Synthesis of a New Class of Triphenylamine-Containing Poly ...
Benzenetricarboxamide-cored Triphenylamine Dendrimer: Nano ... · S1 Supporting information ....
Transcript of Benzenetricarboxamide-cored Triphenylamine Dendrimer: Nano ... · S1 Supporting information ....
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
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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,
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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.
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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.
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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,
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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
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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.
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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
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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.
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Figure S1. 1H NMR of 5 in CDCl3
N
Br
Br
N
O
O
5
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Figure S2. 13C NMR of 5 in CDCl3
N
Br
Br
N
O
O
5
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Figure S3. 1H NMR of 6 in CD2Cl2
N
N NO
O
6N
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Figure S4. 13C NMR of 6 in CD2Cl2
N
N NO
O
6N
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Figure S5. 1H NMR of 2 in DMSO-d6
N NH
22
NN
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Figure S6. 13C NMR of 2 in CD2Cl2
N NH
22
NN
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Figure S7. 1H NMR of 1 in CDCl3
N NH
21
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Figure S8. 1H NMR of 9 in CDCl3
NO
NO
O
N
9
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Figure S9. 1H NMR of G0 in CDCl3:DMSO-d6 (5:2)
O
O
ON
N H
NNH
N
N H
G0
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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
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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
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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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