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Electronic Supporting Information for:

Fluorescence Property and Aggregation Behavior of Tetraphenylethene-

Perylenebisimide Dyads

Yi Jia Wang a, Zeyu Li a, Jiaqi Tong a, Xiao Yuan Shen a, Anjun Qin ab, Jing Zhi Sun a,*, and Ben Zhong Tang abc,* aMoE Key Laboratory of Macromolecule Synthesis and Functionalization, Department of Polymer Science and Engineering, Zhejiang University, Hangzhou 310027, China. E-mail: sunjz@zju.edu.cn; Fax: +86 571 87953734; Tel: +86 571 87953734 b Guangdong Innovative Research Team, State Key Laboratory of Luminescent Materials and Devices, South China University of Technology, Guangzhou 510640, China. c Department of Chemistry, Institute for Advanced Study, State Key Laboratory of Molecular NeuroScience, and Division of Biomedical Engineering, The Hong Kong University of Science & Technology, Clear Water Bay, Kowloon, Hong Kong, China. E-mail: tangbenz@ust.hk; Fax: +852-23581594; Tel: +852-23587375

Table of Contents

Synthetic details (2)

Fig.S1 1H NMR spectra of M1 in d-DMSO. (5)

Fig.S2 FT-IR spectra of PTCDA and M1. (5)

Fig.S3 1H NMR and 13C NMR spectrum of TPE-NH2 (M2) in CDCl3. (6)

Fig.S4 1H NMR and 13C NMR spectrum of TPE-N-PBI in CDCl3. (7)

Fig.S5 FT-IR spectra of M1 and TPE-N-PBI. (8)

Fig.S6 FT-IR spectra of PTCDA and DTPE-N-PBI. (9)

Fig.S7 MALDI-TOF mass spectra of M1. (9)

Fig.S8 MALDI-TOF mass spectra of TPE-N-PBI. (10)

Fig.S9 MALDI-TOF mass spectra of DTPE-N-PBI. (10)

Fig. S10 Cyclic voltammograms of M1 and TPE-N-PBI in DCM. (11)

Fig. S11 X-ray diffraction patterns of DTPE-N-PBI aggregates at different sites. (11)

Table S1 Optical and electronic properties of M1, TPE-N-PBI and DTPE-N-PBI. (12)

 

Electronic Supplementary Material (ESI) for Journal of Materials Chemistry C.This journal is © The Royal Society of Chemistry 2015

 

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Synthetic details.

1. Potassium 9-carboxy-1,3-dioxo-1,3-dihydrobenzo-[5,10]-anthrax-[2,1,9-def]isochromene-8-

carboxylate (1).

3,4,9,10-perylenetetracarboxylic dianhydride (PTCDA) (1.96 g, 5 mM) was dissolved in a

5% potassium hydroxide (22.4 g, 20 mM) solution at 90 °C under nitrogen. Then 14.0 g of 10%

acetic acid was added dropwise into the flask over 30 min. The suspension was stirred for another

1 h at the same temperature. The precipitated product 1 was filtered at room temperature, washed

with water, and dried at 130 °C. Yield: 67%. The product was used for further reaction without

purification.

O O

O

O

O

O

OOH

OK

O

O

O

O

KOH

HAcO

O

O

N

O

OH2O, PrOH

NH2

M11

Scheme S1 Synthetic route to precursor compound M1.

2. 9-(2-Ethylhexyl)-1H-isochromeno[6',5',4':10,5,6]anthrax-[2,1,9-def]isoquinoline-1,3,8,10-

(9H)-tetraone (M1):

The synthetic route is shown in Scheme 1 and the experiment procedures are described as

following. A mixture of compound 1 (1.25 g, 2.79 mM) and a 4.4 molar ratio of

2-ethylhexylamine (1.59 g, 12.3 mM) and 12 mL of H2O-PrOH (v/v = 1:1 ) mixture as solvent

was stirred at room temperature for 4 h and heated at 90 °C for another 2 h with stirring. The

reaction mixture was then acidified with 10% hydrochloric acid, and the resulting precipitate was

filtered and washed with water to remove residual amine. After which, the residue was stirred into

hot 10% potassium hydroxide solution, and to the mixture was added 8% potassium chloride to

separate the precipitated potassium salt of M1 and the symmetrically substituted diimide from the

soluble, unreacted compound 1. The solid was then added into water and the insoluble,

symmetrically substituted diimide was removed. The filtrate was acidified with 20% hydrochloric

acid. The precipitate was filtered, washed with water, and dried to yield M1 in 10% yield. FT-IR

(KBr): υ = 769, 1732, 1698, 1656, 1594, 1404, 1321, 1245, 1022, 810, 739 cm-1. 1H NMR (400

MHz, d-DMSO, δ): 8.90-8.32 (m, 8H), 4.12-3.94 (m, 2H), 2.00-1.82 (m, 1H), 1.48-1.18 (m, 8H),

0.99-0.74 (m, 6H). HRMS (MALDI-TOF, m/z): [M]+ calcd. for C32H25NO5: 503.1733, found:

503.1737 (see Fig. S1, S2 and S7).

OO

NH2

Zn, TiCl4THF

NH2M2

Scheme S2. Synthetic route to amino-functionalized tetraphenylethene M2.

 

3  

3. 4-(1,2,2-Triphenylvinyl)aniline (TPE-NH2, M2):

The synthetic route is shown in Scheme 2 and the experiment details are described below. Zinc

dust (1.2 g, 18 mmol) was added into a 250 mL two-necked round-bottomed flask. The flask was

degassed and flushed with dry nitrogen three times, after which THF (60 mL) was injected. The

mixture was cooled to −5 to 0 °C by an ice-salt bath, then titanium tetrachloride (1 mL, 9 mmol)

was added slowly. The mixture was allowed to warm to 25 °C and kept for 0.5 h and then refluxed

at 74 °C for 2 h. The mixture was cooled to −5 to 0 °C again, treated with 0.5 mL of pyridine, and

stirred for 10 min. Then a THF solution (10 mL) of benzophenone (0.58 g, 3.2 mmol) and

4-aminobenzophenone (0.51 g, 2.6 mmol) was added slowly. After refluxing overnight, the

reaction was quenched with a 10% potassium carbonate aqueous solution and extracted with DCM.

The organic layer was washed with brine and dried over anhydrous magnesium sulfate. After

filtration and solvent evaporation, the residue was purified by silica gel column chromatography,

using petroleum ether/DCM (5:1 by volume) as eluent. The target compound (0.47 g) was

obtained as a light yellow solid in 51.6% yield. 1H NMR (400 MHz, CDCl3, δ): 7.23-6.94 (m,

15H), 6.90-6.75 (d, J = 9.6 Hz, 2H), 6.50-6.40 (d, J = 9.6 Hz, 2H), 4.00-3.50 (s, 2H). 13C NMR

(100 MHz, CDCl3, δ): 144.48, 144.38, 144.32, 141.04, 139.80, 132.75, 131.70, 131.62, 131.59,

127.95, 127.79, 127.78, 126.55, 126.39, 126.35, 115.24 (see Fig. S3).

N N

O

O

O

O

ZnAc2imidazole

180oC

TPE-N-PBI

O

O

O

N

O

O M1 NH2M2

+

Scheme S3. Synthetic route to mono-TPE modified PBI (TPE-N-PBI).

4. 2-(2-Ethylhexyl)-9-(4-(1,2,2-triphenylvinyl)phenyl)anthrax-[2,1,9-def:6,5,10-d'e'f']diiso-

quinoline-1,3,8,10(2H,9H)-tetraone (TPE-N-PBI):

The typical synthetic procedures are described as below and the synthetic route is shown in

Scheme 3. M1 (0.5 g, 1 mmol), M2 (0.7 g, 2 mmol), zinc acetate (0.1 g) and imidazole (10 g) were

added into a 100 mL two-necked round-bottomed flask. The flask was degassed and flushed with

dry nitrogen three times. And then the mixture was heated to 180 °C and stirred for 24h and then

cooled to room temperature. The mixture was poured into 100 mL of ice water and the precipitate

was filtered and washed with water. After drying, the residue was purified by silica gel column

chromatography, using petroleum ether/DCM (1:1 by volume) as eluent. The target compound

(0.20 g) was obtained as a dark red solid in 24.1% yield. FTIR (KBr): υ = 1697, 1657, 1595, 1440,

1403, 1354, 1256, 1179, 1125, 1075, 852, 810, 747, 700, 625, 584 cm-1. 1H NMR (400 MHz,

CDCl3, δ): 8.69-8.31 (m, 8H), 7.25−7.03 (m, 19H), 4.20-4.04 (m, 2H), 1.99-1.83 (m, 1H),

1.47-1.20 (m, 8H), 1.00-0.81 (m, 6H). 13C NMR (100 MHz, CDCl3, δ): 167.97, 163.62, 163.42,

144.37, 143.90, 143.62, 143.58, 142.02, 140.37, 134.65, 134.18, 133.32, 132.69, 132.39, 131.74,

131.63, 131.58, 131.24, 131.07, 129.70, 129.20, 129.01, 128.15, 128.06, 127.96, 127.89, 126.32,

 

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126.16, 123.58, 123.39, 38.99, 38.21, 32.14, 30.60, 29.90, 29.55, 29.16, 23.99, 23.30, 23.20, 22.90,

14.32, 14.25, 11.19, 10.85. HRMS (MALDI-TOF, m/z): [M]+ calcd. for C58H44N2O4: 832.3301,

found: 832.3318 (see Fig. S4, S5 and S8).

OO

O

O

O

ONH2

ZnAc2, Quinoline

215oC NN

O

O

O

ODTPE-N-PBI

+

M2

Scheme S4. Synthetic route to dual-TPE modified PBI (DTPE-N-PBI).

5. 2,9-Bis(4-(1,2,2-triphenylvinyl)phenyl)anthra[2,1,9-def:6,-5,10-d'e'f']diisoquinoline-1,3,8,10-

(2H,9H)-tetraone (DTPE-N-PBI):

PTCDA (0.5 g, 1 mmol), M2 (0.7 g, 2 mmol) and zinc acetate (0.1 g) was added into a 100 mL

two-necked round-bottomed flask. The flask was degassed and flushed with dry nitrogen three

times, after which quinoline (20 mL) was injected. The mixture was stirred at 215 °C for 36 h and

then cooled to room temperature. The mixture was poured into 100 mL of ice water and the

precipitate was filtered. The residue was stirred into 10% hydrochloric acid, and the resulting

precipitate was filtered and washed with water. After that, the residue was added into hot 10%

potassium hydroxide and was stirring at 90 °C for 0.5 h. The precipitate was filtered, washed with

DCM, THF and methanol and dried to yield DTPE-N-PBI in 44.2% yield. FT-IR (KBr): υ = 1709,

1670, 1594, 1506, 1404, 1346, 1253, 1174, 810, 748, 700 cm-1. HRMS (MALDI-TOF, m/z): [M]+

calcd. for C76H46N2O4: 1050.3458, found: 1050.3488 (see Fig. S6 and S9).

 

5  

 

9.0 8.5 4 3 2 1 0

*

NO

O

O

O

O

a

Chemical shift (ppm)

a

*

 

 

Fig.S1 1H NMR spectra of M1 in d-DMSO. The solvent peak is marked with asterisk.  

4000 3000 2000 1500 1000 500Wavenumbers(cm-1)

M1

PTCDA

A

B

-CO-N-CO-

-CO-O-CO-

-CO-O-CO-

 Fig.S2 FT-IR spectra of (A) PTCDA and (B) M1.

 

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7.5 7.0 6.5 4 3

160 150 140 130 120 110 100

NH2

ba

Chemical shift (ppm)

cb

a

c*NH2

b

b

Chemical shift (ppm)

a

c

ac

 

 

Fig.S3 1H NMR and 13C NMR spectrum of TPE-NH2 in CDCl3. The solvent peak is marked with asterisk.

 

 

 

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9 8 7 4 3 2 1 0

170 150 130 40 20 0

N N

OO

O O

**

a

b

a

Chemical shift (ppm)

c

bc*

N N

OO

O O

b

b

Chemical shift (ppm)

ac

a c

  

Fig.S4 1H NMR and 13C NMR spectrum of TPE-N-PBI in CDCl3. The solvent peaks are marked with asterisks.

 

 

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4000 3000 2000 1500 1000 500

Wavenumbers (cm-1)

-CO-N-CO-

-CO-O-CO-

TPE-N-PBI

M1

A

B

-CO-N-CO-

 

 

Fig.S5 FT-IR spectra of (A) M1 and (B) TPE-N-PBI.  

 

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4000 3000 2000 1500 1000 500Wavenumbers(cm-1)

DTPE-N-PBI

PTCDA

A

B

-CO-N-CO-

-CO-O-CO-

 Fig.S6 FT-IR spectra of (A) PTCDA and (B) DTPE-N-PBI.

 jm-C8N-PBI; MW=503

m/z300 320 340 360 380 400 420 440 460 480 500 520 540 560 580 600

%

0

100tan131230_1 148 (2.467) Cm (145:149-1:61) TOF MS EI+

280391.0524

321.0792

313.2758

390.0632

347.0642

346.0565 374.0335368.3523

374.0732

503.1737

392.0557

404.0662

502.1938405.0676433.2071

405.0992 486.1767479.4162458.9422

504.1789

537.4850

523.4736 597.3146576.6326568.6103

Fig.S7 MALDI-TOF mass spectra of M1.  

503.1737

O

O

O

N

O

O

[M]+ calcd: 503.1733

 

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 zeg-wyj-112, MW=832; DCTB

m/z575 600 625 650 675 700 725 750 775 800 825 850 875 900 925 950 975 1000 1025 1050

%

0

100tan130718_3 20 (0.665) Cn (Cen,4, 50.00, Ar); Sb (15,10.00 ); Sm (SG, 2x3.00); Cm (19:37) TOF LD+

292832.3318

582.4009 639.4122595.3915

625.3978751.4575683.4250 731.4409

773.4120 785.4457

833.3345

834.3378

835.3384

855.32161002.6094915.5103877.5060 943.5110 979.5941 1025.5808

 

Fig.S8 MALDI-TOF mass spectra of TPE-N-PBI.  

jm-DTPE-PBI, MW=1050, DCTB

m/z750 775 800 825 850 875 900 925 950 975 1000 1025 1050 1075 1100 1125 1150 1175 1200 1225 1250 1275 1300

%

0

100tan131231_6 15 (0.499) Cn (Cen,4, 30.00, Ar); Sb (15,10.00 ); Sm (SG, 2x3.00); Cm (10:16) TOF LD+

43.91050.3488

813.3389

751.4354

752.4122

760.3997

817.2626

861.4109

819.2783

831.3818

953.4529911.4101862.4084

951.4658987.5630 1033.4922

1001.5515

1051.3485

1052.3606

1114.27391113.28031053.3937

1069.61901163.56321116.2749 1208.6276 1227.5039 1263.4862

1290.5359

Fig.S9 MALDI-TOF mass spectra of DTPE-N-PBI.

832.3318

N N

O

O

O

O

[M]+ calcd: 832.3301 

1050.3488

NN

O

O

O

O

[M]+ calcd: 1050.3458 

 

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2.0 1.5 1.0 0.5 0.0 -0.5 -1.0 -1.5 -2.0

-1.5

-1.0

-0.5

0.0

0.5

1.0

1.5

2.0

2.0 1.5 1.0 0.5 0.0 -0.5 -1.0 -1.5 -2.0

-1.5

-1.0

-0.5

0.0

0.5

1.0

1.5

2.0

Potential (V vs SCE)

Cur

rent

10-5

A

A

Cur

rent

10-5

A

Potential (V vs SCE)

B

 Fig. S10 The cyclic voltammograms of (A) M1 and (B) DTPE-N-PBI measured in DCM containing 0.1M [nBu4N]+[PF6]- at a scan rate of 50 mV/s. AgCl was used as reference electrode and ferrocene as a calibration. To obtain well-resolved CV signal, the concentration of TPE-N-PBI and M1 in DCM was 1.0×10-4 M, which was higher than that used in the optical spectrum measurements.

Fig. S11 Typical X-ray diffraction patterns of DTPE-N-PBI aggregates at different areas. Only dispersive halos can be observed on the patterns. The images were recorded on a high resolution transmittance electron microscope (HRTEM) instrument.

 

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Table S1 Data Summary of the Optical and Electromnic Properties of M1, TPE-N-PBI and

DTPE-N-PBI  

M1 TPE-N-PBI DTPE-N-PBI λabs,sol / nm 521 527 527 λem,sol / nm 535 539 539 λem,agg / nm 524 529 523 ΦF, sol / % 57.86 0.32 0.39 ΦF, agg / % 36.91 0.55 1.48 ΦF, film / % 0.9 0.5 0.5

HOMOcal / eV -6.21 -5.34 -5.34 LUMO cal / eV -3.67 -3.43 -3.41 ΔE cal / eV 2.54 1.91 1.93

HOMOmeas / eV -6.20 -6.40 LUMO meas / eV -3.88 -4.12 ΔE meas / eV 2.32 2.28