Supporting Information
Dendronized Copolymers Functionalized with Crown Ethers and Their Further
Modification through Host-Guest Interaction
Xingquan Xiong, Yongming Chen*
State Key Laboratory of Polymer Physics and Chemistry, Joint Laboratory of Polymer Sciences and
Materials, Institute of Chemistry, The Chinese Academy of Sciences, Beijing 100190, China.
Shu Feng, Wei Wang*
The Key Laboratory of Functional Polymer Materials and Institute of Polymer Chemistry, College of
Chemistry, Nankai University, Tianjin 300071, China.
8
O
O
O
7
O
6
O
O
5
O
3
4
1
N
2
O
O
O
H-8
O
O
H-7
H-Ar
H-5
H-6
H-1,2
H-3
H-4
8
7
6
5
4
3
2
ppm
Figure 1. 1H NMR spectrum of crown ether-functionalized maleimide 2 in CDCl3 with assignment.
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11 10
O
O
O
9
O
O
8
O
O
76
5
N
O
O
O
O
O
3 1
4 2
C-11
C-10
C-1,2
C-9
C-3,4
C-7
200
180
160
C-8
140
120
100
80
60
C-5 C-6
40
20
0
ppm
Figure 2. 13 C NMR spectrum of monomer 2 in CDCl3 with assignment.
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Figure S3. 1H NMR spectrum of 1[G2]2 in CDCl3 with assignment.
Figure S4. 13C NMR spectrum of 1[G2]2 in CDCl3 with assignment.
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Figure S5. Partial 1H NMR (400 MHz, CDCl3/CD3CN, 5:1, V/V, 298 K) spectra of (a) monomer 2, (b) 3,
and (c) 3n2 (u = uncomplexed, c = complexed, and * = solvent residue).
Figure S6. Partial 1H NMR (400 MHz, CDCl3/CD3CN, 5:1, V/V, 298 K) spectra of (a) monomer 2, (b) 4,
and (c) 4n2 (u = uncomplexed, c = complexed, and * = solvent residue).
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Figure S7. Partial 1H NMR (400 MHz, CDCl3/CD3CN, 5:1, V/V, 298 K) spectra of (a) monomer 2, (b) 5,
(c) 5n2 (u = uncomplexed, c = complexed, and * = solvent residue).
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Figure S8. Partial 1H NMR (400 MHz, CDCl3/CD3CN, 5:1, V/V, 298 K) spectra of (a) the copolymer
1[G2]2, (b) 3, and (c) 3n1[G2]2 (u = uncomplexed, c = complexed, and * = solvent residue).
Figure S9. Partial 1H NMR (400 MHz, CDCl3/CD3CN, 5:1, 298 K) spectra of base-acid cycles. (a) as
prepared 3n1[G2]2, (b) treated with Et3N, and (c) treated with TFA (u = uncomplexed, c= complexed,
and * = solvent residue).
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Figure S10. Partial 1H NMR (400 MHz, CDCl3/CD3CN, 5:1, V/V, 298 K) spectra of (a) the copolymer
1[G1]2, (b) 4, and (c) 4n1[G1]2 (u = uncomplexed, c = complexed, and * = solvent residue).
Figure S11. Partial 1H NMR (400 MHz, CDCl3/CD3CN, 5:1, 298 K) spectra of (a) 4n1[G1]2, (b) Et3Ntreated, (c) TFA-treated, (d) acid-base reaction after three cycles of 4n1[G1]2 (u = uncomplexed, c=
complexed, and * = solvent residue).
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Figure S12. Partial 1H NMR (400 MHz, CDCl3/CD3CN, 5:1, V/V, 298 K) spectra of (a) the copolymer
1[G2]2, (b) 4n1[G2]2 and (c) 4 (u = uncomplexed, c = complexed, and * = solvent residue).
Figure S13. Partial 1H NMR (400 MHz, CDCl3/CD3CN, 5:1, 298 K) spectra of (a) 4n1[G2]2, (b) Et3Ntreated, and (c) TFA-treated (u = uncomplexed, c= complexed, and * = solvent residue).
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Figure S14. Partial 1H NMR (400 MHz, CDCl3/CD3CN, 5:1, V/V, 298 K) spectra of (a) the copolymer
1[G1]2, (b) 5, and (c) 5n1[G1]2 (u = uncomplexed, c = complexed, and * = solvent residue).
Figure S15. Partial 1H NMR (400 MHz, CDCl3/CD3CN, 5:1, 298 K) spectra of (a) 5n1[G1]2, (b) Et3Ntreated, (c) TFA-treated, and (d) acid-base reaction after three cycles (u = uncomplexed, c= complexed,
and * = solvent residue).
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Figure S16. Partial 1H NMR (400 MHz, CDCl3/CD3CN, 5:1, V/V, 298 K) spectra of (a) the copolymer
1[G2]2, (b) 5n1[G2]2, and (c) 5 (u = uncomplexed, c = complexed, and * = solvent residue).
Figure S17. Partial 1H NMR (400 MHz, CDCl3/CD3CN, 5:1, 298 K) spectra of (a) 5n1[G2]2, (b) Et3Ntreated, (c) TFA-treated (u = uncomplexed, c= complexed, and * = solvent residue).
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Figure S18. Fluorescence spectral change of 3n1[G2]2 (2.5×10-5 M in CH2Cl2 solution, λexc = 290 nm)
upon addition of Et3N and TFA, respectively.
Figure S19. Fluorescence spectral change of 4n1[G1]2 (2.5×10-5 M in CH2Cl2 solution, λexc = 290 nm)
upon addition of Et3N and TFA, respectively.
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Figure S20. Fluorescence spectral change of 4n1[G2]2 (2.5×10-5 M in CH2Cl2 solution, λexc = 290 nm)
upon addition of Et3N and TFA, respectively.
Synthesis of compounds 3 and 4
Benzylamine (10.0 mmol) was added to a solution of an aldehyde compound (10.0 mmol) in
anhydrous toluene (20.0 mL). The resulting mixture was heated at 110oC for 3 h and then evaporated to
dryness. Then the crude product was issolved in MeOH (15.0 mL), NaBH4 (20 mmol) was added to the
solution at 0oC, which was stirred for 8 h after warming to room temperature. Water (10 mL) was added
carefully to quench the excess NaBH4. The solvent was then evaporated off, and the residue was
partitioned between water and CHCl3. The organic extracts were dried and the solvent was removed in
vacuo. Then the residue was dissolved in THF and a fewdrops of HPF6 were added to the solution. The
THF was then removed and the aqueous solution was extracted with CH2Cl2 several times. The organic
extracts were dried (MgSO4) and the solvent concentrated to dryness to yield 4 or 5 as a light yellow
powder.
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O
+
PhMe
PhCH2NH2
reflux
N
4a
NaBH4
HPF6
THF/MeOH
THF
N
H
4b
N PF6
H2
4
Scheme S1. Synthesis of hexafluorophosphate organic salt 4.
NH2
O
H
N
PhMe
+
OH
reflux
NaBH4
MeOH/THF
(1:1,V:V)
5a
OH
H
N
OH
HPF6
H2
N PF6
OH
THF
5b
5
Scheme S2. Synthesis of hexafluorophosphate organic salt 5.
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Figure S21. 1H NMR spectrum of 4 with assignment in CDCl3/CD3CN (5:1, V: V, 298 K).
Figure S22. 1H NMR spectrum of 5 with assignment in CDCl3/CD3CN (5:1, V: V, 298 K).
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