Benzenetricarboxamide-cored Triphenylamine Dendrimer: Nano ... · S1 Supporting information . Benzenetricarboxamide-cored Triphenylamine Dendrimer: Nano-Particle Film Formation by

S1

Supporting information

Benzenetricarboxamide-cored Triphenylamine

Dendrimer: Nano-Particle Film Formation by

Electrochemical Method

Man-kit Leung a,b *, You-Shiang Lina, Chung-Chieh Leea, Chih-Cheng Changa, Yu-Xun Wanga, Cheng-Po,

Kuoa, Nirupma Singha, Kun-Rung Lina, Chih-Wei Huc, Chen-Ya Tsengc, Kuo-Chuan Ho b,c *

aDepartment of Chemistry, bInstitute of Polymer Science and Engineering, and cDepartment of Chemical Engineering,

National Taiwan University, 1, Roosevelt Road Section 4, Taipei, Taiwan 106, ROC

Materials (about 1, 3, 4, 7-9, G0) S2 Preparation of 2 S2 Preparation of 5 S3 Preparation of 6 S4 Preparation of 9 S4 Preparation of G0 S5 Preparation of G1 S6 UV-Vis, Fluorescence, and Aggregation Induced Emission Experiments S8 Electrochemical studies and Electrochemical Welding S8 Figure S1 1H NMR of 5 S10 Figure S2 13C NMR of 5 S11 Figure S3 1H NMR of 6 S12 Figure S4 13C NMR of 6 S13 Figure S5 1H NMR of 2 S14 Figure S6 13C NMR of 2 S15 Figure S7 1H NMR of 1 S16 Figure S8 1H NMR of 9 S17 Figure S9 1H NMR of G0 S18 Figure S10 13C NMR of G0 S19 Figure S11 1H NMR of G1 S20 Figure S12 13C NMR of G1 S21

Electronic Supplementary Material (ESI) for RSC AdvancesThis journal is © The Royal Society of Chemistry 2013

S2

Synthetic Procedures

Materials:

Although compound 1 is commercially available, it has been prepared according to according to

literature procedures as follows.1 The proton NMR is attached as in Figure S7. Compounds 3, 4, 7,

and 8 are commerically available. Compounds 92 and G03 are known compounds and were

prepared according to the procedure listed below.

(1) References for preparation of 1, see. (a) Wu, C.-S.; Lee, S.-L.; Chen, Y. J. Polym. Sci., Part A: Polym. Chem.,

2011, 49, 3099-3108 (b) Lee W.-Y.; Kurosawa, T.; Lin, S.-T.; Higashihara, T.; Ueda, M.; Chen, W.-C. Chem. Mater.

2011, 23, 4487-4497.

(2) Reference for 9. See Azumaya, Is.; Kagechika, H.; Yamaguchi, K.; Shudo, K. Tetrahedron, 1995, 51, 5277-5290.

(3) Reference for G0, see Michiko, T.; Shunichi, O.; Toshio, E. Jpn. Kokai Tokkyo Koho, 1995, JP7316549 (A)

“Organic electroluminescence device material and organic electroluminescence device produced by using the same

material.”

Compound 2

NN

N

NH2

2

To an oven-dried 2-necked round-bottom flask were placed 6 (0.20g, 0.23mmol) and ethanol

(9.12mL) with stirring for 5 min at r.t. Hydrazine hydrate (5mL, 0.11mmol) was then added. The

reaction mixture was refluxed at 80 oC for 3 h, and cooled to r.t. The crude solid product that

precipitated was collected by filtration and washed with ethanol to afford 2 as glassy solid (0.14g,

80%). The product could be recrystallized from CH2Cl2/MeOH to give analytical sample: mp.

180-183 oC, FT-IR (KBr) ʋmax: 3446 cm-1.1H NMR (400 MHz, DMSO-d6) δ 7.49 (m 8H), 7.28 (m,


S3

8H), 7.04-6.85 (m, 20H), 6.84 (d, J = 8.8 Hz, 2H), 6.57 (d, J = 8.8 Hz, 2H), 5.10 (s, 2H), 13C NMR

(100 MHz, CD2Cl2) δ: 148.09, 147.43, 146.96, 144.32, 138.43 , 135.21, 133.92, 129.61, 128.44,

127.47, 127.40, 124.62, 124.50, 123.20, 122.93, 116.32. Anal. Calcd for C54H42N4: C, 86.83, H,

5.67, N, 7.50. Found: C, 86.98; H, 5.82; N, 7.45.

Compound 5

N

BrBr

N OO5

A solvent free procedure was adopted in this synthesis. A mixture of tri(4-bromophenyl)amine (9.83

g, 20.4 mmol), phathalimide (1.0 g, 6.80 mmol), CuI (387.6 mg, 2.04 mmol), K3PO4 (2.16 g, 10.2

mmol), N, N'-dimethylethylene-1,2-diamine (0.3 mL, 2.04 mmol) was heated at 140 oC under argon

for 24 h. After cooling, the mixture was quenched by addition of water. The product was extracted

with CH2Cl2 (2 x 200 mL). The extracts were combined, dried over anhydrous MgSO4, and

concentrated under reduced pressure by rotavapor to give a crude mixture that was further purified

by using liquid column chromatography on silica gel, using CH2Cl2: hexane (3: 2) as eluent to give

the essentially pure product. The product can be recrystallized from CH2Cl2/MeOH to give 5 as

yellowish solid (57%): Mp. 249-251 oC; FT-IR (KBr) ʋmax: 1712 cm-1. 1H NMR (400 MHz,

CDCl3) δ 7.95 (dd, J = 5.6, 3.2 Hz, 2H), 7.77 (dd, J = 5.6, 3.2 Hz, 2H), 7.36 (d, J = 8.8 Hz, 4H),

7.28 (d, J = 8.8 Hz, 2H), 7.12 (d, J = 8.8 Hz, 2H), 6.98 (d, J = 8.8 Hz, 4H); 13C NMR (100 MHz,

CDCl3) δ 167.15, 146.37, 145.90, 134.28, 132.39, 131.57, 127.42, 126.18, 125.92, 123.61, 116.14

(only 10 sets of aromatic carbons were observed). HRMS (FAB) calcd for C26H16Br2N2O2

545.9579 (M+), found: 545.9580. Anal. Calcd for C26H16Br2N2O2 C, 56.96; H, 2.94; N, 5.11.


S4

Found: C, 57.17; H, 3.33; N, 5.21.

Compound 6

NN

N

N OO

6

To a 2-necked round-bottom flask were placed 5 (3.80 g, 6.93 mmol),

4-(diphenylamino)phenylboronic acid (10.6 g, 36.7 mmol), Pd(PPh3)4 (180 mg, 0.156 mmol) and

Na2CO3 (2.30 g, 21.7 mmol) and injected a degassed solution of benzene (40.0 mL), water (21.6

mL) and ethanol (7.44 mL) under the argon atmosphere. The reaction mixture was refluxed at 80 oC

for 24 h. The reaction mixture was cooled to r.t. and quenched by addition of water (50 mL) The

product was extracted with CH2Cl2 (30 × 2 mL). The organic extracts were combined and dried

over anhydrous MgSO4. After removal of the solvent under reduced pressure, the crude product was

purified by liquid column chromatography (DCM: n-hexane, 3:2) on silica gel to give product 6 as

yellow solid (85%): mp. 180-183 oC, FT-IR (KBr) ʋmax: 1713 cm-1. 1H NMR (400 MHz, CD2Cl2) δ:

7.93 (dd, J = 3.2 Hz, 5.6 Hz, 2H), 7.80 (dd, J = 3.2 Hz, 5.6 Hz, 2H), 7.50-7.44 (m, 8H), 7.31-7.22

(m, 16H), 7.12-7.09 (m, 12H), 7.05 - 7.01 (m, 4H), 13C NMR (100 MHz, CD2Cl2) δ: 167.71,

148.03, 147.72, 147.30, 146.48, 135.99, 134.82, 134.77, 132.21, 129.63, 127.93, 127.83, 127.68,

126.11, 125.36, 124.74, 124.33, 123.87, 123.63, 123.31. HRMS (FAB) calcd for C62H44N4O2

876.3464 (M+), found: 876.3474. Anal. Calcd for C62H44N4O2 C, 84.91, H, 5.06, N, 6.39. Found: C,

84.54, H, 5.14, N, 6.12.


S5

Compound 92

N

O

N

O

O N

9

To an oven dried 2-necked round-bottom flask were placed N-methylaniline (282 mg, 0.3 mL, 2.64

mmol), 1,3,5-tricarboxylic chloride benzene (200 mg, 0.735mmol), N,N-dimethylaminopyridine

(110 mg, 0.904 mmol), dried CH2Cl2 (10 mL), and freshly dried and distilled triethylamine (3.0 mL)

under argon. The reaction mixture was refluxed at 80 oC for 4 h and then cooled to r.t. The mixture

was quenched by addition of water. The product was extracted with CH2Cl2. The extracts were

combined and dried over anhydrous MgSO4. After removal of the solvent under vacuum, the crude

product was purified by column chromatography on silica gel (CH2Cl2: hexane = 2: 3) to give 9 as

white powder (83%). 1H-NMR (400 MHz, CDCl3): δ 7.20-7.18 (m, 9H), 7.07 (s, 3H), 6.64 (d, J = 8

Hz, 6H), 3.33 (s, 9H); ESI m/z calcd. for C30H27N3O3 477.5, found 478.5 (M++H).

Dendrimer G03

N

HN O

OO N

HN

N

HN

G0

To an oven dried 2-necked round-bottom flask were placed 1 (535.6 mg, 2.06 mmol), 1, 3,


S6

5-tricarboxylic chloride benzene (130.0 mg, 0.6mmol), N,N-dimethylaminopyridine (DMAP) (12.0

mg, 0.1 mmol), dried CH2Cl2 (8.8 mL), and triethylamine (2.2 mL) under argon. The mixture was

refluxed for 24 h. The mixture was quenched by addition of water. The product was extracted with

CH2Cl2. The organic extracts were dried over MgSO4. After removal of the solvent under vacuum,

the crude product was purified by recrystallization from CH2Cl2/MeOH to give G0 (83%). mp.

228-230 oC; 1H-NMR (400 MHz, CDCl3:DMSO-d6 = 5:2, with CH2Cl2 as an internal standard): δ

10.28 (s, 3H), 8.67 (s, 3H), 7.68 (d, J = 8.8 Hz, 6H), 7.15 (m, 12H), 6.95 (m 18H), 6.88 (m

6H); 13C-NMR (100 MHz, CDCl3:DMSO-d6 = 5:2): δ 163.78, 146.87, 142.77, 134.96, 133.72,

128.51, 124.00, 122.85, 121.79, 120.99 (only 9 sets of aromatic carbon NMR signal were recorded)

Dendrimer G1

O

O

O

N

N

N

NH

N N

N

NH

N

N

N

NH

G1

To an oven dried 2-necked round-bottom flask were placed 2 (154 mg, 0.206 mmol),

1,3,5-tricarboxylic chloride benzene (13 mg, 0.06 mmol), N, N-dimethylaminopyridine (11 mg, 0.09


S7

mmol), dried CH2Cl2 (0.88 mL), amd triethylamine (0.22 mL) under argon and refluxed for 48 h.

After removal of the solvent under vacuum, the crude product was purified by liquid column

chromatography on silica gel (CH2Cl2: hexane = 3: 2, then CH2Cl2: CHCl3 = 5: 1), and

recrystallized from CH2Cl2/MeOH to give G1 (65%): mp. 275-280 oC; 1H NMR (400 MHz,

CDCl3:DMSO-d6 = 5:2): δ 10.26 (s, 3H), 8.67 (s, 3H), 7.70 (d, J = 8.4 Hz, 6H), 7.38-7.34 (m, 24H),

7.15 (t, J = 8.0 Hz, 24H), 7.06-6.91 (m, 66H); 13C NMR (100 MHz, CDCl3:DMSO-d6 = 5:2): The

solubility of G1 is so low that only NMR signals for the major aromatic carbons could be recorded

as follow. δ 147.46, 146.92, 136.58, 134.08, 129.13, 127.54, 127.31, 125.99, 124.30, 123.76, 122.83,

122.83, 121.02; MALDI-TOF m/z calcd for C171H126N12O3 2396.9087, found 2396.7304 (with

matrix DHP); Anal. calcd. for C171H126N12O3: C, 85.69; H, 5.30; N, 7.01; found C, 85.18; H, 4.91;

N, 7.05.


S8

UV-Vis absorption, Fluorescence, and AIE measurements:

The UV-Vis absorption spectra were measured in CH2Cl2 at room temperature. While the

concentration of 1 x 10-5 M for G0, 1, and 2 and the concentration of 4×10-6 M for G1 were used in

the measurements. In the fluorescence measurements, the concentration of 1×10-6 M for G0 and G1

in THF was adopted. The photoluminescence intensity was very low. The low temperature

fluorescence spectra and intensity of G0 (1 x 10-5 M) and G1 (5×10-6 M) were also measured in

THF at 77 K. Fluorescence intensity enhancement was observed. In adition, when the solution

was deposited on TLC plate and dried, strong photoluminescence was observed, indicating that the

aggregation induced emission (AIE) effect may exist. The AIE effect has been intensively studied

by Tang and many other teams. Therefore, the AIE experiments were carried out as follows: A

solution of G0 and G1 in THF was added drop-wise to deionized water with vigorous stirring at

room-temperature. The final concentration was 1 x 10-5 M and 5×10-6 M respectively. The ratio of

THF/H2O was varied from 9:1 to 1:9. Fluorescence intensity of the samples was recorded and

shown in the manuscript.

Electrochromic cell fabricated from the nano-particles of G1. A working cell was constructed

using the solvent resist tape (3M) in the experiment, with the cell surface-area of 1 cm x 1 cm being

defined. A layer of the electrochemically polymerized G1 was deposited (5 CV cycles) on the ITO

surface by using CV method. After electropolymerization, the layer was rinsed with

1,2-dichlorobenzene (ODCB) in order to remove any monomeric or soluble oligomeric residues.

The solvent was then removed by heating the sample plate at 80 oC for about 15 min. The

electropolymerized film functioned as a primer to increase the adhesion of the nano-particles in the

next step. G1 nano-particle suspension (5 x 10-6 M) in aqueous THF:H2O (1:9) was applied to

fill-up the cell. Data and statistics on the particle size distribution were collected based on the SEM

image. The plate was heated to dry on a hot-plate at 80 oC until the solvent was completely dried. A

film from the nano-particles could then be obtained. Noteworthy to remind is that the high Tg of


S9

158 oC for G1 would help to maintain the nano-particle in spherical shapes. This is further

evidenced by the high-resolution SEM analysis. However, the nano-particles are still soluble in

many organic solvents in this stage. In order to have the particles crosslinked electrochemically, we

have to figure out a solvent system that could be used in the coming electrochemical crosslinking

experiment without causing any re-dissolution problems. After a series of try and error, we finally

figured out that propanenitrile is an appropriate solvent to use. So in the last step, electrochemical

crosslinking of the nano-particles on the ITO surface was carried out in a supporting electrolyte of

TBAP in propanenitrile. In the first anodic scan, three characteristic waves of G1 could be clearly

seen. However, the CV wave pattern was changed and reached to a stable new pattern after several

repeated CV cycles. The peak currents in each latter CV cycles remain almost the same, indicating

that leaching of the G1 based materials from the film is insignificant. This was further supported by

the high resolution SEM imaging. The spherical shape of the particles could be maintained after the

electrochemical treatment. After the electrochemical treatments, the film is no longer soluble in

CH2Cl2. Therefore the electrochromic measurements were carried out in Bu4NClO4/CH2Cl2. At the

neutral state, the plate highly fluoresces in green color. The intensity is much stronger than that of

the electrochemically deposited G1 film due to the larger thickness of the film from the

nanoparticles. When the film was electrochemically oxidized to the first doping state, the color of

the plate turned into brown-red at 0.9 V. The photoluminescence was completely quenched in this

state. Further oxidation at 1.2 V would lead the film into the second doping state, with a deep-blue

color being observed. Cycling of the opto-physical properties could be achieved by switching the

applied electrical potentials between 0 – 1.25 V. The device is robust and the fluorescence intensity

remains unchanged after many redox cycles. Following is the SEM of the electrochemically fused

G1-particle film.


S10


S11

Figure S1. 1H NMR of 5 in CDCl3

N

Br

Br

N

O

O

5


S12

Figure S2. 13C NMR of 5 in CDCl3

N

Br

Br

N

O

O

5


S13

Figure S3. 1H NMR of 6 in CD2Cl2

N

N NO

O

6N


S14

Figure S4. 13C NMR of 6 in CD2Cl2

N

N NO

O

6N


S15

Figure S5. 1H NMR of 2 in DMSO-d6

N NH

22

NN


S16

Figure S6. 13C NMR of 2 in CD2Cl2

N NH

22

NN


S17


N NH

21


S18


NO

NO

O

N

9


S19

Figure S9. 1H NMR of G0 in CDCl3:DMSO-d6 (5:2)

O

O

ON

N H

NNH

N

N H

G0


S20

Figure S10. 1H NMR of G0 in CDCl3:DMSO-d6 (5:2), with CH2Cl2 as an internal standard.

O

O

ON

N H

NNH

N

N H

G0

CH2Cl2 internal standard

CDCl3

DMSO-d6


S21

Figure S11. 1H NMR of G1 in CDCl3:DMSO-d6 (5:2), with CH2Cl2 as an internal standard.

O

O

ON

N H

NNH

N

N H

G1

R=

N

R

R

RR

R

R


S22

Figure S12. 13C NMR of G1 in CDCl3:DMSO-d6 (5:2), with CH2Cl2 as an internal standard. The

solubility of G1 is so low that only some major aromatic signals could be collected after overnight

scanning.

O

O

ON

N H

NNH

N

N H

G1

R=

N

R

R

RR

R

R

DMSO-d6

CDCl3


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Benzenetricarboxamide-cored Triphenylamine Dendrimer: Nano ... · S1 Supporting information . Benzenetricarboxamide-cored Triphenylamine Dendrimer: Nano-Particle Film Formation by