A controlled iso-specific polymerization of 2-vinylpyridine catalyzed by

arylamide-ligated rare-earth metal aminobenzyl complexes

Min Li,a,† Chaopan Wang,a,† Jue Chen,c Zhiyong Guo,a Zehuai Mou,a and Yunjie

Luo*,a,b

a School of Material Science and Chemical Engineering, Ningbo University, Ningbo

315211, P. R. China

b State Key Laboratory of Polymer Physics and Chemistry, Changchun Institute of

Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, P. R. China

c School of Biological and Chemical Engineering, Ningbo Institute of Technology,

Zhejiang University, Ningbo 315100, P. R. China

Corresponding author: E-mail: luoyunjie@nbu.edu.cn

† Min Li and Chaopan Wang contributed equally to this work

Table of ContentsSFig. 1. 1H NMR spectrum of (2,5-Me2C4H2NCH2CH2NC6H5)Sc(CH2C6H4NMe2-o)2 (1)SFig. 2. 13C NMR spectrum of (2,5-Me2C4H2NCH2CH2NC6H5)Sc(CH2C6H4NMe2-o)2 (1)SFig. 3. 1H NMR spectrum of (2,5-Me2C4H2NCH2CH2NC6H5)La(CH2C6H4NMe2-o)2 (2)SFig. 4. 13C NMR spectrum of (2,5-Me2C4H2NCH2CH2NC6H5)La(CH2C6H4NMe2-o)2 (2)SFig. 5. 1H NMR spectrum of (2,5-Me2C4H2NCH2CH2NC6H5)Lu(CH2C6H4NMe2-o)2 (3)SFig. 6. 13C NMR spectrum of (2,5-Me2C4H2NCH2CH2NC6H5)Lu(CH2C6H4NMe2-o)2 (3)SFig. 7. 1H NMR spectrum of (2,5-Me2C4H2NCH2CH2NC6H5)2Y(CH2C6H4NMe2-o) (4)SFig. 8. 13C NMR spectrum of (2,5-Me2C4H2NCH2CH2NC6H5)2Y(CH2C6H4NMe2-o) (4)SFig. 9. 1H NMR spectrum of (2,5-Me2C4H2NSiMe2NC6H5)Lu(CH2C6H4NMe2-o)2 (5)SFig. 10. 13C NMR spectrum of (2,5-Me2C4H2NSiMe2NC6H5)Lu(CH2C6H4NMe2-o)2 (5)SFig. 11. 1H NMR spectrum of (2,5-Me2C4H2NSiMe2NC6H5)Y(CH2C6H4NMe2-o)2 (6)SFig. 12. 13C NMR spectrum of (2,5-Me2C4H2NSiMe2NC6H5)Y(CH2C6H4NMe2-o)2 (6)SFig. 13. GPC curve of representative polymerSFig. 14－16. Selected microstructure analysis of P2VP

Electronic Supplementary Material (ESI) for Dalton Transactions.This journal is © The Royal Society of Chemistry 2018

0.51.01.52.02.53.03.54.04.55.05.56.06.57.07.5f1 (ppm)

2.03

2.01

6.00

6.01

6.09

1.02

2.01

1.00

1.90

2.00

1.01

2.00

2.02

4.01

2.04

1.45

1.48

1.87

2.22

2.27

2.74

2.77

3.20

3.22

3.56

5.92

6.26

6.28

6.69

7.04

7.05

7.16

7.18

SFig. 1 1H NMR spectrum of (2,5-Me2C4H2NCH2CH2NC6H5)Sc(CH2C6H4NMe2-o)2 (1)

0102030405060708090110130150f1 (ppm)

12.89

41.66

43.72

45.65

47.38

105.96

114.63

116.65

119.13

122.12

127.75

128.06

130.25

142.81

143.05

152.30

SFig. 2 13C NMR spectrum of (2,5-Me2C4H2NCH2CH2NC6H5)Sc(CH2C6H4NMe2-o)2 (1)

Sc

N

NN

N

Sc

N

NN

N

=

hexane=

N

-NMe2

SFig. 3 1H NMR spectrum of (2,5-Me2C4H2NCH2CH2NC6H5)La(CH2C6H4NMe2-o)2 (2)

SFig. 4 13C NMR spectrum of (2,5-Me2C4H2NCH2CH2NC6H5)La(CH2C6H4NMe2-o)2 (2)

La

N

NN

N

La

N

NN

N

hexane=

hexane=

0.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.0f1 (ppm)

4.10

6.00

12.09

2.04

2.06

2.00

2.01

1.00

2.00

2.00

2.00

2.00

2.03

1.49

1.96

2.15

2.87

3.44

5.91

6.20

6.21

6.65

7.05

7.09

7.11

7.16

7.19

SFig. 5 1H NMR spectrum of (2,5-Me2C4H2NCH2CH2NC6H5)Lu(CH2C6H4NMe2-o)2 (3)

102030405060708090100110120130140150f1 (ppm)

12.89

42.10

43.81

44.16

50.05

105.82

113.10

115.53

119.97

128.06

128.25

130.20

139.71

142.96

153.40

SFig. 6 13C NMR spectrum of (2,5-Me2C4H2NCH2CH2NC6H5)Lu(CH2C6H4NMe2-o)2 (3)

Lu

N

NN

N

Lu

N

NN

N

hexane=

=

hexane=

N

-NMe2-Me

SFig. 7 13C NMR spectrum of (2,5-Me2C4H2NCH2CH2NC6H5)2Y(CH2C6H4NMe2-o) (4)

SFig. 8 13C NMR spectrum of (2,5-Me2C4H2NCH2CH2NC6H5)2Y(CH2C6H4NMe2-o) (4)

NY

N

N

N

N

NY

N

N

N

N

-Me

-NMe2

hexane=

=

hexane=

N

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.5f1 (ppm)

201712291H

6.00

4.02

11.7

76.

13

1.79

1.96

2.00

2.93

3.93

1.99

0.47

1.36

1.57

2.05

2.20

6.05

6.23

6.24

6.71

6.73

7.03

7.04

7.10

SFig. 9 1H NMR spectrum of (2,5-Me2C4H2NSiMe2NC6H5)Lu(CH2C6H4NMe2-o)2 (5)

0102030405060708090110130150f1 (ppm)

20180328

17.0

5

43.3

448

.80

110.

8011

9.57

120.

5112

0.98

125.

3212

8.21

130.

2813

0.77

133.

7213

9.90

142.

5914

8.17

SFig. 10 13C NMR spectrum of (2,5-Me2C4H2NSiMe2NC6H5)Lu(CH2C6H4NMe2-o)2 (5)

Lu

N

NNSi

N

Lu

N

NNSi

N

hexane=

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.5f1 (ppm)

w-9'

6.00

3.93

12.0

86.

09

1.85

1.98

4.99

4.08

2.04

0.49

1.59

1.99

2.22

6.02

6.18

6.75

7.03

7.11

7.12

7.14

SFig. 11 1H NMR spectrum of (2,5-Me2C4H2NSiMe2NC6H5)Y(CH2C6H4NMe2-o)2 (6)

0102030405060708090100110120130140150f1 (ppm)

w-9‘ C

17.0

6

43.1

844

.91

110.

8811

9.92

120.

0412

0.88

124.

4012

9.67

131.

3813

3.89

137.

18

SFig. 12 13C NMR spectrum of (2,5-Me2C4H2NSiMe2NC6H5)Y(CH2C6H4NMe2-o)2 (6)

Y

N

NNSi

N

Y

N

NNSi

N

SFig. 13 GPC curve for representative polymer

SFig. 14 The 13C NMR spectrum of P2VP obtained from 2-VP by using catalyst 1 as initiator in

toluene at 25 °C (run 1, Table 1) in CD3OD.

SFig. 15 The 13C NMR spectrum of P2VP obtained from 2-VP by using catalyst 4 as initiator in

toluene at 25 °C (run 5, Table 1) in CD3OD.

1

23456

n

N

12

3

45

6

7

7

SFig. 16 The 13C NMR spectrum of P2VP obtained from 2-VP by using catalyst 5 as initiator in

toluene at 25 °C (run 9, Table 1) in CD3OD.