Electric Supporting Information

Unexpectedly Large Binding Constants of Azulenes withFullerenes**

A. F. M. Mustafizur Rahman, Sumanta Bhattacharya, Xiaobin Peng, TakahideKimura, and Naoki Komatsu*

Equipments Fluorescence spectra were recorded on a Hitachi F-4500 spectrometer. Particle sizeanalysis was performed on a Nanotrac UPA-UT151 (Microtrac Inc.).

Theoretical Calculation

Elucidation of enthalpies of association (ΔH0) for both fullerene complexes of

azulene and porphyrin were performed by ab initio Hartree-Fock method using Slater

type orbital basis set. Before the calculation, the geometry of the complexes as well as

individual host and guest was optimized by ab initio Hartree-Fock method using 3-

21G* basis set. The BSSE corrections were incorporated before start of each

calculation.

Determination of Binding Constants of Azulenes with Fullerenes The binding constants were determined by fluorescence spectra shown below (Figs.S1 – S7).

Supplementary Material (ESI) for Chemical CommunicationsThis journal is (c) The Royal Society of Chemistry 2008

0

1000

2000

3000

4000

5000

625 675 725 775 825

Emission Wavelength, nm

Fluo

rese

nce

Inte

nsity

y = 78947x + 1R2 = 0.9943

1

1.2

1.4

1.6

1.8

0 0.000002 0.000004 0.000006 0.000008 0.00001[C70]

F0 /

F

Fig. S1 Fluorescence Spectra (λex = 341 nm) of azulene (8.46 x 10-5 mol/dm3) in the

presence of C70 (0 – 8.15 x 10-6 mol/dm3) in toluene at 298K (a) and Stern-Volmer plot (λem =

753nm, correlation coefficient: 0.994) (b).

a

b

Supplementary Material (ESI) for Chemical CommunicationsThis journal is (c) The Royal Society of Chemistry 2008

0

500

1000

1500

2000

2500

3000

3500

625 675 725 775 825Emission wavelength, nm

Fluo

rese

nce

inte

nsity

y = 67413x + 1R2 = 0.9968

1

1.2

1.4

1.6

1.8

0 0.000002 0.000004 0.000006 0.000008 0.00001[C60]

F0 /

F

Fig. S2 Fluorescence Spectra (λex = 344 nm) of 1,3-dichloroazulene (2.55 x 10-5

mol/dm3) in the presence of C60 (0 – 9.26 x 10-6 mol/dm3) in toluene at 298K (a) and

Stern-Volmer plot (λem = 753nm, correlation coefficient: 0.997) (b).

a

b

Supplementary Material (ESI) for Chemical CommunicationsThis journal is (c) The Royal Society of Chemistry 2008

0

500

1000

1500

2000

2500

3000

3500

625 675 725 775 825Emission wavelength, nm

Fluo

rese

nce

inte

nsity

y = 73075x + 1R2 = 0.9948

1

1.2

1.4

1.6

1.8

2

0.000000 0.000002 0.000004 0.000006 0.000008 0.000010 0.000012[C70]

F0 /

F

Fig. S3 Fluorescence Spectra (λex = 344 nm) of 1,3-dichloroazulene (2.55x 10-5

mol/dm3) in the presence of C60 (0 – 1.164 x 10-5 mol/dm3) in toluene at 298K (a)

and Stern-Volmer plot ((λem = 753 nm, correlation coefficient: 0.995) (b).

a

b

Supplementary Material (ESI) for Chemical CommunicationsThis journal is (c) The Royal Society of Chemistry 2008

0

100

200

300

400

500

600

700

350 370 390 410 430 450Emission Wavelength, nm

Fluo

rese

nce

Int.

y = 174807x + 1R2 = 0.9965

0

1

2

3

4

5

6

0 0.000005 0.00001 0.000015 0.00002 0.000025 0.00003[C60]

F0 /

F

Fig. S4 Fluorescence Spectra (λex = 350 nm) of 4,6,8-trimethylazulene (1.96 x 10-

5 mol/dm3) in the presence of C60 (0 – 2.52 x 10-5 mol/dm3) in toluene at 298K (a)

and Stern-Volmer plot ((λem = 392 nm, correlation coefficient: 0.997) (b).

a

b

Supplementary Material (ESI) for Chemical CommunicationsThis journal is (c) The Royal Society of Chemistry 2008

0

100

200

300

400

350 370 390 410 430 450Emission Wavelength, nm

Fluo

rese

nce

Int.

y = 154928x + 1R2 = 0.9948

0.5

1.5

2.5

3.5

4.5

0 5E-06 0.00001 1.5E-05 0.00002 2.5E-05[C70]

F0 /

F

Fig. S5 Fluorescence Spectra (λex = 350 nm) of 4,6,8-trimethylazulene (1.96 x 10-

5 mol/dm3) in the presence of C70 (0 – 2.00 x 10-5 mol/dm3) in toluene at 298K (a)

and Stern-Volmer plot ((λem = 392 nm, correlation coefficient: 0.995) (b).

a

b

Supplementary Material (ESI) for Chemical CommunicationsThis journal is (c) The Royal Society of Chemistry 2008

0

500

1000

1500

2000

2500

3000

625 650 675 700 725 750 775 800 825 850 875Emission Wavelength, nm

Fluo

rese

nce

Inte

nsity

y = 56788x + 1R2 = 0.9987

0.9

1

1.1

1.2

1.3

1.4

0 0.000002 0.000004 0.000006 0.000008[C60]

F0 /

F

Fig. S6 Fluorescence Spectra (λex = 351 nm) of guaiazulene (1.48 x 10-5

mol/dm3) in the presence of C60 (0 – 6.16 x 10-6 mol/dm3) in toluene at 298K

(a) and Stern-Volmer plot ((λem = 785 nm, correlation coefficient: 0.999) (b).

a

b

Supplementary Material (ESI) for Chemical CommunicationsThis journal is (c) The Royal Society of Chemistry 2008

0

500

1000

1500

2000

2500

3000

625 675 725 775 825 875Emission Wavelength, nm

Fluo

rese

nce

Inte

nsity

y = 88323x + 1R2 = 0.9989

0.8

1

1.2

1.4

1.6

1.8

2

0 0.000002 0.000004 0.000006 0.000008 0.00001[C70]

F0 /

F

Fig. S7 Fluorescence Spectra (λex = 351 nm) of guaiazulene (1.48 x 10-5

mol/dm3) in the presence of C70 (0 – 8.47 x 10-6 mol/dm3) in toluene at 298K

(a) and Stern-Volmer plot ((λem = 785 nm, correlation coefficient: 0.999) (b).

a

b

Supplementary Material (ESI) for Chemical CommunicationsThis journal is (c) The Royal Society of Chemistry 2008