4000

6000In

tens

ity (a

.u.)

M/Z

TPPP-C12 834.419

Fig. S35. MALDI-MS spectra of TPPP-C12.

S12. References

1 M. Krzeszewski, B. Thorsted, J. Brewer and D. T. Gryko, J. Org. Chem., 2014, 79, 3119-3128.2 M. Krzeszewski, D. Gryko and D. T. Gryko, Acc. Chem. Res., 2017, 50, 2334-2345.