Star-Shaped Ladder-Type Ter(p-phenylene)s for … Supplementary Information 1 Star-Shaped Ladder-Type Ter(p-phenylene)s for Efficient Multiphoton Absorption Lei Guo,a, King Fai Li,b

Electronic Supplementary Information

1

Star-Shaped Ladder-Type Ter(p-phenylene)s for Efficient

Multiphoton Absorption

Lei Guo,a, King Fai Li,b Man Shing Wong,*a and Kok Wai Cheah*b

a Department of Chemistry and Institute of Advanced Materials, Hong Kong

Baptist University, Hong Kong, China.

b Department of Physics and Institute of Advanced Materials, Hong Kong

Baptist University, Hong Kong, China.

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


2

Synthesis:

Palladium-catalyzed borylation of triazole-substituted phenyl bromide 11

with

bis(pinacolato)diborane using PdCl2(dppf) as a catalyst afforded triazole-substituted

arylboronic ester 2 in good yield (89%). Palladium-catalyzed Suzuki cross-coupling

of boronic ester 2 with diethyl 2,5-dibromoterephthalate using Pd(OAc)2/PPh3 as a

catalyst yielded the triazole-based key intermediate 3 in 50% yield. Similarly, the

other two key intermediates for the construction of star-shaped terphenylene skeleton,

6 and 7 were prepared accordingly by means of Suzuki cross-coupling of carbazole-2

or diphenylamine-substituted3 boronic acid with diethyl 2,5-dibromoterephthalate.

On the other hand, bromination of triphenylamine was conducted in the presence of

three-fold N-bromosuccinimide at 0 oC affording the corresponding

tribromophenylamine 8 in 90% yield. The conversion of tribromide 8 to trispinacol

boronate 9 was efficiently carried out via a two-step protocol including

bromine-lithium exchange and boronation.4 Three-fold palladium-catalyzed Suzuki

cross-coupling of boronic ester 9 with the key bromide intermediate 3 or 6 or 7

afforded various star-shaped ter(p-phenylene)s 10a-c, respectively in moderate to

good yield (55-80%). Subsequently, nucleophilic addition of freshly prepared

4-decylphenyl lithium and followed by triflic acid catalyzed ring closure reaction

afforded the corresponding desired ladder-type ter(p-phenylene)s, N(TL)-Ph(3)-TAZ,

N(TL)-Ph(3)-CBZ, and N(TL)-Ph(3)-NPh in a reasonable yield. All the newly

synthesized star-shaped ladder-type ter(p-phenylene)s were fully characterized with

1H NMR,

13C NMR, HRMS, and elemental analysis and found to be in good

agreement with their structures.



3

Reagents and conditions: (a) PdCl2(dppf), bis(pinacolato)diboron, KOAc, 1,4-dioxane, 80 °C;

(b) diethyl 2,5-dibromoterephthalate, Pd(OAc)2, PPh3, 4 M K2CO3, H2O/EtOH/toluene, 75 °C;

(c) 1) n-BuLi, THF, -78 °C. 2) B(OMe)3, -78 °C, then r.t. overnight; (d) diethyl

2,5-dibromoterephthalate, Pd(OAc)2, PPh3, 4 M K2CO3, H2O/EtOH/toluene, 45 °C; (e) NBS,

DMF, 0 °C; (f) 1) n-BuLi, THF, -78 °C, 2) 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-

dioxaborolane (PINBOP), -78 °C to r.t., overnight; (g) Pd(OAc)2, PPh3, 4 M K2CO3,

H2O/EtOH/toluene, reflux; (h) 1-bromo-4-decylbenzene, n-BuLi, THF, -70 °C, 1.5 h, then r.t.

overnight; (i) CF3SO3H, CH2Cl2, 24 h.

Scheme S1 Synthesis of star-shaped ladder-type ter(p-phenylene)s,

N(TL)-Ph(3)-TAZ, N(TL)-Ph(3)-CBZ, and N(TL)-Ph(3)-NPh.



4

Physical Characterization:

300 350 400 450 500

0.0

3.0x104

6.0x104

9.0x104

1.2x105

1.5x105

Wavelength / nm

Mo

lar

Ab

sorp

tiv

ity

/ M

-1cm

-1

N(TL)-Ph(3)-NPh

N(TL)-Ph(3)-TAZ

N(TL)-Ph(3)-CBZ

N(L)-Ph(3)-NPh

TATL-Ph(3)-NPh

(a)

400 440 480 520 560 6000.0

0.2

0.4

0.6

0.8

1.0

Wavelength / nm

No

rm

ali

zed

In

ten

sit

y /

a.u

.

N(TL)-Ph(3)-NPh

N(TL)-Ph(3)-TAZ

N(TL)-Ph(3)-CBZ

(L)-Ph(3)-NPh

TATL-Ph(3)-NPh

(b)

Fig. S1 UV-Vis absorption and fluorescence spectra of star-shaped oligomers in

CHCl3 with (L)-Ph(3)-NPh as a reference.

300 350 400 450 500 5500.0

0.2

0.4

0.6

0.8

1.0

No

rm

ali

zed

Ab

sorp

tio

n I

nte

sity

Wavelength / nm

N(TL)-Ph(3)-NPh

N(TL)-Ph(3)-TAZ

N(TL)-Ph(3)-CBZ

(L)-Ph(3)-NPh

TATL-Ph(3)-NPh

(a)

400 480 560 6400.0

0.2

0.4

0.6

0.8

1.0(b) N(TL)-Ph(3)-NPh

N(TL)-Ph(3)-TAZ

N(TL)-Ph(3)-Cbz

(L)-Ph(3)-NPh

TATL-Ph(3)-NPh

Wavelength / nm

No

rm

ali

zed

In

ten

sit

y /

a.

u.

Fig. S2 UV-Vis absorption and fluorescence spectra of star-shaped oligomers in DMF

with (L)-Ph(3)-NPh as a reference.

400 450 500 5500.0

0.2

0.4

0.6

0.8

1.0(a)

Wavelength / nm

2P

EF

Norm

ali

zed

In

ten

sit

y /

a.u

.

N(TL)-Ph(3)-NPh

N(TL)-Ph(3)-CBZ

N(TL)-Ph(3)-TAZ

Excitation at 800nm

with 10-5

M in toluene

400 450 500 5500.0

0.2

0.4

0.6

0.8

1.0(b)

Wavelength /nm

Excitation at 1270nm

with 10-5 M in toluene

N(TL)-Ph(3)-NPh

N(TL)-Ph(3)-CBZ

N(TL)-Ph(3)-TAZ

3P

EF

No

rm

ali

zed

In

ten

sit

y /

a.u

.

Fig. S3 (a) 2PA, and (b) 3PA induced photoluminescence spectra of the star-shaped

oligomers excited at 800 nm and 1270 nm, respectively measured in toluene at a

concentration of ~10-5

M.



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Table S1. Summary of photophysical and thermal properties of star-shaped ladder-

type ter(p-phenylene)s.

λmaxa

/nm (ε)

λemab

/nm

λmaxc

/nm (ε)

λembc

/nm

λmaxf

/nm

λemf

/nm

ΦFLa 2PA

λmaxg/nm

σ2g

σ2,Mh 3PA

λmaxi/nm

σ3i

σ3,Mj Tdec

k

/˚C

(L)-Ph(3)-NPh 405

(0.77)

417,

404

(0.64)

421,

444

403 428 0.85d 419 127 0.086 418 0.202 1.39 435

N(TL)-Ph(3)-

NPh

429

(1.74)

443 423

(1.35)

451 427 457 0.86d 445 2579 0.66 444 2.45 6.32 463

N(TL)-Ph(3)-

TAZ

429

(1.34)

450 431

(1.30)

464 425 493 0.84d 453 1620 0.39 450 3.35 5.77 400

N(TL)-Ph(3)-

CBZ

423

(1.33)

443 416

(1.09)

450 419 469 0.96e 443 1887 0.49 442 2.23 7.98 438

aMeasured in toluene, ε × 10

5 M

-1·cm

-1.

bExcited at 400 nm.

cMeasured in chloroform, ε× 10

5 M

-1·cm

-1.

dAverage of two

independent measurements using Norharman (Φ330–390 = 0.58) as a standard. eAverage of two independent measurements

using coumarin 6 (Φ420 = 0.78) as a standard. fMeasured in DMF.

g2PA cross-section (GM) determined by

two-photon-induced fluorescence method using 700 nm femtosecond laser pulses in toluene at a concentration of ~10-5

M. hσ2,M = 2PA cross-section scaled by molecular weight, the unit is GM/g..

i3PA cross-section (× 10

-76 cm

6s

2) determined

by comparing the fluorescence intensity with that of PhNOF(4)-TAZ-OF(4)-NPh using 1270 nm femtosecond laser

pulses in toluene at a concentration of ~10-5

M. jσ3,M = 3PA cross-section scaled by molecular weight, the unit is × 10

-80

cm6s

2/g.

kDetermined by thermal gravimetric analyzer with a heating rate of 20 ˚C/min under N2.

Experimental:

All the solvents were dried by the standard methods wherever needed. 1H NMR

spectra were recorded using either a Bruker advanced Ⅲ 400 NMR spectrometer

with a reference of the residual CHCl3 7.26 ppm. 13

C NMR spectra were recorded

using a Bruker advanced-Ⅲ 400 NMR spectrometer with a reference of the residual

CHCl3 77.16 ppm. Mass spectrometer (MS) measurements were carried out using fast

atom bombardment (FAB) on the API ASTAR PulsarⅠHybrid Mass Spectrometer or

matrix-assisted laser desorption ionization-time-of-flight (MALDI-TOF) technique.

Thermal stabilities were determined by thermal gravimetric analyzer (PE-TGA6) with

a heating rate of 20 oC/min under N2. All the physical measurements were performed



6

in toluene including electronic absorption (UV-Vis) recorded by a Varian Cary 100

Scan Spectrophotometer and fluorescence spectra determined by a PTI Luminescence

Spectrophotometer. The fluorescence quantum yields in toluene were determined by

dilution method using norharman (Φ 330~390 nm = 0.58) and coumarin 6 (Φ 420 nm = 0.78)

as a standard.

Multiphoton Absorption Measurements

The two-photon absorption (2PA) cross-section was measured by the 2PA induced

fluorescence method. The 2PA cross-sections σ2 was obtained by comparing their 2PA

induced up-converted fluorescence to that of Rhodamine 6G (both at the

concentration of 10-5

mol/L).5

Where ФF is the fluorescence quantum yield, c is the concentration, n is the refractive

index, and S is the intensity of upconversed fluorescence. σTPF

is the two-photon

excitation cross-section. The cal subscript refers to the standard reference solution.

Similarly, the three-photon absorption cross-section was determined by comparing the

fluorescence intensity of the molecules with that of PhN-OF(4)-TAZ-OF(4)-NPh at

1300 nm.6

For the femtosecond pulse experiment, the excitation source is an optical parametric

amplifier pumped by a mode-locked Ti:sapphire laser oscillator–amplifier system.

The pulse width of the laser is 120 fs, and its repetition rate is 1 kHz. The

fluorescence is collected by a telescope system which consists of a lens f = 15 cm and

a lens f = 30 cm. A monochromator connected with a GaAs PMT is used as the

recorder for the MPA induced up-converted fluorescence.

In the experiment, all of three star-shaped ladder-type ter(p-phenylene)s were

dissolved in the toluene with a concentration of d0 = 0.01 mol L-1

. A 1-cm long quartz

cell filled with the oligomer solution was pumped by fs laser pulses. The laser with

wavelength ranging from 600 nm to 2 μm is focused at the centre of the cell via a len

F

TPF

2

c a l

c a lc a lT P F

c a l

T P F

c n S

Snc



7

with focal length, f of 10 cm. We use laser power meters Newport Model 818-IR with

response bandwidth of 0.78–1.8 μm to measure the input laser power. And the power

meters Newport Model 818-UV with response bandwidth of 0.19–1.1 μm was used

to measure the lasing output. Two filters (BG38) are placed behind the cell to cut off

the transmitted pump laser.

Synthesis of compound 2. A mixture of compound 1 (1.09 g, 2.53 mmol),

bis(pinacolato)diboron (0.77 g, 3.04 mmol), potassium acetate (1.01 g, 10.3 mmol),

1,4-dioxane (40 mL) and PdCl2(dppf) (41 mg, 0.056 mmol) was allowed to heat at

80 °C for 24 h under nitrogen atmosphere. After solvent removal under vacuum, the

residue was diluted with water and extracted with ethyl acetate. The combined organic

phase was washed with brine, dried over anhydrous sodium sulfate and evpoarted to

dryness to afford a black grey solid. The crude product was purified through a short

silica gel column chromatography to obtain a white solid product of 1.09 g (89% yield)

which was directly used in the next step.

Synthesis of compound 3. A mixture of compound 2 (1.38 g, 2.89 mmol), diethyl

2,5-dibromoterephthalate (2.22 g, 5.84 mmol), palladium(II) acetate (38 mg, 0.17

mmol), triphenylphosphine (90 mg, 0.34 mmol), 4 M potassium carbonate (3 mL) and

ethanol (2 mL) were added with toluene (40 mL) in a 100 mL round-bottom flask.

The solution mixture was refluxed at 75 °C for 24 h under nitrogen atmosphere. After

that, the reaction mixture was quenched with 6 M HCl (6 mL) and extracted with

ethyl acetate. The combined organic layer was washed with brine water, dried over

anhydrous sodium sulfate and evaporated in vacuum. The crude product was purified

by silica gel column chromatography to afford a white solid of 0.95 g (50% yield). 1H

NMR (400 MHz, CDCl3, δ) 8.07 (s, 1H), 7.69 (s, 1H), 7.54-7.46 (m, 5H), 7.38-7.30

(m, 4H), 7.24-7.22 (m, 4H), 4.41 (q, J = 7.2 Hz, 2H), 4.05 (q, J = 7.2 Hz, 2H), 1.40 (t,

J = 7.2 Hz, 3H), 1.28 (s, 9H), 0.98 (t, J = 7.2 Hz, 3H). 13

C NMR(100 MHz, CDCl3, δ)

166.5, 165.6, 154.9, 154.1, 153.5, 141.1, 140.2, 135.5, 135.2, 135.0, 134.5, 133.0(d),

130.1, 128.8, 128.5, 128.1, 126.2, 125.7, 123.3, 120.6, 62.3, 61.8, 34.9, 31.2, 14.3,



8

13.8. MS (MALDI-TOF, m/z) 652.7 [M]+.

Synthesis of 9-(p-bromophenyl)-9H-carbazole 4 according to the literature.7

To a

three-necked flask containing 1,4-dibromobenzene (17.7 g, 75 mmol), carbazole (8.36

g, 50 mmol), 1,10-phenanthroline (0.9 g, 5 mmol), CuCl (0.5 g, 5 mmol) and K2CO3

(20.7 g, 150 mmol) was added 150 ml of o-xylene. The solution mixture was heated at

110 °C for 48 h under N2 protection. After cooling to r.t., the organic phase was

separated and condensed. The crude product was purified by silica gel column

chromatography followed by recrystallization in ethanol to afford a white crystals of

12.1g in 75% yield. 1

H NMR (400 MHz, CDCl3, δ): 8.16-8.14 (m, 2H), 7.76-7.72 (m,

2H), 7.48-7.37 (m, 6H); 7.32-7.29 (m, 2H). 13

C NMR(100 MHz, CDCl3, δ) 140.7,

136.9, 133.2, 128.8, 126.2, 123.6, 121.0, 120.5, 120.3, 109.6.

Synthesis of compound 5. To a solution of 4 (2.18 g, 6.76 mmol) in 60 mL dry THF

was added n-BuLi (4.2 mL, 2.4 M in hexane) dropwise at -78 °C with well nitrogen

protection. After stirring at -65 °C for another 1.5 h, trimethoxyborane (1.6 mL, 13.5

mmol) was then added into the mixture. The reaction mixture was warmed up slowly

to r.t. while maintaining a good stirring overnight. After that, the mixture was

quenched with ice water, diluted with ethyl acetate and separated. The aqueous phase

was extracted with ethyl acetate. The combined organic extract was washed with brine,

dried over anhydrous sodium sulfate and concentrated in vacuo followed by

purification through a short silica gel column to obtain a white solid of 1.65 g (85%

yield), which was used directly in the next step.

Synthesis of compound 6. A mixture of compound 5 (1.65 g, 5.7 mmol), diethyl

2,5-dibromoterephthalate (4.33 g, 11.4 mmol), Pd(AcO)2 (13 mg), PPh3 (30 mg), 4 M

K2CO3 (3 mL), ethanol (10 mL) and toluene (50 mL) was heated at 45 °C for 24 h

under nitrogen atmosphere with good magnetic stirring. After cooling to room

temperature, the reaction mixture was poured into water, acidified with 3 mL of 6 M

HCl and extracted with ethyl acetate. The combined organic layer was dried over

anhydrous Na2SO4, evaporated to dryness. The residue was purified by silica gel

column chromatography to afford a white solid of 1.24g (40% yield).

1H NMR (400 MHz, CDCl3, δ): 8.18-8.16 (m, 3H), 7.87 (s, 1H), 7.65-7.53 (m, 4H),



9

7.48-7.42 (m, 4H), 7.34-7.30 (m, 2H), 4.46 (q, J = 7.2 Hz, 2H), 4.22 (q, J = 7.2 Hz,

2H), 1.45 (t, J = 7.2 Hz, 3H), 1.15 (t, J = 7.2 Hz, 3H). 13

C NMR (100 MHz, CDCl3, δ):

166.6, 165.6, 140.8, 140.6, 138.6, 137.6, 135.6, 135.1, 134.6, 133.2, 129.9, 126.8,

126.1, 123.6, 120.6, 120.5, 120.5, 120.3, 109.8, 62.3, 61.9, 14.3, 14.0. MS

(MALDI-TOF, m/z) 543.7 [M]+.

Synthesis of compound 7. The procedure for the preparation of compound 6 was

followed using 4-(diphenylamino)phenylboronic acid4 (3.47 g, 12 mmol), diethyl

2,5-dibromoterephthalate (4.56 g, 12 mmol), Pd(OAc)2 (68 mg), Ph3P (80 mg) 2M

K2CO3 (24 mL), Ethanol (4 ml) and toluene (70 mL). The residue was purified by

column chromatography giving 5.4 g (53% yield) of a yellow solid. 1

H NMR (400

MHz, CDCl3, δ): 8.05 (s, 1H), 7.80 (s, 1H), 7.30-7.26 (m, 4H), 7.20-7.03 (m, 10H),

4.43 (q, J = 7.2 Hz, 2H), 4.20 (q, J = 7.2 Hz, 2H), 1.44 (t, J = 7.2 Hz, 3H), 1.17 (t, J =

7.2 Hz, 3H); 13

C NMR (100 MHz, CDCl3, δ): 167.0, 165.6, 147.7, 147.5, 140.8, 135.2,

134.6 (d), 133.0, 132.8, 129.4, 129.2, 124.7, 123.3, 122.9, 119.6, 62.1, 61.7, 14.3,

13.8. MS(MALDI-TOF, m/z) 545.1 [M]+.

Synthesis of tris(4-bromophenyl)amine 8. To a solution of triphenylamine (4.01 g,

16.4 mmol) in DMF (80 mL) in an ice-bath was added dropwise a solution of

N-bromosuccinimide (9.06 g, 50.9 mmol) in DMF (30 mL). After complete addition,

the solution mixture was warmed up to room temperature. After stirring overnight, the

reaction was quenched with ice-water, extracted with ethyl acetate, and then separated.

The combined organic layers was washed with brine, dried over anhydrous sodium

sulfate and evaporated in vacuum, followed by recrystallization from ethanol to afford

a white solid of 7.13 g in 90% yield. 1H NMR (400 MHz, CDCl3, δ) 7.35 (dd, J = 6.8

Hz, 2.0 Hz, 2H), 6.92 (dd, J = 6.8 Hz, 2.0 Hz, 2H). MS(MALDI-TOF, m/z) 482.1

[M]+.

Synthesis of compound 9. To a solution of tris(4-bromophenyl)amine 8 (2.01 g, 4.17

mmol) in 80 mL dry THF was added n-BuLi (10 mL, 2.5 M in hexane) dropwise at

-78 °C with well nitrogen protection. After stirring at -65 °C for another 1.5 h,

2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (2.7 mL, 13.8 mmol) was then

added into the mixture. The reaction mixture was warmed up slowly to r.t. and stirred



10

overnight. After that, the mixture was quenched with ice water, diluted with ethyl

acetate and separated. The aqueous phase was extracted with ethyl acetate and the

combined organic extract was washed with brine, dried over anhydrous sodium sulfate

and concentrated in vacuo followed by recrystallization from n-hexane to obtain a

white solid of 1.56 g in 60% yield. 1H NMR (400 MHz, CDCl3, δ) 7.68 (d, J = 8.4 Hz,

2H), 7.07 (d, J = 8.8 Hz, 2H), 1.34 (s, 36H). 13

C NMR (100 MHz, CDCl3, δ) 149.7,

135.9, 123.4, 83.7, 24.8. MS(MALDI-TOF, m/z) 623.2 [M]+.

Synthesis of compound 10a. A mixture of compounds 3 (0.95 g, 1.45 mmol),

compound 9 (0.226 g, 0.36 mmol), palladium(II) acetate (33 mg, 0.14 mmol),

triphenylphosphine (76 mg, 0.29 mmol), 4 M potassium carbonate (1.5 mL) and

ethanol (2 mL) were added with toluene (35 mL) in a 100 mL round-bottom flask.

The reaction mixture was refluxed for 2 days under nitrogen atmosphere. After

cooling to room temperature, the reaction mixture was poured into water, acidified by

3 mL of 6 M HCl and extracted with CH2Cl2. The combined organic layer was dried

over anhydrous Na2SO4, evaporated to dryness. The residue was purified by silica gel

column chromatography to afford a yellow solid of 0.42 g (60% yield). 1H NMR (400

MHz, CDCl3, δ): 7.85 (s, 3H), 7.75 (s, 3H), 7.54-7.46 (m, 15H), 7.38-7.27 (m, 24H),

7.25-7.18 (m, 12H), 4.19 (q, J = 7.2 Hz, 6H), 4.06 (q, J = 7.2 Hz, 6H), 1.28 (s, 27H),

1.15 (t, J = 7.2 Hz, 9H), 0.97 (t, J = 7.2 Hz, 9H). 13

C NMR (100 MHz, CDCl3, δ):

168.3, 168.0, 155.0, 154.3, 153.1, 147.1, 141.6, 140.8, 139.8, 135.5, 134.7, 133.6,

133.5, 132.0, 131.9, 130.2, 129.9, 129.6, 128.6, 128.5, 128.1, 126.3, 125.6, 124.0,

123.8, 61.6, 31.2, 14.0, 13.9. HRMS (MALDI-TOF, m/z) [M]+ Calcd. For

C72H60N1O12, 1959.8644; Found 1959.8683.

Synthesis of compound 10b. A mixture of compound 6 (0.32 g, 0.59 mmol),

compound 9 (92 mg, 0.15 mmol), palladium(II) acetate (7 mg), triphenylphosphine

(76 mg, 0.29 mmol), 4 M K2CO3 (0.5 mL), ethanol (5 mL) and toluene (15 mL) was

refluxed for 24 h under nitrogen atmosphere with good magnetic stirring. After

cooling to room temperature, the reaction mixture was poured into water, acidified by

3 mL of 6 M HCl and extracted with CH2Cl2. The combined organic layer was dried

over anhydrous Na2SO4, evaporated to dryness. The residue was purified by silica gel



11

column chromatography to afford a yellow solid of 0.207 g (85% yield). 1

H NMR

(400 MHz, CDCl3, δ): 8.18 (d, J = 7.8 Hz, 6H), 7.99 (s, 3H), 7.96 (s, 3H), 7.69-7.63

(m, 12H), 7.52-7.44 (m, 12H), 7.42-7.38 (m, 6H), 7.35-7.39 (m, 12H), 4.32-4.23 (m,

12H), 1.25 (t, J = 7.1 Hz, 9H), 1.17 (t, J = 7.1 Hz, 9H). 13

C NMR(100 MHz, CDCl3,

δ): 168.3, 168.0, 147.2, 140.1, 139.4, 137.3, 134.8, 133.8, 133.6, 132.2, 132.1, 130.1,

129.7, 126.8, 126.1, 124.1, 123.6, 120.5, 120.2, 109.8, 61.6, 14.1, 14.0. MS

(MALDI-TOF, m/z) 1629.9 [M]+.

Synthesis of compound 10c. A mixture of compound 7 (0.88 g, 1.62 mmol),

compound 9 (0.25 g, 0.41 mmol), palladium(II) acetate (36 mg, 0.16 mmol),

triphenylphosphine (76 mg, 0.29 mmol), 4 M K2CO3 (1.5 mL), ethanol (2 mL) and

toluene (35 mL) was refluxed for 2 days under nitrogen atmosphere. After cooling to

room temperature, the reaction mixture was poured into water, acidified by 3 mL of 6

M HCl and extracted with CH2Cl2. The combined organic layer was dried over

anhydrous Na2SO4, evaporated to dryness and the residue was purified by silica gel

column chromatography to afford 0.37 g (55% yield) of a yellow solid. 1H NMR (400

MHz, CDCl3, δ): 7.82 (s, 3H) 7.81 (s, 3H), 7.31-7.27 (m, 15H), 7.25-7.19 (m, 15H),

7.15-7.10 (m, 18H), 7.06-7.02 (m, 6H), 4.23-4.16 (m, 12H), 1.15 (q, J = 7.2 Hz, 18H).

13C NMR (100 MHz, CDCl3, δ): 168.6, 168.5, 147.7, 147.6, 147.1, 140.4, 140.1,

134.9, 133.9, 133.6, 133.5, 131.9, 129.6, 129.4, 124.7, 124.0, 123.2, 61.5, 14.0(d).

MS(MALDI-TOF, m/z) 1635.9 [M]+.

Synthesis of N(TL)-Ph(3)-NPh. To a flame-dried 100 mL two necked round-bottom

flask under nitrogen protection was added 1-bromo-4-decylbenzene (2.03 g, 6.84

mmol) and anhydrous THF (15 mL). The solution was cooled to –70 °C and 2.5 M

n-BuLi (2.2 mL, 5.5 mmol) was added dropwise over 15 min. The reaction mixture

was stirred at –70 °C for another 1.5 h before compound 10c (361 mg, 0.22 mmol) in

5 mL THF was added. The reaction was allowed to warm up to r.t. and stirred

overnight before being quenched with 1 M HCl (20 mL) at 0 °C. The reaction mixture

was diluted with ethyl acetate and extracted with ethyl acetate twice. The combined

organic layer was washed with brine, dried over anhydrous sodium sulfate, filtered

and concentrated in vacuo, affording 2.4 g of yellow oil which was used directly in



12

the next step. To a solution of compound obtained above in 40 mL CH2Cl2 was added

CF3SO3H (0.15 M, 10 mL) in CH2Cl2/THF (100/1). The solution mixture was stirred

for 24 h at r.t. before being quenched with water. The reaction mixture was extracted

with CH2Cl2 twice. The combined organic layer was washed with water, dried over

anhydrous sodium sulfate, filtered and concentrated in vacuo. The crude product was

purified by silica gel column chromatography giving a yellow solid 568 mg in 65%

yield. 1H NMR (400 MHz, CDCl3, δ): 7.61 (s, 4H), 7.50 (br, 4H), 7.34 (br, 4H),

7.24-7.18 (m, 17H), 7.14-7.12 (m, 14H), 7.09 -7.00 (m, 40H), 6.99-6.95 (m, 19H),

2.59-2.51 (m, 24H), 1.58-1.54 (m, 24H), 1.29-1.27 (m, 192H), 0.92-0.87 (m, 36H).

13C NMR (100 MHz, CDCl3, δ): 153.4, 153.1, 151.4, 150.9, 147.8, 147.1, 143.4,

143.3, 141.2, 141.1, 139.1, 135.2, 129.2, 128.3, 128.2, 124.0, 122.7, 122.2, 121.6,

120.6, 117.4, 117.3, 64.7, 35.7, 32.1(d), 31.6, 31.5, 29.8(d), 29.7(d), 29.5(d), 22.8,

14.3. HRMS (MALDI-TOF, m/z) [M]+ Calcd. For C288H354N4, 3871.7918 Found

3871.8123. Anal. Calcd for C288H354N4 C 89.34, H 9,22, N 1.45; Found C 89.11, H

9.35, N 1.36.

Synthesis of N(TL)-Ph(3)-CBZ. A similar synthetic procedure for the preparation of

N(TL)-Ph(3)-NPh was followed by using compound 10b (144 mg, 0.088 mmol),

1-bromo-4-decylbenzene (657 mg, 2.21 mmol), and n-BuLi (0.74 mL, 2.5 M in

hexane), THF (20 ml) in the first step, and CF3SO3H (0.15 M, 6 mL) and CH2Cl2 (10

ml) in the second step. A yellow solid was obtained in a total yield of 35%. 1

H NMR

(400 MHz, CDCl3, δ): 8.13 (d, J = 7.7 Hz, 6H), 7.87-7.70 (m, 7H), 7.62-7.51 (m, 8H),

7.39-7.33 (m, 14H), 7.29-7.22 (m, 24H), 7.12-7.07 (m, 25H), 7.01-6.99 (m, 12H),

2.56 (q, J = 6.8 Hz, 24H), 1.61-1.55 (m, 24H), 1.31-1.25 (m, 168H), 0.87 (t, J = 6.6

Hz, 36H). 13

C NMR (100 MHz, CDCl3, δ): 143.2, 143.1, 141.6, 141.3, 140.8, 128.5,

128.3, 128.3, 126.0, 123.5, 120.4, 120.0, 110.0, 65.0, 64.8, 35.7, 32.1, 32.0, 31.6, 31.5,

29.8(t), 29.7, 29.6, 29.5(d), 22.8, 14.3. HRMS (MALDI-TOF, m/z) [M+H]+ Calcd.

For C288H349N4, 3866.7527 Found 3866.7359. Anal. Calcd for C288H348N4: C 89.48, H

9.07, N 1.45; Found: C 89.72, H 9.14, N 1.42.

Synthesis of compound N(TL)-Ph(3)-TAZ. A similar synthetic procedure for the

preparation of N(TL)-Ph(3)-NPh was followed by using compound 10a (360 mg,



13

0.184 mmol), 1-bromo-4-decylbenzene (1.77 g, 5.96 mmol), 2.5 M n-BuLi (1.8 mL,

4.5 mmol), THF (20 ml) in the first step, and CF3SO3H (0.15 M, 5 mL) and CH2Cl2

(20 mL) in the second step. A yellow solid was obtained in a total yield of 38%.

1H

NMR (400 MHz, CDCl3, δ): 7.63-7.56 (m, 11H), 7.35-7.27 (m, 22), 7.24-7.20 (m, 4H),

7.16-7.10 (m, 11H), 7.03-6.89 (m, 48H), 6.80-6.78 (m, 3H), 2.58-2.49 (m, 24H),

1.60-1.54 (m, 24H), 1.33-1.25 (m, 195H), 0.90-0.87 (m, 36H). 13

C NMR (100 MHz,

CDCl3, δ): 154.8, 154.5, 153.3, 152.0, 151.8, 151.4, 146.9, 143.0, 142.7, 142.2, 141.3,

141.2, 140.7, 138.0, 135.1, 134.8, 130.1, 129.8, 128.6, 128.3, 128.2(d), 128.1, 127.9,

126.5, 125.6, 123.3, 121.6, 120.7, 120.2, 118.4, 117.2, 64.6(d), 35.7(d), 34.9, 32.1(d),

31.6, 31.5, 31.2, 29.8, 29.7, 29.5(d), 22.8, 14.3. HRMS (MALDI-TOF, m/z) [M+]

Calcd. For C306H378N10, 4195.9980, Found 4196.0002. Anal. Calcd for C306H378N10: C

87.58, H 9.08, N 3.34; Found: C 87.70, H 9.25, N 3.16.

References:

1 P. L. Wu, X. J. Feng, H. L. Tam, M. S. Wong and K. W. Cheah, J. Am. Chem. Soc.

2009, 131, 886.

2 Y.-H. Sun, X.-H. Zhu, Z. Chen, Y. Zhang and Y. Cao, J. Org. Chem. 2006, 71,

6281.

3 Z. H. Li and M. S. Wong, Org. Lett. 2006, 8, 1499.

4 J. Cremer and P. Baüerle, J. Mater. Chem. 2006, 16, 874.

5 E. Zojer, D. Beljonne, P. Pacher and J. L. Brédas, Chem. Eur. J. 2004, 10, 2668.

6 X. J. Feng, P. L. Wu, K. F. Li, M. S. Wong and K. W. Cheah, Chem. Eur. J. 2011,

17, 2518

7 Q. Zhang, J. S. Chen, Y. X. Cheng, L. X. Wang, D. G. Ma, X. B. Jing and

F. S. Wang, J. Mater. Chem. 2004, 14, 895.


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