S1

Electric Supplementary information for

Argentivorous Molecules Bearing Three

Aromatic-Side Arms: Selective Synthesis of

Triple-Armed Cyclens and Their Complexing

Property towards Ag+

Yoichi Habata,*,†,‡ Juli Kizaki,† Yasuhiro Hosoi,† Mari Ikeda,‡,§ and Shunsuke Kuwahara†,‡

†Department of Chemistry, Faculty of Science, and ‡Research Center for Materials with

Integrated Properties, Toho University, 2-2-1 Miyama, Funabashi, Chiba 274-8510, Japan

§Education Center, Faculty of Engineering, Chiba Institute of Technology, 2-1-1 Shibazono,

Narashino, Chiba 275-0023, Japan

Electronic Supplementary Material (ESI) for Dalton Transactions.This journal is © The Royal Society of Chemistry 2014

S2

Table of Contents

Figures S1 –S8 1H NMR S1–S7

Figures S9 and S10 HH-COSY of meso-9a/AgPF6 S7–S8

Figure S11 HMBC of meso-9a/AgPF6 S8

Figure S12a and S12b HMQC meso-9a/AgPF6 S9

Figure S13 HH-COSY of meso-9c S10

Figure S14 HH-COSY of meso-9c/AgPF6 S10

Figures S15 – S23 FAB-MS of meso-6 –meso-9d S11–S12

Figure S24 – S26 UV-Vis spectral chagnes and logK

calculation of meso-9a, 9c, and 9d. S13–S15

Table S1. Ag-N distances of Ag+ complexes S16

S3

HNNH

NHHN

OO

Figure S1. 1H NMR spectra of meso-6 in CDCl3.

HNNH

NHN

OO

Figure S2. 1H NMR spectra of meso-7a in CDCl3.

S4

HNNH

NHN

F

F

OO

Figure S3. 1H NMR spectra of meso-7b in CDCl3.

Figure S4. 1H NMR spectra of meso-8a in CDCl3.

HNNH

NHN

S5

Figure S5. 1H NMR spectra of meso-8b in CDCl3.

NNH

NN

Figure S6. 1H NMR spectra of meso-9a in CD2Cl2.

HNNH

NHN

F

F

S6

NNH

NN

D

DD

D

DD

D

D

DD

D

D

Figure S7. 1H NMR spectra of meso-9b in CD2Cl2.

NNH

NN

F

F

F

F

Figure S7. 1H NMR spectra of meso-9c in CD2Cl2.

S7

NNH

NN

F

F

F

F

F

F

Figure S8. 1H NMR spectra of meso-9d in CD2Cl2.

He H f

H f He

Figure S9. HH-COSY of meso-9a/AgPF6

NNH

NN Hf

Hf

HeHe

meso-9a

S8

H d H c

Ha

Hb

Figure S10. HH-COSY of meso-9a/AgPF6

NNH

NN

Ha

Hb

Hc

Hc

Hd

Hd

meso-9a

Figure S11. HMBC of meso-9a-AgPF6

He H f

C1

C2

NNH

NN

C2

C1

HfHf

HeHe

meso-9a

S9

Figure S12a. HMQC of meso-9a-AgPF6

Ha

C1

Hb

C2

NNH

NN

C1Ha

meso-9a

NNH

NN

C2Hb

meso-9a

Figure S12b. HMQC of meso-9a-AgPF6

S10

Figure13. HH-COSY of meso-9c in CD2Cl2

NNH

NN

F

F

F

F

meso-9c

Ha

Ha

Hb

Hb

Hb

HbHc

HcHc

Hd

Hd

Ha Hb

H d H c

Ha

Hb

H c

H d

Ha Hb H c

H d

Ha

Hb

H c

H d

Figure14. HH-COSY of meso-9c/AgPF6 in CD2Cl2

NNH

NN

F

F

F

F

meso-9c/AgPF6

Ha

Ha

Hb

Hb

Hb

HbHc

HcHc

Hd

Hd

S11

Figure S15. FAB-MS of meso-6.

Figure S16. FAB-MS of meso-7a.

Figure S17. FAB-MS of meso-7b.

Figure S18. FAB-MS of meso-8a.

Figure S19. FAB-MS of meso-8b.

HNNH

NHN

meso-8a (crude)

HNNH

NHHN

OO

meso-6

HNNH

NHN

F

F

meso-8b (crude)

HNNH

NHN

OO

meso-7a

HNNH

NHN

F

F

OO

meso-7b

S12

NNH

NN

meso-9a

Figure S20. FAB-MS of meso-9a.

Figure S21. FAB-MS of meso-9b.

Figure S22. FAB-MS of meso-9c.

Figure S23. FAB-MS of meso-9d.

NNH

NN

D

DD

D

DD

D

D

DD

D

D

meso-9b

NNH

NN

F

F

F

F

meso-9c

NNH

NN

F

F

F

F

meso-9dF

F

S13

Hyperquad refinement output. Version number 1.1.33Produced at 2014/06/17 20:02:05from data stored in I:\Dropbox\0000_HyperSpec\001_Juli\Bz\Bz.HQDProject title </intro><iterations>Initial Sigma =4.7008E-03Iteration 1 relativeParameter shift new valueLog beta AB 0.0000 5.6335

New sigma =4.7008E-03Change =563.3518%</iterations><results>HypSpec. Refinement concluded at 2014/06/17 20:02:06Data from I:\Dropbox\0000_HyperSpec\001_Juli\Bz\Bz.HQDProject title: Converged in 1 iterations with sigma = 4.7008E-03

standardLog beta value deviationAB 5.6335 0.0369AB2 was ignored

Figure S24. Ag+-ion-induced UV-Vis spectral chngnes and logK calculation by HyperSpec of meso-9a.

NNH

NN

meso-9a

Titration curve at 255nm

0.15

0.17

0.19

0.21

0.23

0.25

0.0 0.5 1.0 1.5 2.0

Guest/Host

Abs

S14

Hyperquad refinement output. Version number 1.1.33Produced at 2014/06/17 20:03:10from data stored in I:\Dropbox\0000_HyperSpec\001_Juli\35F_Bz\35F_Bz.HQDProject title </intro><iterations>Initial Sigma =2.5739E-04Iteration 1 relativeParameter shift new valueLog beta AB 0.0000 6.5812

New sigma =2.5739E-04Change =658.1167%</iterations><results>HypSpec. Refinement concluded at 2014/06/17 20:03:10Data from I:\Dropbox\0000_HyperSpec\001_Juli\35F_Bz\35F_Bz.HQDProject title: Converged in 1 iterations with sigma = 2.5739E-04

standardLog beta value deviationAB 6.5812 0.0296

Figure S25. Ag+-ion-induced UV-Vis spectral changes and logK calculation by HyperSpec of meso-9c.

Titration curve at 260nm

0.24

0.26

0.28

0.3

0.32

0.34

0.0 0.5 1.0 1.5 2.0

Guest/Host

Abs

NNH

NN

F

F

F

F

meso-9c

S15

Hyperquad refinement output. Version number 1.1.33Produced at 2014/06/17 20:05:39from data stored in I:\Dropbox\0000_HyperSpec\001_Juli\35F\35F.HQDProject title </intro><iterations>Initial Sigma =1.1186E-03Iteration 1 relativeParameter shift new valueLog beta AB 0.0000 6.4916

New sigma =1.1186E-03Change =649.1624%</iterations><results>HypSpec. Refinement concluded at 2014/06/17 20:05:39Data from I:\Dropbox\0000_HyperSpec\001_Juli\35F\35F.HQDProject title: Converged in 1 iterations with sigma = 1.1186E-03

standardLog beta value deviationAB 6.4916 0.0198

Figure S26. Ag+-ion-induced UV-Vis spectral changes and logK calculation by HyperSpec of meso-9d.

NNH

NN

F

F

F

F

meso-9d F

F

Titrarion curve at 260nm

0.18

0.2

0.22

0.24

0.26

0.28

0.0 0.5 1.0 1.5 2.0

Guest/Host

Abs

S16

Table S1. Ag-N distances of Ag+ complexes with 9a, 9b, 9c, and tetra-armed cyclens previously reported.

　 Ag–N distances (Å) Mean Average Deviation Ref #

9a/AgClO4 2.402 2.52 2.193 2.428 0.073

2.515 2.491 2.466 2.389

9b/AgPF6 2.379 2.399 2.546 2.629 0.099

9c/AgClO4 2.49 2.495 2.424 2.375 0.047

4-Ph 2.494 2.494 2.455 2.455 0.020 1

3,5-diF 2.495 2.457 2.404 2.426 0.031 1

4-F 2.473 2.467 2.432 2.442 0.017 1

4-Me 2.476 2.464 2.44 2.424 0.019 1

4-NO2 2.474 2.476 2.441 2.418 0.023 1

4-PhO 2.429 2.47 2.441 2.471 0.018 1

3,5-diF,4-Me 2.459 2.428 2.463 2.463 0.013 2

MeS-CC 2.471 2.509 2.541 2.568 0.026 3

　 2.566 2.51 2.554 2.529 　

References

1) Y. Habata, M. Ikeda, S. Yamada, H. Takahashi, S. Ueno, T. Suzuki, and S. Kuwahara, Org. Lett., 2012,

14, 4576–4579.

2) Y. Habata, Y. Oyama, M. Ikeda, and S. Kuwahara, Dalton Trans., 2013, 42, 8212–8217.

3) T. Gyr, H. R. Macke, and M. Henning, Angew. Chem. Int. Ed. Eng., 1997, 36, 2786–2788.

N N

NN

F

F

F

F

4-FN N

NN

4-Ph

N N

NN

Me

Me

Me

Me

4-FN N

NN

F F

F

F

FF

F

F

3,5-diF

N N

NN

O2N

NO2

NO2

NO2

4-NO2

N N

NN

O

O

O

O

4-PhON N

NN

Me

Me

F

F F

F

3,5-diF,4-Me

N N

NN

S

S

S

SMeSCC