Efficient Functionalizations of Heteroatom Bridged Calix[2]arene[2]triazines on the Larger Rim

Transcription

1 Supporting Information for Efficient Functionalizations of Heteroatom Bridged Calix[2]arene[2]triazines on the Larger Rim Hai-Bo Yang, De-Xian Wang,* Qi-Qiang Wang, Mei-Xiang Wang* Beijing ational Laboratory for Molecular Sciences, Laboratory of Chemical Biology, Institute of Chemistry, Chinese Academy of Sciences, Beijing, , China Table of Contents Copies of 1 H and 13 C MR Spectra for 6-9, 12a-e, 13a-c 2-36 UV-vis Titration of 12a-c with Cu 2+, Fe 2+, Co 2+, i 2+, Zn 2+ and 13a-c with Cu ESI-MS of the Complexs 12a-c with Cu(Cl 4 )

2 1 H MR of 6 6 2

3 6 3

4 13 C MR of 6 6 4

5 1 H MR of 7 H H 7 5

6 H H 7 6

7 13 C MR of 7 H H 7 7

8 1 H MR of 8 H 8 8

9 H 8 9

10 13 C MR of 8 H 8 10

11 H 8 11

12 1 H MR of 9 H H H Cl 9 12

13 H H H Cl 9 13

14 13 C MR of 9 H H H Cl 9 14

15 H H H Cl 9 15

16 1 H MR of 12a 12a 16

17 12a 17

18 13 C MR of 12a 12a 18

19 1 H MR of 12b 12b 19

20 12b 20

21 13 C MR of 12b 12b 21

22 1 H MR of 12c H H 12c 22

23 13 C MR of 12c H H 12c 23

24 1 H MR of 12d H H 12d 24

25 13 C MR of 12d H H 12d 25

26 1 H MR of 12e H H H H 12e 26

27 13 C MR of 12e H H H H 12e 27

28 1 H MR of 13a Cl 13a 28

29 Cl 13a 29

30 13 C MR of 13a Cl 13a 30

31 1 H MR of 13b Cl 13b 31

32 Cl 13b 32

33 13 C MR of 13b Cl 13b 33

34 1 H MR of 13c Cl H 13c 34

35 Cl H 13c 35

36 13 C MR of 13c Cl H 13c 36

37 UV-vis Titration of 12a-c with Cu 2+, Fe 2+, Co 2+, i 2+, Zn 2+ and 13a-c with Cu 2+ ( Perchlorate salts were used as metal ion sources unless indicated) A 0 -A Absorbance Cu [12a]/[12a]+[Cu 2+ ] Wavelength (nm) Figure S1. UV-vis titration of 12a ( mol L -1 ) upon the addition of Cu 2+ in a mixture of acetonitrile and water (4 : 1). The concentrations of Cu 2+ are 0, 0.766, 1.53, 2.30, 3.06, 4.60, 7.66, 13.79, 22.98, ( 10-5 mol L -1 ), respectively. Insert is the Job plot of the complexation between 12a and Cu 2+ ion in a mixture of acetonitrile and water (4 : 1), and the total concentration of 12a and Cu 2+ is mol L

38 1.0 Absorbance 0.5 Cu Wavelength (nm) Figure S2. UV-vis titration of 12a ( mol L -1 ) upon the addition of CuCl 2 in a mixture of acetonitrile and water (4 : 1). The concentrations of CuCl 2 are 0, 0.773, 1.55, 2.32, 3.09, 4.64, 6.18 ( 10-5 mol. L -1 ), respectively Absorbance Wavelength (nm) Figure S3. UV-vis titration of 12a ( mol L -1 ) upon the addition of Fe 2+ in a mixture of acetonitrile and water (4 : 1). The concentrations of Fe 2+ are 0, 0.836, 1.67, 2.51, 3.34, 4.18 ( 10-5 mol L -1 ), respectively. 38

39 Absorbance Wavelength (nm) Figure S4. UV-vis titration of 12a ( mol L -1 ) upon the addition of Co 2+ in a mixture of acetonitrile and water (4 : 1). The concentrations of Co 2+ are 0, 0.972, 1.94, 2.92, 3.89, 4.86 ( 10-5 mol L -1 ), respectively Absorbance Wavelength (nm) Figure S5. UV-vis titration of 12a ( mol L -1 ) upon the addition of i 2+ in a mixture of acetonitrile and water (4 : 1). The concentrations of i 2+ are 0, 0.864, 1.73, 2.59, 3.45, 4.32 ( 10-5 mol L -1 ), respectively. 39

40 Absorbance Wavelength (nm) Figure S6. UV-vis titration of 12a ( mol L -1 ) upon the addition of Zn 2+ in a mixture of acetonitrile and water (4 : 1). The concentrations of Zn 2+ are 0, 0.828, 1.66, 2.48, 3.31, 4.14 ( 10-5 mol L -1 ), respectively A 0 -A Absorbance Cu [12b]/[12b]+[Cu 2+ ] Wavelength (nm) Figure S7. UV-vis titration of 12b ( mol L -1 ) upon the addition of Cu 2+ in a mixture of acetonitrile and water (4 : 1). The concentrations of Cu 2+ are 0, 0.766, 1.53, 2.30, 3.06, 4.60, 6.13, 7.66, 13.79, ( 10-5 mol L -1 ), respectively. Insert is the Job plot of the complexation between 12b and Cu 2+ ion in a mixture of acetonitrile and water (4 : 1), and the total concentration of 12b and Cu 2+ is mol L

41 Absorbance Cu Wavelength (nm) Figure S8. UV-vis titration of 12b ( mol L -1 ) upon the addition of CuCl 2 in a mixture of acetonitrile and water (4 : 1). The concentrations of CuCl 2 are 0, 0.796, 1.59, 2.39, 3.18, 3.98 ( 10-5 mol L -1 ), respectively Absorbance Wavelength (nm) Figure S9. UV-vis titration of 12b ( mol L -1 ) upon the addition of Fe 2+ in a mixture of acetonitrile and water (4 : 1). The concentrations of Fe 2+ are 0, 0.836, 1.67, 2.51, 3.76, 5.02, 6.27, 7.52 ( 10-5 mol L -1 ), respectively. 41

42 Absorbance Wavelength (nm) Figure S10. UV-vis titration of 12b ( mol L -1 ) upon the addition of Co 2+ in a mixture of acetonitrile and water (4 : 1). The concentrations of Co 2+ are 0, 0.486, 0.972, 1.46, 1.94, 2.92, 3.89 ( 10-5 mol L -1 ), respectively Absorbance Wavelength (nm) Figure S11. UV-vis titration of 12b ( mol L -1 ) upon the addition of i 2+ in a mixture of acetonitrile and water (4 : 1). The concentrations of i 2+ are 0, 0.862, 1.724, 2.59, 3.45, 4.31 ( 10-5 mol L -1 ), respectively. 42

43 Absorbance Wavelength (nm) Figure S12. UV-vis titration of 12b ( mol L -1 ) upon the addition of Zn 2+ in a mixture of acetonitrile and water (4 : 1). The concentrations of Zn 2+ are 0, 0.414, 0.828, 1.24, 1.66, 2.48, 3.31 ( 10-5 mol L -1 ), respectively Absorbance A-A Cu 2+ [12c]/[12c]+[Cu 2+ ] Wavelength (nm) Figure S13. UV-vis titration of 12c ( mol L -1 ) upon the addition of Cu 2+ in a mixture of acetonitrile and water (4 : 1). The concentrations of Cu 2+ are 0, 0.552, 1.10, 1.66, 2.21, 3.31, 4.42, 6.62, 8.83, ( 10-5 mol L -1 ), respectively. Insert is the Job plot of the complexation between 12c and Cu 2+ ion in a mixture of acetonitrile and water (4 : 1), and the total concentration of 12c and Cu 2+ is mol L

44 1.5 Absorbance Cu Wavelength (nm) Figure S14. UV-vis titration of 12c ( mol L -1 ) upon the addition of CuCl 2 in acetonitrile. The concentrations of CuCl 2 are 0, 0.773, 1.55, 2.32, 3.09, 3.87, 4.64, 5.41, 6.18 ( 10-5 mol L -1 ), respectively. 1.5 Absorbance Wavelength (nm) Figure S15. UV-vis titration of 12c ( mol L -1 ) upon the addition of Fe 2+ in a mixture of acetonitrile and water (4 : 1). The concentrations of Fe 2+ are 0, 0.428, 0.836, 1.67, 2.51, 3.34, 4.18, 5.85, 6.69 ( 10-5 mol L -1 ), respectively. 44

45 1.5 Absorbance Wavelength (nm) Figure S16. UV-vis titration of 12c ( mol L -1 ) upon the addition of Co 2+ in a mixture of acetonitrile and water (4 : 1). The concentrations of Co 2+ are 0, 0.972, 1.94, 2.92, 3.89, 4.86, 5.83, 6.81, 7.78, 8.75 ( 10-5 mol L -1 ), respectively. 1.5 Absorbance Wavelength (nm) Figure S17. UV-vis titration of 12c ( mol L -1 ) upon the addition of i 2+ in a mixture of acetonitrile and water (4 : 1). The concentrations of i 2+ are 0, 0.864, 1.73, 2.59, 3.45, 4.32, 5.18, 6.05, 6.91, 7.78 ( 10-5 mol L -1 ), respectively. 45

46 1.5 Absorbance Wavelength (nm) Figure S18. UV-vis titration of 12c ( mol L -1 ) upon the addition of Zn 2+ in a mixture of acetonitrile and water (4 : 1). The concentrations of Zn 2+ are 0, 0.828, 1.66, 2.48, 3.31, 4.14, 4.97, 5.80, 6.62, 7.45 ( 10-5 mol L -1 ), respectively Absorbance Cu(Cl 4 ) Wavelength (nm) Figure S19. UV-vis titration of 13a ( mol L -1 ) upon the addition of Cu 2+ in a mixture of acetonitrile and water (4 : 1). The concentrations of Cu 2+ are 0, 0.257, 0.514, 0.771, 1.03, 1.54, 2.06 ( 10-5 mol L -1 ), respectively. 46

47 Absorbance Wavelength (nm) Figure S20. UV-vis titration of 13b ( mol L -1 ) upon the addition of Cu 2+ in a mixture of acetonitrile and water (4 : 1). The concentrations of Cu 2+ are 0, 0.513, 1.03, 2.05, 2.57, 3.59, 4.62 ( 10-5 mol L -1 ), respectively A-A Absorbance [13c]/[13c]+[Cu 2+ ] 0.2 Cu Wavelength (nm) Figure S21. UV-vis titration of 13c ( mol L -1 ) upon the addition of Cu 2+ in a mixture of acetonitrile and water (4 : 1). The concentrations of Cu 2+ are 0, 0.257, 0.514, 0.771, 1.03, 1.29, 3.08 ( 10-5 mol L -1 ), respectively. The insert is the job plot of the complexation between 13c and Cu 2+ ion in a mixture of acetonitrile and water (4:1), and the total concentration of 13c and Cu 2+ is mol L -1 47

48 ESI-MS of 12a Cu(Cl4)2 + [12a+H] [Cu-12a]+ 48

49 experimental [Cu-12a] + Calcd. for [Cu-12a] + Calcd. for [Cu 2-12a 2 ] 2+ 49

50 ESI-MS of 12b Cu(Cl4)2 [Cu-12b]+ 50

51 experimental [Cu-12b] + Calcd. for [Cu-12b] + Calcd. for [Cu 2-12b 2 ] 2+ 51

52 ESI-MS of 12c Cu(Cl4)2 [Cu-12c]+ [12c+H]+ 52

53 experimental [Cu-12c] + Calcd. for [Cu-12c] + Calcd. for [Cu 2-12c 2 ] 2+ 53