Electronic Supplementary Material (ESI) for Chemical ... · performed on Art. 5554 (Merck KGaA), and Silica Gel 60N (Kanto Chemical Co.), ... then was added to 2•Cl in CH 2 Cl 2

Supporting Information

Synthesis and Properties of Boron Complexes of [14]triphyrins(2.1.1)

Daiki Kuzuhara,*a

ZhaoLi Xue,a Shigeki Mori,

b Tetsuo Okujima,

c Hidemitsu Uno,

c

Naoki Aratania and Hiroko Yamada

*a,d

aGraduate School of Materials Science, Nara Institute of Science and Technology,

8916-5 Takayama-cho, Ikoma 630-0192, Japan,

bDepartment of Molecular Science, Integrated Center for Sciences, Ehime University,

Matsuyama 790-8577, Japan,

cGraduate School of Science and Engineering, Ehime University, Matsuyama, 790-8577,

Japan,

dCREST, JST, Chiyoda-ku 102-0075, Japan,

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

Instrumentation and Materials

1H NMR,

11B NMR and

13C NMR spectra were recorded on a JEOL JNM-ECX400

spectrometer at ambient temperature using tetramethylsilane as an internal standard.

High-resolution ESI-TOF-MS was measured on a JEOL JMS-700 spectrometer. UV-vis

spectra were measured on a JASCO UV/VIS/NIR Spectro-photometer V-570.

Fluorescence spectra were measured on a JASCO FP-6600. Fluorescence quantum

yields were measured on an Absolute PL Quantum Yield Measurement System

C9920-02.

Materials Thin-layer chromatography (TLC) and gravity column chromatography were

performed on Art. 5554 (Merck KGaA), and Silica Gel 60N (Kanto Chemical Co.),

respectively. All solvents and chemicals were reagent grade quality, obtained

commercially and used without further purification. For spectral measurements, spectral

grade were purchased from Nacalai tesque Inc.

Xray Analysis. X−ray crystallographic data were recorded on a Rigaku R-AXIS

RAPID/S. The diffraction data were processed with Crystal Structure of the Rigaku

program, solved with the SIR-97 programS1

and refined with the SHELX-97 program.S2

Theoretical calculations All density functional theory calculations were achieved with

the Gaussian09 program package. The geometry was fully optimized at the Becke’s

three-parameter hybrid functional combined with the Lee-Yang-Parr correlation

functional abbreviated as the B3LYP level of density functional theory with 6-31G**

basis set. Equilibrium geometries were verified by the frequency calculations, where no

imaginary frequency was found. Based on the B3LYP/6-31G** optimized geometry,

time dependent density functional theory (TDDFT) was conducted at the

B3LYP/6-31G** level of theory.


Synthesis

Synthesis of 2•BF4

To a mixture of 1S3

(20 mg, 0.045 mmol) in toluene (2 ml) was added BPhCl2 (0.4 ml)

under an Ar atmosphere. After stirring for 5 h, the reaction was quenched with MeOH

and the solvent was removed under a reduced pressure. The residue was purified by

silica gel column chromatography (10% MeOH in CHCl3) to give 2•Cl. AgBF4 (100

mg) then was added to 2•Cl in CH2Cl2 (5 ml). The appeared precipitate was filtrated,

and the filtrate was purified by recrystallization from MeOH/H2O to give 2•BF4 as

yellow solids. Yield: 91% (25 mg, 0.041 mmol). 1H NMR (400 MHz, CDCl3): δ 9.94 (s,

2H, meso), 9.87 (s, 2H, meso), 6.26 (m, 1H, pPh), 5.99 (m, 2H,

mPh), 3.82-3.64 (m, 8H),

6.53 (s, 6H, -Me), 3.22 (m, 2H, mPh), 2.01 (m, 4H), 1.71 (t, 6H, J = 7.3 Hz), 1.59 (m,

4H), 1.02 (t, 6H, J = 7.3 Hz) (ppm); 11

B NMR (128 MHz, CDCl3): δ -14.2 (ppm); 13

C

NMR (125 MHz, CDCl3): δ 150.5, 146.8, 145.2, 144.6, 144.1, 141.6, 126.8, 126.6,

120.1, 107.9, 34.5, 25.7, 22.9, 19.2, 17.7, 14.1, 11.5 (ppm); HRMS (ESI-TOF): calcd

for C36H43BN3 [M-BF4]+

527.3586, found 527.3589.

Synthesis of 4•BF4


To a mixture of 3S4

(25 mg, 0.036 mmol) in toluene (10 ml) was added BPhCl2 (0.3 ml)

under an Ar atmosphere. After stirring for 5 h, the reaction was quenched with MeOH

and the solvent was removed under a reduced pressure. The residue was purified by

silica gel column chromatography (10% MeOH in CHCl3) to give 4•Cl. AgBF4 (100

mg) then was added to 2•Cl in CH2Cl2 (5 ml). The appeared precipitate was filtrated,

and the filtrate was purified by recrystallization from CHCl3/hexane to give 4•BF4 as

purple solids. Yield: 85% (26 mg, 0.030 mmol) 1H NMR (400 MHz, CDCl3): δ 8.14 (m,

2H, -Ph), 8.05-7.96 (m, 10H, -Ph), 7.77 (m, 2H, benzo), 7.68 (m, 2H, -Ph), 7.61 (m, 4H,

-Ph), 7.55 (m, 2H, benzo), 7.52 (m, 2H, benzo), 7.44 (m, 2H, benzo), 7.12 (m, 2H,

benzo), 6.88 (m, 2H, -Ph), 6.52 (m, 1H, pPh), 6.40 (m, 2H, benzo), 6.28 (m, 2H,

mPh)

4.01 (m, 2H, oPh) (ppm);

11B NMR (128 MHz, CDCl3): δ -11.7 (ppm);

13C NMR (128

MHz, CDCl3): δ 144.4, 143.5, 143.2, 140.0, 139.0, 135.9, 135.4, 134.5, 133.9, 131.5,

131.5, 130.9, 130.8, 130.7, 130.6, 130.5, 129.7, 129.0, 127.7, 127.5, 127.3, 126.9, 125.9,

125.6, 122.2 (ppm); HRMS (ESI-TOF): calcd for C58H37BN3 [M-BF4]+

785.3117, found

785.3117.


Supporting Figure

Figure S1 Kohn-Sham orbitals and calculated energy levels of 1a, 2a+, 3 and 4

+ at the

B3LYP/6-31G** level using Gaussian 09 program.

-1.94

-2.16

-5.00-5.34

-8.61 -8.62 -8.64

-5.25

-5.40

-8.04

LUMO

HOMO-3

HOMO-1

HOMO

HOMO-2

LUMO+1

LUMO

HOMO-1

HOMO

LUMO+1

N

N

NH

Ph Ph

PhPh

N

N

NB

Ph

PhPh

Ph Ph

+

-1.71

-2.07

-5.24 -5.36-5.77

-5.99

-8.74 -8.81

-9.24 -9.35

LUMO+1

LUMO

HOMO

HOMO-1

HOMO-2

HOMO-3

N

N

NH N

N

NB

Ph

+

LUMO

HOMO-1

HOMO

LUMO+1

1a 2a+

3 3+


Figure S2. Absorption spectra in CH2Cl2 and calculated TD-DFT oscillator strengths of

2•BF4.

Figure S3. Absorption spectrum in CH2Cl2 and calculated TD-DFT oscillator strengths

of 4•BF4.


Figure S4. Cyclic voltammogram of 2•BF4 (top) and 4•BF4 (bottom) in acetonitrile

containing the 0.1 M (nBu)4NPF6 as supporting electrolyte. Working electrode: glassy

carbon; counter electrode: platinum wire; reference electrode: Ag/AgNO3.


Figure S5 H-H COSY spectrum of 2•BF4 in CDCl3.

Figure S6. 13

C NMR spectrum of 2•BF4 in CDCl3.

X : parts per Million : Proton

10.0 9.0 8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 0

Y :

par

ts p

er M

illi

on :

Pro

ton

11

.01

0.0

9.0

8.0

7.0

6.0

5.0

4.0

3.0

2.0

1.0

0-1

.0

abundance

0 2.0 4.0 6.0 8.0 10.012.0

pro

ject X

abun

dan

ce

010

.0

project Y (

thou

sand

ths)

-1.0

01.0

2.0

3.0

4.0

5.0

6.0

7.0

8.0

9.0

10

.011

.012

.013

.01

4.0

15.0

X : parts per Million : Carbon13

160.0 150.0 140.0 130.0 120.0 110.0 100.0 90.0 80.0 70.0 60.0 50.0 40.0 30.0 20.0 10.0 0

15

0.4

67

14

6.8

24

14

5.1

94

14

4.5

74

14

4.1

07

14

1.5

90

12

6.7

83

12

6.5

82

12

0.1

18

10

7.9

23

3

4.5

45

2

5.7

16

2

2.9

42

1

9.2

23

1

7.7

17

1

4.1

32

11

.47

1


Figure S7 H-H COSY spectrum of 4•BF4 in CDCl3.

Figure S8. 13

C NMR spectrum of 4•BF4 in CDCl3.

X : parts per Million : Proton

8.0 7.0 6.0 5.0 4.0

Y :

par

ts p

er M

illi

on :

Pro

ton

8.0

7.0

6.0

5.0

4.0

abundance

0 1.0 2.0

abun

dan

ce

01.0

2.0

3.0

(th

ou

sand

ths)

010

.02

0.0

30.0

40.0

X : parts per Million : Carbon13

150.0 140.0 130.0 120.0 110.0 100.0 90.0 80.0 70.0 60.0 50.0 40.0 30.0 20.0 10.0 0

14

0.0

45

13

9.0

44

13

5.3

92

13

4.5

44

13

3.9

15

13

2.3

60

13

1.5

31

13

1.4

93

13

1.3

31

13

0.9

11

13

0.7

78

13

0.6

54

13

0.5

68

13

0.4

92

12

9.0

61

12

8.9

57

12

7.7

17

12

7.5

17

12

7.3

36

12

6.8

59

12

5.8

58

12

5.6

00

12

2.2

44

7

7.4

60

7

7.3

46

7

7.1

46

7

6.8

31

0

.11

6


Figure S8. Crystal structure of 2•BF4. Thermal ellipsoids represent 30% probability.


Figure S9. Crystal structure of 4•BF4. Thermal ellipsoids represent 30% probability.


References

S1) A package for crystal structure solution and refinement, Istituto di Cristallografia,

Italy; A. Altomare, M. C. Burla, M. Camalli, G. Cascarano, C. Giacovazzo, A.

Guagliardi, A. G. G. Moliterni, G. Polidori, R. Spagna, J. Appl. Crystallogr. 1999, 32,

115.

2) SHELXL-97, program for refinement of crystal structures from diffraction data,

University of Göttingen, Göttingen, Germany; "A short history of SHELX". G. M.

Sheldrick, Acta Cryst., 2008, A64, 112.

3) D. Kuzuhara, H. Yamada, Z.-L. Xue, T. Okujima, S. Mori, Z. Shen, H. Uno, Chem.

Commun. 2011, 47, 722.

4) a) Z.-L. Xue, Z. Shen, J. Mack, D. Kuzuhara, H. Yamada, T. Okujima, N. Ono, X.-Z.

You, N. Kobayashi, J. Am. Chem. Soc. 2008, 130, 16478; b) Z.-L. Xue, J. Mack, H. Lu,

L. Zhang, X.-Z. You, D. Kuzuhara, M. Stillman, H. Yamada, S. Yamauchi, N.

Kobayashi, Z. Shen, Chem. Eur. J. 2011, 17, 4396.


Documents

Electronic Supplementary Material (ESI) for Chemical ... · performed on Art. 5554 (Merck KGaA), and Silica Gel 60N (Kanto Chemical Co.), ... then was added to 2•Cl in CH 2 Cl 2