Supporting Information

for

Angew. Chem. Int. Ed. 200460174

© Wiley-VCH 2004

69451 Weinheim, Germany

1

Arylamine-substituted Hexa-peri-hexabenzocoronenes: Facile

Synthesis and Their Potential Applications as “Coaxial” Hole

Transport Materials Jishan Wu,a Martin Baumgarten,a Michael G. Debije,b John M. Warman,b Klaus

Müllen*, a

a Max-Planck Institut für Polymerforschung, Ackermannweg 10, D-55128, Mainz,

Germany

b IRI, Delft University of Technology, Mekelweg 15, 2629 JB Delft, the Netherlands

I. General

Unless otherwise noted, all starting materials were purchased from Aldrich, Acros,

ABCR, and used as received. THF and toluene for water-free reactions were refluxed

over potassium under argon and freshly distilled before use. Compound 10 [1], 15 [2] and

16 [3] were prepared according to the literatures.

1H NMR and 13C NMR spectra were recorded in deuterated solvents such as CD2Cl2,

C2D2Cl4 on a Bruker DPX 250 and Bruker DRX 500. Field desoption (FD) mass spectra

were obtained on a VG Instruments ZAB 2-SE-FPD. High resolution MALDI mass

spectra were recorded on a Bruker Reflex II-TOF Spectrometer using a 337 nm nitrogen

laser with TCNQ as matrix [4]. Elemental analysis was carried on a Foss Heraeus-Vario

EL. Differential scanning calorimetry (DSC) was measured on a Mettler DSC 30 with

heating and cooling rate of 10 K/min. A Zeiss Axiophot with a nitrogen flushed Linkam

THM 600 hot stage was used to characterize optical textures. 2-D X-ray diffraction of

oriented fibers was conducted using a rotating anode (Rigaku, 18kw) X-ray beam (CuKα,

pinhole collimation, double graphite monochromator) with the beam perpendicular to the

fiber axis and the 2D patterns were recorded by a CCD camera. Cyclic and differential

2

voltammetry of compounds 1-5 were recorded using a standard three-electrode cell: a Pt

disc as working electrode, a Pt wire as counter electrode and a nonaqueous AgNO3/Ag

electrode as reference. Normally, 1 mg/mL solution of 1-5 in 1,2-dichlorobenzene were

used and 0.1 M tetrabutyl ammonium hexafluorophosphorate (TBAPF6) was used as

supporting electrolyte. The electrochemical potentials in each measurements were

calibrated by an internal standard of ferrocenium/ferrocene(Fc+/Fc). The titration of

compounds 1-5 (about 1.0x10-5 M in dry dichloromethane) by oxidants such as SbCl5 and

THClO4 (about 1.0x10-3 M) [5] were conducted under argon in a quartz cuvette equipped

with a septum and recorded by a Perkin-Elmer Lambda 9 UV-vis-NIR

spectrophotometer. Electron spin resonance spectroscopy (ESR) were recorded on CW

X-band ESP 300E equipped with an NMR gauss meter (Brucker ER035), a frequency

counter (Brucker ER 041 XK) and a variable temperature control continues flow N2

cryostat (Brucker B-VT 2000).

The pulse-radiolysis time-resolved microwave conductivity technique (PR-TRMC), as

applied to the study of the conductive properties of discotic materials, has been described

fully elsewhere.[6] Briefly, roughly 30 mg powder samples are compressed into Perspex

sample holders which are insterted into a Ka-band (ca 30 GHz) microwave cell. A

uniform, micromolar concentration of charge carriers is produced in the sample by a 5

nanosecond pulse of 3 MeV electrons from a Van de Graaff accelerator. Any change in

the conductivity of the sample resulting from the formation of mobile charge carriers is

monitored (without the need of electrode contacts) as a decrease in the microwave power

reflected by the sample cell. The one-dimensional, intracolumnar charge carrier mobility

is determined from the end-of-pulse conductivity per unit dose, ∆σeop/D (Sm2/J), using

the relationship

Σµ1D = 3 ⋅∆σeop

D⋅

Ep

Wp (1)

3

In (1), Ep is the average energy deposited in eV per ionization event and Wp is the

probability that initially formed ion-pairs survive to the end of the pulse. The value of Ep

was taken to be 25 eV, and the values of Wp, which were all within the range 0.39 ± 0.11

for the present compounds, were calculated as described previously.[6] The factor of 3 in

(1) takes into account the fact that the organized columnar domains within the bulk

samples investigated are randomly orientated and that charge transport is expected to be

highly anisotropic and to occur almost exclusively along the axis of the macrocyclic

stacks. The mobility sum, Σµ = µ(+) + µ(-), is used in (1) since the PR-TRMC technique

does not allow the determination of the separate contributions of the positive and

negative charge carriers.

All the AFM measurements were made using tapping mode operation on a Nanoscope

IIIa Multimode scanning probe microscope from Digital Instruments (Santa Barbara, CA)

using an “E” and “J” vertical engage scanner. Tapping mode etched silicon probes (force

constant f0 = 320~350 KHz) with about 5~10 nm radiuses were used for imaging. The

solutions of compound 1-5 (3 mg/mL in chloroform) were spin-coated onto different

substrates such as silicon wafer, HOPG and quartz with a spin rate of 1000 rpm. The UV-

vis absorption spectra of the thin film were recorded on Perkin-Elmer Lambda 9

spectrophotometer at room temperature.

4

II. Synthesis and characterization

Compounds 1, 2 were synthesized by Buchwald-Hartwig coupling reactions between the

mono- (17) and para-dibromo HBC (18) [7], respectively, as shown in SI-scheme 1.

Br

RR

R

R R

NH

OCH3H3CO

Br

RR

Br

R R

NH

OCH3H3CO

1Pd2(dba)3-P(tert-Bu)3-NaOBut

toluene, 80°C

18

17

2Pd2(dba)3-P(tert-Bu)3-NaOBut

toluene, 80°C

R= n-C12H25

SI-scheme 1. Synthesis of compounds 1,2 by Pd-catalyzed Buchwald-Harwig coupling.

The synthesis of the D3h symmetry HBC building blocks such as 7 is a big challenge.

Several attempts to make appropriate C3 symmetry hexaphenylbenzene precursors

carrying functionalizable bromine or iodine sites have been done. For example, the

Co2(CO)8 catalyzed cyclotrimerization was carried out on unsymmetric tolane derivatives

19 and two structural isomers 20 (a+b), one desired 1,3,5-isomer (a) and another

undesired 1,2,4-isomer (b), were obtained (SI-scheme 2). However, several attempts to

separate these two isomers by column chromatography failed due to the small difference

in polarity. Regioregular cyclotrimerization of acetyl substituted arylenes with TiCl4 or

5

Br

R

Co2(CO)8

Br

BrBr

R

R R

R

BrBr

R

R Br

+

1,3,5-isomer 1,2,4-isomerR=n-C12H25 or

3

1920

a b SI-scheme 2. Attempted synthesis of C3-symmetric hexaphenylbenene derivatives by Co-

catalyzed cyclotrimerization.

SiCl4 is a powerful method to make 1,3,5-substituted benzene (C3 symmetry), and it is

noteworthy that such Lewis acid promoted condensation-trimerization was used in the

practical synthesis of C60 fullerene.[8] Herein, a similar precursor 23 was designed and

synthesized, which was made by nucleophilic substitution reaction[9] between carboxylic

chloride 21 and benzyl lithium-cuprates bromide 22 (SI-scheme 3). However, several

attempts to cyclotrimerize 23 with SiCl4 and TiCl4 under different conditions failed to

give the desired hexaphenylbenzene precursor 24. This failure is most probably due to the

steric hindrance arising from the additional phenyl ring. These drawbacks drive us to

change the idea: instead of making the hexaphenylbenzene precursors, we designed and

synthesized a tris-biphenylylbenzene 14 precursor and finally the D3h symmetry HBC

building block 7 carrying three active iodo groups was obtained as described in the main

text.

6

I

II

LiCuBr

ICl

OO

I

+(i) SiCl4

(ii) TiCl4

or

21

2223

24 SI-scheme 3. Attempted synthesis of the C3 -symmetric hexaphenylbenzene precursor 24

by SiCl4 mediated condensation-cyclotrimerization.

All the new compounds were well characterized by standard NMR and mass

spectroscopy, and elemental analysis and some data for compounds 1-5 was presented

below (SI-figure 1).

880 885 890 895 900 905 910 915 9200

1000

2000

3000

4000

5000

6000

7000

Inte

nsity

m/z

899.

45

I

I I

C42H15I3Mol. Wt.: 900.28

SI-figure 1(a). Isotope resolved MALDI mass spectrum of compound 7 (TCNQ as

matrix). The isotopic distribution is in good agreement with the simulated results,

indicating an exact loss of 12 hydrogens during the cyclodehydrogenation. Further

structural proof is the 1H NMR spectrum of soluble compound 3 (see below) which is

prepared from building block 7.

7

1-Di(4’-methoxyphenyl)amino-4,7,10,13,16-pentadodecyl-hexa-peri-hexabenzocoronene

(1) - a general procedure of Buchwald-Hartwig coupling reactions

200 mg mono bromo HBC 16, 38 mg di(4-methoxyphenyl) amine, 2.5 mg Pd2(dba)3,

0.91 mg tri-tert-butyl phosphorous (20mg/ml in toluene, 45.3 µL), 20 mg NaOBut, and

2.0 ml dry toluene were put together into a Schlenk tube in glove box. The mixture was

stirred at 80 °C overnight. After cooling down, the solvent was removed under vacuum

and the residue was purified by column chromatography (silica gel, PE/DCM=4:1 to

DCM) to afford 143 mg yellow powder (65%). FD MS (8 kV): m/z= 1592.10 (100%),

calcd.1591.50. 1H NMR (500 MHz, 413 K, C2D2Cl4): δ ppm 8.95 (br, Ar-H in HBC core,

8 H), 8.77 (s, Ar-H, HBC core, 2 H), 8.59 (s, Ar-H in HBC core, 2 H), 7.38 (d, J= 8.2 Hz,

Ar-H in –PhO-, 4H), 7.00 (d, J= 8.2 Hz, Ar-H in –PhO-, 4H), 3.88 (s, OCH3, 6H), 3.26

(t, J= 7.6 Hz, Ar-CH2-, 6H), 3.16 (t, J=7.5 Hz, 4H), 2.09~1.98 (m, Ar-CH2-CH2-C10H21,

10H), 1.65~0.86 (m, 105 H). 13C NMR (125 MHz, 302 K, C2D2Cl4): δ ppm 158.61,

155.51, 146.49, 145.17, 141.45, 140.27, 129.65, 129.28, 125.93~114.83 (m), 55.57,

36.91, 31.84, 29.78, 29.72, 29.64, 29.31, 22.62, 14.13. Elemental analysis: calcd.. C

87.55%, H 9.56 %, N 0.88 %, O 2.01%; found: C 87.42 %, H 9.70%.

1,10-Bis[di(4’-methoxyphenyl)amino]-4,7,13,16-tetradodecyl-hexa-peri-

hexabenzocoronene (2)

Following the procedure for compound 1, compound 2 was obtained in 76 % yield from

compound 17 after column chromatography (silica gel, PE/DCM= 7:3 to 2:1 and then

hot THF). FD MS (8 KV): m/z= 1651.17 (100%), calcd.1650.44 for C118H140N2O4. 1H

NMR (250 MHz, d8-THF/CS2=2:1): δ ppm 8.94 (s, 4H), 8.77 (s, 4H), 8.57 (s, 4H), 7.30

(d, J=8.8 Hz, 8H), 6.93 (d, J= 8.8Hz, 8H), 3.84 (s, -OCH3, 12H), 3.14 (t, J=7.6 Hz, Ar-

CH2-, 8H), 1.94 (m, Ar-CH2-CH2-C10H21, 8H), 1.56~0.85 (m, 84H). Elemental analysis:

calcd.: C 85.87%, H 8.55 %, N 1.70 %, O 3.88%; found: C 84.53%, H 8.80%.

8

8.

94

57

8.

77

24

8.

59

30

7.

38

97

7.

37

32

7.

00

77

6.

99

13

3.

87

93

3.

27

33

3.

25

81

3.

24

34

3.

17

94

3.

16

35

3.

15

01

2.

09

93

2.

08

53

2.

07

07

1.

99

99

1.

98

58

1.

97

18

1.

65

14

1.

63

80

1.

59

47

1.

58

07

1.

56

48

1.

54

83

1.

53

37

1.

52

09

0.

86

49

( p p m)0 . 01 . 02 . 03 . 04 . 05 . 06 . 07 . 08 . 09 . 01 0 . 0

N

C12H25C12H25

C12H25

C12H25 C12H25

OCH3

OCH3

Hb

HaHc

Hd

He

Hf

Hg

Hh

-OCH3 -CH2-CH2-C10H21-CH2-C11H23

N

C12H25C12H25

N

C12H25 C12H25

H3CO

H3CO

OCH3

OCH3

Ha

Hb

Hc

Hd

He-OCH3

abcde-h

abcde

**

*

*

1

2

SI-figure 1 (b). 1H NMR spectra of 1 (in D4-C2D2Cl4, 413 K) and 2 (d8-THF/CS2=2:1,

room temperature).

9

N

N

N

N

N

N

C8H17

C8H17

C8H17 C8H17

C8H17

C8H17

C8H17

C8H17

C8H17C8H17

C8H17

C8H17

Ha

Hb

Hc

HdHe

*4

12.0

00

12.6

68

25.2

0838

.033

27.4

83

99.9

00

133.

70

Inte

gral

8.88

90

7.62

957.

6149

7.25

737.

2408

7.02

187.

0065

1.71

98

1.39

031.

3695

0.79

11

(ppm)1.02.03.04.05.06.07.08.09.0

N

N

N

C8H17C8H17

C8H17

C8H17 C8H17

C8H17

Ha

Hb

Hc

HeHd

abc d e

*

**

3

ab cde

4

*

SI-figure 1 (c). 1H NMR spectrum of 3 in d8-THF/CS2=2:1 at room temperature, and 4 in

in D4-C2D2Cl4 at 373K.

10

2-Bromo-3’-(trimethylsilyl)biphenyl (11)

1.41 g 1-bromo-2-iodobenzene (9, 5 mmol), 1.07 g 3-(trimethylsilyl)-1-benzoboronic

acid (10, 5.5 mmol) and 144 mg Pd(PPh3)4 were dissolved in 35 ml toluene and then 25

ml 1M aqueous K2CO3 was added. The mixture was degassed by two “freeze-pump-

thaw” cycles and heated to reflux (95 °C in oil bath) for 20 h. After cooling down, the

mixture was poured into water and extracted by 100 ml toluene. The organic layer was

washed by water two times and dried over MgSO4. The solvent was removed under

vacuum and the residue was purified by column chromatography (silica gel, hexane) to

afford 1.42 g colorless liquid (93%). 1H NMR (250 MHz, CD2Cl2): δ ppm 7.72~7.20 (m,

Ar-H, 8H), 0.34 (s, TMS, 9H). 13C NMR (62.5 MHz, CD2Cl2): δ ppm 143.19, 140.73,

134.78, 133.51, 132.96, 131.81, 130.14, 129.14, 127.90, 127.71, 122.93, -1.02. Elemental

analysis: calcd. C 59.01%, H 5.61%, Br 26.17%, Si 10.39%; found: C 57.49%, H 5.75%.

3-(Trimethylsilyl)biphenyl-2’-boronic acid (12)

A solution of 1.2 g compound 11 (3.93 mmol) in 10 ml dry THF was cooled down to -78

°C in a dry-ice-acetone bath, and then 2.94 ml n-BuLi (1.6 M in hexane) was added

dropwise over 15 min. The mixture was stirred at -78 °C for 1.5 h and 494 mg

trimethoxylborane was added dropwise over 15 min. The mixture was allowed to

naturally warm to room temperature over night and then quenched by adding 10 ml

degassed hydrogen chloride solution (1M in water). The mixture was extracted by 40 ml

dichloromethane and the organic layer was washed with water two times, dried over

MgSO4. The filtrate after filtration was concentrated to 4 ml and 40 ml cold ethanol was

added to give white precipitate. The solid was collected, dried under vacuum( 1.0 g) and

submitted to next step without further purification. 1H NMR (250 MHz, CD2Cl2): δ ppm

7.76~7.11 (m, Ar-H), 0.31 (s, TMS).

1,3,5-tris[3’’-(trimethylsilyl)-2’-biphenyl]benzene (13)

180 mg 1,3,5-tribromobenzene, 850 mg compound 12, 61 mg Pd(PPh3)4, 1.45 g K2CO3,

15 ml toluene and 10 ml water were mixed together. The mixture was degassed by two

“freeze-pump-thaw” cycles and then heated to reflux overnight. After standard work-up

and purification by column chromatography (silica gel, PE/DCM=10:1), 250 mg white

solid was obtained (58%). FD MS (8 KV): m/z = 750.9, calcd.: 751.26 (M+) for

11

C51H54Si3. 1H NMR (250 MHz, CD2Cl2): δ ppm 7.55~6.72 (m, Ar-H, 24H), 0.27 (s,

TMS, 27H). 13C NMR (62.5 MHz, CD2Cl2): δ ppm 141.41, 141.26, 140.81, 140.74,

135.45, 131.80, 131.08, 130.68, 130.56, 130.32, 127.67, 127.59, -0.99. Elemental

analysis: calcd.: C 81.54%, H 7.25%, Si 11.22%; found: C 81.75%, H 7.11%.

1,3,5-Tri(3’’-iodo-2’-biphenyl)benzene (14)

200 mg compound 13 was dissolved in 60 ml chloroform. The solution was degassed by

bubbling argon for 20 min and then 1.6 ml iodine monochloride (1.0 M In

dichloromethane) was added. After stirring for 1 h, the reaction was quenched by adding

saturated aqueous sodium disulfite. The orgainic layer was washed by water three times

(40 mLx3) and dried over MgSO4. The solution was concentrated to 5 ml and then 50 ml

cold ethanol was added to precipitate the product. The solid was collected and dried

under vacuum to give 220 mg pure product (91%). FD MS (8KV): m/z= 912.5, calcd.

912.38 (M+) for C42H27I3. 1H NMR (250 MHz, CD2Cl2): δ ppm 7.65~6.78 (m, Ar-H,

27H). 13C NMR (62.5 MHz, CD2Cl2): δ ppm 144.30, 140.72, 140.29, 139.11, 138.97,

135.89, 130.88, 130.54, 130.34, 130.02, 128.34, 127.95, 94.17. Elemental analysis: calcd.

C 55.29%, H 2.98%, I 26.17%; found: C 54.78%, H 3.04%.

1, 7, 13-Triiodo-hexa-peri-hexabenzocoronene (7)

500 mg compound 14 was dissolved in 160 ml fresh dichloromethane. The solution was

degassed by bubbling argon for 20 min and then 3.2 g FeCl3 in 10 ml nitromethane was

added dropwise. Keeping the bubbling of argon through the reaction for 40 min and then

the reaction was quenched by 50 ml methanol. The yellow precipitate was collected,

washed by methanol and dried under vacuum to afford 370 mg yellow powder (75%).

MALDI-TOF MS (TCNQ as matrix): m/z= 899.45, calcd. 900.28 for C42H15I3. Elemental

analysis: calcd.: C 56.03%, H 1.68%, I 42.29%; found: C 57.96%, H 1.61%.

1, 7, 13-Tris[di(4-octylphenyl amino)] hexa-peri-hexabenzocoronene (3)

Following the procedure for compound 1, compound 3 was obtained in 24 % yield from

triiodo HBC 7 after column chromatography (silica gel, PE/DCM/CS2= 8:1:1 to 7:1:1).

FD MS (8 kV): m/z= 1699.1 (100%), calcd.1697.55 for C126H141N3. 1H NMR (250 MHz,

d8-THF/CS2=2:1): δ ppm 8.82 (s, 6H), 8.68 (d, J= 8.1 Hz, 6H), 7.86 (t, J= 7.8 Hz, 3H),

12

7.44 (d, J= 8,8 Hz, 12H), 7.32 (d, J= 8.8 Hz, 12H), 1.84 (br, Ar-CH2-, 12H), 1.47~1.29

(m, 48H), 0.92~0.85 (m, 52H).

Hexakis (4-iodo)-peri-hexabenzocoronene (8)

2 g of compound 15 (0.2862 mmol) was dissolved in 800 ml dichloromethane and the

solution was constantly sparged with argon. Then 8.03 g anhydrous iron (III) chloride in

20 ml nitromethane was added via a syringe. After 24 h the reaction was quenched by

methanol. The yellow precipitate was collected and washed by dichloromethane

methanol until the filtrate was colorless, dried under reduced pressure to give 1.62 g

insoluble product (82%). MALDI-TOF MS (TCNQ as matrix): m/z=1277.61 (100%).

Elemental analysis: calcd.: C 44.29% H 1.30% I 54.41%; Found: C 39.54%, H 0.90%.

Hexa-triarylamine substituted HBC 4

To a frame-dried 25 ml Schlenk flask was added 127.8 mg of compound 18 (0.10 mmol),

17.5 mg Pd(PPh3)4 (2.5 mol % per I), 5.7 mg of copper iodide (5.0 mol % per I), and 10

ml piperidine. The mixture was degassed by bubbling argon for 15 min, then 592 mg 16

was added. The solution was heated to 52 °C overnight, cooled to RT, and 20 ml

methanol was added. The yellow precipitate was collected, followed by column

chromatography (Al2O3, PE/DCM=4:1 to 7:3) to give 212 mg pure compound 4 (61%).

MALDI-MS (TCNQ as matrix): m/z=3473.08, calcd. 3473.21. 1H NMR (500 MHz,

C2D2Cl4, 373 K): δ ppm 8.89 (s, 12H), 7.62 (d, J=7.3 Hz, 12H), 7.25 (d, J= 8.2Hz, 24H),

7.01 (br, 36H), 1.71 (br, 24H), 1.39~0.79 (m, 180H). 13C NMR (125 MHz, C2D2Cl4,

302K): δ ppm 148.34, 145.06, 144.06, 133.36, 132.91, 132.46, 128.80, 128.77, 127.41,

126.98, 123.81, 123.30, 122.26, 121.87, 121.40, 120.95, 119.86, 118.92, 118.73, 118.60,

115.79, 114.45, 113.93, 113.29, 113.20, 113.00, 91.58, 89.35, 57.03, 38.05, 38.05,

32.24~30.32 (m), Elemental analysis: calcd.: C 89.22%, H 8.36 %, N 2.42 %; found: C

88.05%, H 8.44%.

13

III. Thermal behavior. Selected POM images of compounds 1, 2, and 3 were shown in SI-figure 2. Typical fan-

texture for 1 in a hexagonal liquid crystalline phase at 320 °C was observed.

(a) (b)

(c) SI-figure 2. POM textures of compounds 1 at 320 °C (a), 2 at 316 °C (b) and 3 at room

temperature(c) after slow cooling from the melts.

14

Some 2D WAXD patterns for compounds 1-5 at different temperature were shown in SI-

figure 3.

(a) (b)

SI-figure 3. 2D WAXD diagrams for compound 2 in the liquid crystalline phase at 217

°C (a), and compound 4 at room temperature (b).

15

IV. Cyclic and differential pulse voltammetry

0.0 0.2 0.4 0.6 0.8 1.0-0.6

-0.4

-0.2

0.0

0.2

0.4

0.6

0.8

1.0

1.2

Cur

rent

µA

Potential V (vs AgNO3/Ag)0,0 0,2 0,4 0,6 0,8 1,0 1,2 1,4

0,10

0,15

0,20

0,25

0,30

0,35

0,40

0,45

0,50

1.08

00.

973

0.50

4

0.34

2

Cur

rent

µA

Potential V (vs AgNO3/Ag)

0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0-2

-1

0

1

2

3

Cur

rent

µA

Potential V (vs AgNO3/Ag)0,0 0,2 0,4 0,6 0,8 1,0 1,2 1,4

0,2

0,3

0,4

0,5

0,6

0,7

0,8

1.41

6

1.23

0

0.71

6

0.51

2

Cur

rent

µA

Potential V (vs AgNO3/Ag)

0,0 0,2 0,4 0,6 0,8 1,0 1,2 1,4-2

-1

0

1

2

3

4

5

0.76

6

0.90

8

0.58

9

Cur

rent

µA

Potential vs Ag+/Ag

0,0 0,2 0,4 0,6 0,8 1,0 1,2 1,4 1,6 1,80,05

0,10

0,15

0,20

0,25

0,30

0,35

0,40

0,45

0,50

1.24

41.

10

Cur

rent

Potential

0,0 0,2 0,4 0,6 0,8 1,0 1,2 1,4

-1

0

1

2

3

4

0.59

3

0.84

1

1.07

0.91

9

0.72

1

Cur

rent

µA

Potential vs Ag+/Ag

0,0 0,2 0,4 0,6 0,8 1,0 1,2 1,4 1,6 1,80,0

0,1

0,2

0,3

0,4

0,5

0,6

Cur

rent

Potential

0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6

-2

-1

0

1

2

3

4

Cur

rent

µA

Potential vs AgNO3/Ag0.0 0.5 1.0 1.5 2.0

0.0

0.1

0.2

0.3

0.4

0.5

0.6

Cur

rent

µA

Potential vs AgNO3/Ag

0.46

8

0.93

5

(c) 2-CV (d) 2-DPV

(e) 3-CV (f) 3-DPV

CVDPV DPV CV

(g) 4 (h) 5

(a) 1-CV (a) 1-DPV

16

SI-figure 4. Cyclic voltammograms (CV) and differential pulse voltammograms (DPV) of

compounds 1-5 in 1,2-dichlorobenzene and 0.1 M tetrabutylammonium

hexafluorophosphorate. Scan rate: 100 mV/s.

17

V. Morphology of the thin films.

a b

c d

e

SI-figure 5. Representative tapping mode AFM images of spin-coated thin films of

compounds 1 (a, height image), 2 (b, phase image), 3 (c, phase image), 4 (d, phase

image), and 5 (e, phase image) on quartz plates.

18

VI. UV-vis absorption spectra of the thin films.

200 250 300 350 400 450 500 550 6000,0

0,2

0,4

0,6

0,8

1,0

Nor

mal

ized

Inte

nsity

Wavelength nm

1 2 3 4 5

SI-figure 6. Normalized UV-vis absorption spectra of the thin films of compounds 1-5 on

quartz plates.

Compounds Absorption peaks / nm

1 211, 364, 422

2 221, 375, 430

3 215, 243, 298, 316, 404, 428, 493

4 206, 316, 417

5 205, 296, 404

SI-Table 1.The collected UV-vis absorption data for compounds 1-5 in thin films.

19

VII. References:

[1] C. L. Nesloney, J.W. Kelly, J. Org. Chem. 1996, 61, 3127-3137.

[2] J. A. Hyatt, Org. Prep. Proced. Int. 1991, 23, 460-463.

[3] J. Wu, M. D. Watson, K. Müllen, Angew. Chem. 2003, 115, 5487-5491; Angew.

Chem. Int. Ed. 2003, 42, 5329-5333.

[4] L. Przybilla, J. D. Brand, K. Yoshimura, J. Räder, K. Müllen, Anal. Chem. 2000, 72,

4591.

[5] Y. Murata, H. J. Shine, J. Org. Chem. 1969, 34, 3368-3372.

[6] a) P. G. Schouten, J. M. Warman, M. P. de Haas, C. F. van Nostrum, G. H. Gelinck,

R. J. M. Nolte, M. J. Copyn, J. W. Zwikker, M. K. Engel, M. Hanack, Y. H. Chang, W.

T. Ford J. Am. Chem. Soc. 1994, 116, 6880-6894; b) J. M. Warman, A. M. van de Craats

Mol. Cryst. Liq. Cryst. 2003, 396, 41-72.

[7] S. Ito, M. Wehmeier, J. D. Brand, C. Kübel, R. Epsch, J. P. Rabe, K. Müllen, Chem.

Eur. J. 2000, 6, 4327-4342.

[8] L. T. Scott, M. M. Boorum, B. McMahon, S. Hagen, J. Mack, J. Blank, H. Wegner, A.

de Meihere, Science 2002, 295, 1500-1503.

[9] S. C. Berk, M. C. P. Yeh, N. Jeong, P. Knochel, Organometallics 1990, 9, 3053-3064.