Optically Inactive Star Azo Polymers: Photocontrollability, Chiral … · 2015. 8. 20. · 4...

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Supporting Information for

Preferential Chiral Solvation Induced Supramolecular Chirality in

Optically Inactive Star Azo Polymers: Photocontrollability, Chiral

Amplification and Topological Effect

Lu Yin, Yin Zhao, Shunqin Jiang, Laibing Wang, Zhengbiao Zhang, Jian Zhu, Wei

Zhang* and Xiulin Zhu

Scheme S1. The synthetic routes of multi-functional initiators.

Electronic Supplementary Material (ESI) for Polymer Chemistry.This journal is © The Royal Society of Chemistry 2015

2

10 8 6 4 2 0

3.04

12.00 4.33 36.17

24.158.00

17.78

(c) I-6Br

(b) I-4Br

Chemical shift (ppm)

(a) I-3Br6.00

Fig. S1 1H NMR spectra of multi-functional initiators.

6 7 8 9 10RT (mins)

(PAzoMA6)3-1 (PAzoMA6)3-2 (PAzoMA6)3-3 (PAzoMA6)4 (PAzoMA6)6 (PAzoMA11)3

Fig. S2 GPC curves of PAzoMAs.

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Fig. S3 1H NMR spectra of star Azo polymers (PAzoMA6)3 (a, b and c), (PAzoMA6)4

(d), (PAzoMA6)6 (e) and (PAzoMA11)3 (f).

The Mn(NMR) were calculated as follows. The integral ratio of Ic and I(a,d,f) is 4/7

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theoretically. Ic is the integrations at 8.1-7.6 ppm in 1H NMR spectra relative to the

benzene ring (4H) of AzoMA repeating units in star PAzoMA. I(a,d,f) is the

integrations in 1H NMR spectra relative to -OCH3, -OCH2-, -OCH2- (7H) of AzoMA

units in star PAzoMA. I(a,d,f,i) is the integrations at 4.4-3.3 ppm in 1H NMR spectra

including I(a,d,f) and the multi-functional initiators (-CH2-). Equation (S1) as follows：

Mn,NMR = (NI)/(I(4.4-3.3) − 7) × MAzoMA + MI equation (S1)

For I−3Br, I−4Br and I−6Br, the NI is 6, 8 and 16 respectively. MAzoMA is the molecular

weight of AzoMA monomer. MI is the molecular weight of multi−functional initiator.

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Fig. S4 UV−vis spectra of PAzoMA aggregates with different DCE/1R (a) and

DCE/1S (b) volume fractions. The concentration of polymer repeating unit is 8.42 ×

10-5 mol/L. 1-6 stands for (PAzoMA6)3-1, (PAzoMA6)3-2, (PAzoMA6)3-3, (PAzoMA6)4,

(PAzoMA6)6 and (PAzoMA11)3, respectively.

300 350 400 450 500 550 600-60

-45

-30

-15

0

15

30

Ellip

ticity

(mde

g)

Wavelength (nm)

100_1R 60_1R 20_1R 1R-1S 20_1S 60_1S 100_1S

(PAzoMA6)3-1 ee (%)

0

2

4

6

8

Abs

orba

nce

(a)

300 350 400 450 500 550 600-80

-60

-40

-20

0

20

40

(PAzoMA6)3-2 ee (%)

Abso

rban

ce

Ellip

ticity

(mde

g)

Wavelength (nm)

(b)

100_1R 60_1R 20_1R 1R-1S 20_1S 60_1S 100_1S

0

2

4

6

8

300 350 400 450 500 550 600-75

-50

-25

0

25

50

(PAzoMA6)3-3 ee (%)

Abs

orba

nce

Ellip

ticity

(mde

g)

Wavelength (nm)

(c)

100_1R 60_1R 20_1R 1R-1S 20_1S 60_1S 100_1S

0

2

4

6

8

6

300 350 400 450 500 550 600-90

-60

-30

0

30

60

(PAzoMA6)4 ee (%)

Abs

orba

nce

Ellip

ticity

(mde

g)

Wavelength (nm)

(d)

100_1R 60_1R 20_1R 1R-1S 20_1S 60_1S 100_1S

0

2

4

6

8

300 350 400 450 500 550 600-120

-90

-60

-30

0

30

60

(PAzoMA6)6 ee (%)

Ellip

ticity

(mde

g)

Wavelength (nm)

(e)

100_1R 60_1R 20_1R 1R-1S 20_1S 60_1S 100_1S

Abs

orba

nce

0

2

4

6

8

300 350 400 450 500 550 600-45

-30

-15

0

15

30

(PAzoMA11)3 ee (%)

Ellip

ticity

(mde

g)

Wavelength (nm)

(f)

100_1R 60_1R 20_1R 1R-1S 20_1S 60_1S 100_1S

Abs

orba

nce

0

2

4

6

8

Fig. S5 Changes in CD and UV−vis spectra of PAzoMA aggregates with different

enantiopurity of limonene. DCE/(1R + 1S) are 0.25/2.75, 0.4/0.6, 0.5/2.5, 0.3/2.7,

0.5/2.5 and 0.5/2.5 (v/v) for (PAzoMA6)3-1, (PAzoMA6)3-2, (PAzoMA6)3-3,

(PAzoMA6)4, (PAzoMA6)6 and (PAzoMA11)3 respectively. The concentration of

polymer repeating unit is 8.42 × 10-5 mol/L. (a)-(f) stands for (PAzoMA6)3-1,

(PAzoMA6)3-2, (PAzoMA6)3-3, (PAzoMA6)4, (PAzoMA6)6 and (PAzoMA11)3,

respectively.

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Fig. S6 Photoisomerization switching of the UV−vis spectra ((a,b) DCE/1R and (d,e)

DCE/1S) of PAzoMA aggregates by irradiation with 365 nm and 436 nm light. UV-

vis spectra ((c) DCE/1R and (f) DCE/1S) of PAzoMA aggregates by alternating

irradiation with 365 nm and 436 nm light. The irradiation times for 365 nm light and

436 nm light are both 3 min. The absorbance change for trans− and cis−form is taken

from 360 nm (black) and 453 nm (red), respectively. The concentration of polymer

repeating unit is 8.42 × 10-5 mol/L. 1-6 stands for (PAzoMA6)3-1, (PAzoMA6)3-2,

(PAzoMA6)3-3, (PAzoMA6)4, (PAzoMA6)6 and (PAzoMA11)3, respectively.

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Fig. S7 The changes of UV−vis spectra with heating time in the process of thermal

isomerization at 60 oC ((a) DCE/1R and (b) DCE/1S). The concentration of polymer

repeating unit is 8.42 × 10-5 mol/L. 1-5 stands for (PAzoMA6)3-2, (PAzoMA6)3-3,

(PAzoMA6)4, (PAzoMA6)6 and (PAzoMA11)3, respectively.

300 350 400 450 500 550 600-80

-40

0

40

(PAzoMA6)3-1

Ellip

ticity

(mde

g)

Wavelength (nm)

Trans_1R Cis_1R Trans_1S Cis_1S

(a)

0

2

4

6

8

Abs

orba

nce

300 350 400 450 500 550 600-80

-60

-40

-20

0

20

40

Ellip

ticity

(mde

g)

Wavelength (nm)

0

2

4

6

8

(PAzoMA6)3-2

(b)

Abs

orba

nce


300 350 400 450 500 550 600-80

-60

-40

-20

0

20

40(c)

Ellip

ticity

mde

g)

Wavelength (nm)

0

2

4

6

8

(PAzoMA6)3-3

Abso

rban

ce


10

300 350 400 450 500 550 600-80

-40

0

40

(PAzoMA6)4

(d)El

liptic

ity (m

deg)

Wavelength (nm)


0

2

4

6

8

Abso

rban

ce

300 350 400 450 500 550 600-80

-60

-40

-20

0

20

40

(PAzoMA6)6

Ellip

ticity

(mde

g)

Wavelength (nm)


0

2

4

6

8(e)

Abso

rban

ce

300 350 400 450 500 550 600-60

-45

-30

-15

0

15

30

(PAzoMA11)3

(f)

Ellip

ticity

(mde

g)

Wavelength (nm)


0

2

4

6

8

Abs

orba

nce

Fig. S8 Changes in CD and UV−vis spectra of trans− (original) and cis−form

(irradiated by 365 nm light for 3 min) of PAzoMA aggregates in mixed solvents. The

concentration of polymer repeating unit is 8.42 × 10-5 mol/L. (a)-(f) stands for

(PAzoMA6)3-1, (PAzoMA6)3-2, (PAzoMA6)3-3, (PAzoMA6)4, (PAzoMA6)6 and

(PAzoMA11)3, respectively.

300 350 400 450 500 550 600-200

-150

-100

-50

0

50

100

150

200

trans_1R_Origin

cis_1 trans_1 cis_2 trans_2 cis_3 trans_3 cis_4 trans_4 cis_5 trans_5 cis_6 trans_6

trans_1S_Origin

Ellip

ticity

(mde

g)

Wavelength (nm)


(1a)

0 2 4 6-150-120-90-60-30

0306090

120

Ellip

ticity

(mde

g)

Cycle numbers

(PAzoMA6)3-2_1S

(PAzoMA6)3-2_1R

(1b)

-5-4-3-2-101234

g CD

at th

e fir

st c

otto

n ba

nd/1

0-3

300 350 400 450 500 550 600-150

-100

-50

0

50

100 cis_1 trans_1 cis_2 trans_2


Ellip

ticity

(mde

g)

Wavelength (nm)

(2a)

trans_1R_Origin

trans_1S_Origin

0 2 4 6-120

-80

-40

0

40

80(2b)

Ellip

ticity

(mde

g)

Cycle numbers

(PAzoMA6)3-3_1R

(PAzoMA6)3-3_1S

-6

-4

-2

0

2

4

gCD

at t

he fi

rst c

otto

n ba

nd/1

0-3

300 350 400 450 500 550 600-300

-200

-100

0

100

200

300 cis_1 trans_1 cis_2 trans_2 cis_3 trans_3

trans_1S_Origin

trans_1R_Origin

cis_1 trans_1 cis_2 trans_2 cis_3 trans_3 cis_4 trans_4

Ellip

ticity

(mde

g)

Wavelength (nm)

(3a)

0 1 2 3 4-225

-150

-75

0

75

150(3b)

(PAzoMA6)4_1R

Ellip

ticity

(mde

g)

Cycle numbers

(PAzoMA6)4_1S

-9

-6

-3

0

3

6

gCD

at t

he fi

rst c

otto

n ba

nd/1

0-3

300 350 400 450 500 550 600-150

-100

-50

0

50

100

150 cis_1 trans_1 cis_2 trans_2 cis_3 trans_3


Ellip

ticity

(mde

g)

Wavelength (nm)

(4a)

trans_1R_Origin

trans_1S_Origin

0 1 2 3 4 5 6-100

-50

0

50

100

150(4b)

Ellip

ticity

(mde

g)

Cycle numbers

(PAzoMA6)6_1S

(PAzoMA6)6_1R-4

-2

0

2

4

6

gCD

at t

he fi

rst c

otto

n ba

nd/1

0-3

300 350 400 450 500 550 600-100

-50

0

50

100

trans_1R_Origin

trans_1S_Origin



Ellip

ticity

(mde

g)

Wavelength (nm)

(5a)

0 2 4 6-120

-80

-40

0

40

80

Ellip

ticity

(mde

g)

Cycle numbers

(PAzoMA11)3_1S

(PAzoMA11)3_1R-15

-10

-5

0

5

10(5b)

gCD

at t

he fi

rst c

otto

n ba

nd/1

0-4

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Fig. S9 Changes in CD spectra (a) and the maximum CD and gCD values (b) of

PAzoMA aggregates in DCE/(1R or 1S) during 365 nm light irradiation (3 min) and

heating-cooling treatment (60 oC for 40 min then cooling to room temperature). The

concentration of polymer repeating units is 8.42 × 10-5 mol/L. 1-5 stands for the


respectively.

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Fig. S10 TEM images of PAzoMA aggregates during chiroptical switching process.

(a−d for 1R/DCE and e−h for 1S/DCE). The original trans−form (a and e), after the

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first 3 min 365 nm light irradiation (b and f), after the heating−cooling treatment (c

and g), after the second 3 min 365 nm light irradiation (d and h). 1−5 stands for the


respectively.

Optically Inactive Star Azo Polymers: Photocontrollability, Chiral … · 2015. 8. 20. · 4...

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Transcript of Optically Inactive Star Azo Polymers: Photocontrollability, Chiral … · 2015. 8. 20. · 4...