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Supporting information

A Triple-Monomer Methodology to Construct Controllable Supramolecular Hyperbranched Alternating PolymersHui Li, Xiaodong Fan*, Xiaomeng Shang, Miao Qi, Haitao Zhang, and Wei Tian*

The Key Laboratory of Space Applied Physics and Chemistry, Ministry of Education and Shaanxi Key Laboratory of Macromolecular Science and Technology, School of Science, Northwestern Polytechnical University, Xi’an 710072, P. R. China

E-mail: xfand@126.com, happytw_3000@nwpu.edu.cn

1. Materials and methods……………………………………………2

2. Self-sorting complexation studies…………………………..……2

3. 1H-1H COSY and NOESY NMR experiment……………………6

4. 2D Diffusion-Ordered NMR Spectroscopy……………………...8

5. Discussion of the association constants of the two self-sorting

binding interactions …………………………………………….10

6. Stimuli-Responsiveness of supramolecular hyperbranched

alternating polymer……………………………………………...10

7. Synthesis of the intermediates and monomers………………….11

Electronic Supplementary Material (ESI) for Polymer Chemistry.This journal is © The Royal Society of Chemistry 2016

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1. Materials and MethodsCompound 1S1, 2S1, 3S2, 4S3, M1S2, M4S1

, M5S4, E3S1 were synthesized according to

the literature procedure. The other reagents and solvents were either employed as purchased or dried prior to use by usual laboratory methods. Column chromatography was performed on silica gel (200-300 mesh). All reactions were carried out in nitrogen atmosphere unless noted.

1H NMR, 13C NMR, 1H-1H COSY, NOESY spectra were recorded on a Bruker AVANCE III 400 MHz spectrometer or a Bruker Avance DMX 500 spectrophotometer with use of the deuterated solvent as the lock and the residual solvent or TMS as the internal reference.Viscosity measurements were performed with Ubbelohde micro viscometers (Shanghai Liangjing Glass Instrument Factory) at 298 K in chloroform/acetone (1.5/1, v/v). The two-dimensional diffusion-ordered NMR spectra were recorded on a Bruker DRX600 spectrometer. Transmission electron microscope (TEM) experiments were carried out on a JEM-2100 instrument. High-resolution electrospray ionization mass spectra (HR-ESI-MS) were obtained on a Bruker Esquire 3000 plus mass spectrometer equipped with an ESI interface and ion trap analyzer. High-resolution MALDI mass spectrometry (MALDI-FT-ICR-MS) was performed on a solariX MALDI-FTMS instrument. Dynamic light scattering (DLS) measurements were carried out on a Brookhaven BI-9000AT system (Brookhaven Instruments Corporation, USA), using a 200-mW polarized laser source (λ = 630 nm).

2. Self-sorting complexation studies on model compounds 1–4

OOO

O

O OO O

O

NNN

CN

O

H2NPF6

O

O O

OH

H

4

H

H

H1

H2

H3

H4

H5

H6

H8

H13

H14

H20H19

H16

H10H9

H7H11

H17H15

H18

1 2

3 4

H12

According to our previous workS5, a mixed CDCl3-CD3COCD3 (1.5:1, v/v) solution of equimolar Benzo-21-crown-7 (B21C7), dialkylammonium salt, pillar[5]arene, and TAPN(4) can self-sort to form B21C7/dialkylammonium salt complex and Pillar[5]arene /TAPN complex. Here, we also prepared four model compounds 1-4 to study a self-sorting process in CDCl3 /CD3COCD3 (1.5:1, v/v). As shown in Fig. S1-S4, the slow-exchange complexation between B21C7 (1) moiety and dialkylammonium salt moiety (2) and the strong inclusion interaction between pillar[5]arene

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(3) and TAPN (4) were observed. Furthermore, 1H NMR spectrum of a mixed solution of equimolar four model compounds clearly showed that self-sorting organization of complexation between 1 and 2 and inclusion interaction between 3 and 4 occurred (Fig. S5).

Fig. S1 1H NMR spectrum (400 MHz, chloroform-d3/acetone-d6(1.5/1, v/v), 298 K) of (a) 1, (b) an equimolar solution of 1 and 2, (c) 2. The concentration of each compound is 5 mM, Peaks of uncomplexed monomers and the complexed monomers, are designated as uc and c, respectively. the signals of protons H5, H7, H8 of 2 were all split into two sets of peaks, corresponding to uncomplexed molecules (H5uc, H7uc, H8uc) and complexed monomers (H5c, H7c, H8c), which reflected the slow-exchange complexation between the B21C7 and dialkylammonium salt moieties.

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Fig. S2 1H NMR spectrum (400 MHz, chloroform-d3/acetone-d6(1.5/1, v/v), 298 K) of (a) 4, (b) an equimolar solution of 1 and 4, (c) 1. Signals affiliated with solvents are denoted by star symbols. Peak shifts were not observed, indicating that B21C7 can not form complex with TAPN.

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Fig. S3 1H NMR spectrum (400 MHz, chloroform-d3/acetone-d6(1.5/1, v/v), 298 K) of (a) 3, (b) an equimolar solution of 3 and 4, (c) 4. The concentration of each compound is 3 mM. The signals of protons H15, H16, H17, H18

of 4 were obviously shifted upfield and were broaden, indicating 4 was threaded into the cavity of 3. This is similar to the previous report by Li’s groupS3.

Fig. S4 1H NMR spectrum (400 MHz, chloroform-d3/acetone-d6(1.5/1, v/v), 298 K) of (a) 2, (b) an equimolar

solution of 3 and 2, (c) 3. The concentration of each compound is 5 mM, signals affiliated with solvents are

denoted by star symbols. peak shifts were not observed almost, indicating that the dialkylammonium salt was not

able to complex with pillar[5]arene or had very weak complexation in CDCl3/CD3COCD3 mixed solvent.

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Fig. S5 1HNMR spectrum (400 MHz, chloroform-d3/acetone-d6 (1.5/1, v/v), 298 K) of an equimolar mixture of (a)

1 and 2; (b) 1, 2, 3, and 4; (c) 3 and 4. The concentration of each compound is 6 mM, Signals affiliated with

solvents are denoted by star symbols. The peak shifts of 1 and 2 in (b) were same in those of the mixture of 1 and 2

in (a), and 3 and 4 in (c), respectively. These 1H NMR spectrums clearly showed that self-sorting organization of

complexation between 1 and 2 and inclusion interaction between 3 and 4 occurred.

3. 1H-1H COSY NMR and NOESY NMR experimentTo identify the signals of polymers, the 1H-1H COSY was performed at a concentration of 24.0

mM. As shown in Fig. S6, COSY provides great help for us to assign stacked peaks, For example, it is difficult to identify proton H19c because H19c stack with H8c, H9c. However, through the strong correlation between the protons H19c and H20c on AC, these stacked peaks are clearly identified. Furthermore, the correlation between H11c and H12c on AC, H13c and H14c on AC, H20c and H21c on AC were also observed at the same time. With the assistance of 1H-1H COSY NMR and comparison of the spectra of four model compounds. The signals of complicated concentration-dependent 1H NMR spectra (Fig. 1) were accurately identified.

NOESY NMR spectroscopy was further employed to study the formation of SHAP. As shown in Fig. S7, the strong correlation between H17br from AC and HEO from E3 indicated that the dialkylammonium salt moiety of AC was complexed tightly with the B21C7 moiety of E3 in the mixed solvent. On the other hand, the correlation between H11-14br on AC and H9br on D3, between H11-14br on AC and H10br on D3, were also observed. These correlation indicated that TAPN threaded into the cavity of pillar[5]arene. All observed correlation supported a alternating arrangement of (D3-AC-E3-AC)n.

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Fig. S6 Partial COSY NMR (400 MHz, CDCl3/CD3COCD3 = 1.5/1, v/v, 298 K) spectrum of a solution of 1:3:1

molar ratio of D3, AC (24 mM) and E3. Peaks of complexation proton are designated by c. Signals affiliated with

solvents are denoted by star symbols.

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Fig. S7 NOESY NMR (400 MHz, CDCl3/CD3COCD3 = 1.5/1, v/v, 298 K) spectrum of a solution of 1:3:1 molar

ratio of D3, AC (60 mM) and E3. Peaks of hyperbranched polymers are designated by br. Signals affiliated with

solvents are denoted by star symbols.

4. 2D Diffusion-Ordered NMR Spectroscopy The diffusion coefficients (D) of mixtures of D3, AC and E3 (molar ratio 1:3:1) were

performed at different concentrations in CDCl3/CD3COCD3 (1.5/1, v/v). At a very low concentration (2 mmol), we can see that there are two species (Fig. S8), including uncomplexed E3 and complexed branched oligomers. It should be noted that the signals of uncomplexed D3 could not be observed from the DOSY spectra at such a low concentration, which can attribute to stronger association constant between pillar[5]arene moiety and TAPN moiety compared to the binding constant between B21C7 and dialkylammonium salt. As the concentration of monomers increased, larger polymeric structures were gradually produced. From Fig. S9, we can only see DOSY signals of the supramolecular hyperbranched alternating polymers. That means the formation of bigger supramolecular hyperbranched alternating polymers.

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Fig. S8 Representative DOSY spectra (600 MHz, CDCl3/CD3COCD3 = 1.5/1, v/v, 298 K) of a solution of 1:3:1

molar ratio of D3, AC (2 mM), and E3.

Fig. S9 Representative DOSY spectra (600 MHz, CDCl3/CD3COCD3 = 1.5/1, v/v, 298 K) of a solution of 1:3:1

molar ratio of D3, AC (120 mM), and E3

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5. Discussion of the association constants of the two self-sorting

binding interactions 1) Benzo-21-Crown-7/Dialkylammonium Salt binding interaction:

We use model compound 1 and 2 to determine the binding constant Ka of the B21C7/Dialkylammonium recognition according to 1H NMR single point method S6. The Ka could be calculated from integrations of complexed and uncomplexed peaks in 1H NMR spectra. The experiment was performed at 4.00 mM CDCl3/CD3COCD3(1.5/1,v/v)solution. Using the reference method, Ka value was calculated as below: [(1.25/2.25) × 4 × 10-3]/[(1-1.25/2.25) × 4 × 10-3]2 = 705 M-1 in CDCl3/CD3COCD3 solution(1.5/1, v/v), the experiment was repeated for three times and the average Ka was determined to be 690 ± 45M-1, which is close to the literature value.S5

Fig. S10 1HNMR spectra (400 MHz, CDCl3/CD3COCD3 = 1.5/1, v/v, 298 K) of 4.00 mM 1 and 2.

2) Pillar[5]arene/TAPN binding interaction:The binding constant was referred by our previous workS5: Ka {[3.4]/[3][4] } is equal to (9.10 ± 0.2)× 103 M-1 in CDCl3/CD3COCD3 (1.5/1,v/v)

6. Stimuli-Responsiveness of supramolecular alternating

hyperbranched polymer investigated by NOESY experiments

NOESY experiments were also performed to study the reversible process. As shown in Fig.

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S11, the correlation between H17br from AC and HEO from E3 disappeared after the addition of K+, the broad peaks of the proton NMR spectra became sharp and simple, suggesting that the polyether ring of the B21C7 group of E3 was occupied by K+ and the large aggregates were disassembled into low-molecular-weight species. Upon subsequent addition of B18C6, the correlation between H17br from AC and HEO from E3 recovered and the peaks became broad again, indicating the supramolecular hyperbranched alternating polymer was reformed.

Fig. S11. Partial NOESY NMR spectra (400 MHz, CDCl3–CD3COCD3 = 1.5/1, v/v, 298 K) of (a) a solution of

1:3:1 molar ratio of D3, AC (60 mM), and E3, (b) after addition of 1 equiv. KPF6, and (c) after addition of 1 equiv.

B18C6.

7. Synthesis of the intermediates and monomers Design and Synthesis of Monomers. The synthetic routes of the desired compounds

are shown in Scheme S1. Compound AC was prepared by the click reaction of M6 and M7 in the presence of copper salt and sodium ascorbate. Here the length between dialkylammonium salt group and TAPN moiety on AC were designed to have totally 5 atoms in preventing the formation of gels/precipitates. Monomer D3 was synthesized by coupling between core1,3,5-tris(bromoethynyl)benzene (M4) and compound M2, in which the core M4 serves as the backbone to ensure the rigidity of the monomer D3 and increases the solubility of D3 in organic solvents. Monomer E3 was obtained using similar synthetic method as D3. These monomers were fully characterized.

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OO O

O

OOOO

O

OOO

OO

O

O

O O

Br Br

Br

Pd(PPh3)2Cl2,

Et3N,35℃

CuI

E3

O

O

OO

O

OO

O

O

O

O OO

OO

O

OO

Br Br

Br

Si

Pd(PPh3)2Cl2, CuI ,Et3 N

TMSTMS

TMS

TBAF

NBS, AgNO3

Br Br

Br

Pd(PPh3)2Cl2,

Et3N,35℃

CuI

OO

O

O

HH 4

H H

DMF, K2CO3

OO

O

OH

HH 4

H HBr

OO

O

O

HH 4

H H

O

O

O

O

HH

4

H

H

O

O

O

O H

H

4

H

H

+

O NH2

PF6 O NH2

NN

N

NCNCN

NN+

PF6

O H

ONH2 CuSO4.5H2O

sodium ascorbate1)methanol, refux2)NaBH43)HCl/H2O4)NH4PF6/H2O

1

D3

AC

H3H1

H2

H4

HEO

H5

H6

H7

H8

H9

H10

H11

H12

H13

H14

H15

H16

H17

H18 H19

H20

H21

M1 M2

M3 M4

M4

M5 M6 M7

Scheme S1 Synthetic routes of the homotritopic monomer D3, homotritopic monomer E3, and heteroditopic monomer AC.

Synthesis of Compound M6

Compound M5 (2.00g, 12.5mmol) and propylamine (0.71 g, 12.5mmol) were

dissolved in methanol (60 mL) and heated at 65 ℃ under N2 atmosphere overnight.

After the reaction mixture was cooled to ambient temperature, NaBH4(0.95 g, 25mmol) was added to the solution in small portion and the mixture was stirred at room temperature for another 12 h. Water (30 mL) was added to quench the remaining NaBH4, and 2 M HCl was added to acidify the amine. The solvent was removed under reduced pressure to give a white solid which was dissolved in deionized water/methanol (100 mL, 5:1, v/v). A saturated aqueous solution of NH4PF6 was added to afford a white precipitate which was filtered off and washed with

deionized water to afford M6 as a white solid (1.96 g, 45%). Mp: 151.1-151.9℃.1H

NMR (400 MHz, CD3CN, 298 K) δ (ppm): 0.95 (t, J = 7.6 Hz, 3H), 1.68 (m, 2H), 2.83 (t, J = 2.4 Hz, 1H), 2.97 (t, J = 8.0 Hz, 2H), 4.09 (s, 2H), 4.77 (d, J = 2.4 Hz, 2H), 7.05 (d, J = 8.4 Hz, 2H), 7.42 (d, J = 8.8 Hz, 2H), 13C NMR (100 MHz, CD3CN) δ

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(ppm): 158.48, 131.75 , 123.39, 115.23, 78.47, 76.14, 55.60, 51.01, 49.31, 19.13, 10.12. HR-ESI-MS (C13H18F6NOP): m/z calcd for [M-PF6

-]+ = 204.1383, found =204.1382

Fig. S12 1H NMR spectrum (400 MHz, CD3CN, 298 K) of compound M6

Fig. S13 13C NMR spectrum (100 MHz, CD3CN, 298 K) of compound M6

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Fig. S14 High-resolution electrospray ionization mass spectrum of compound M6

Synthesis of Compound AC

A mixture of M6 (1.71 g, 4.9 mmol) and M7 (0.61 g, 4.9 mmol) in a solution of tetrahydrofuran and water (3:1, 50 mL) in the presence of CuSO4•5H2O (122.3 mg,

0.49 mmol) with sodium ascorbate (277.3 mg, 1.40 mmol) was stirred at 50℃ for 12

h. The reaction mixture was poured into saturated brine (100 mL) and the resulting solution was extracted with dichloromethane (50 mL×3). The combined organic phase was concentrated and purified by flash column chromatography (CH3OH/CH2Cl2, 30:1 v/v) to afford compound AC as a white solid (1.15 g, 50%). Mp: 49.5-50.8℃. 1H NMR (400 MHz, CD3CN, 298 K) δ (ppm): 0.95 (t, J = 7.2 Hz, 3H), 1.58 (m, 2H), 1.66 (m, 2H), 1.97 (m, 2H), 2.40 (t, J = 7.2 Hz, 2H), 2.97 (m, 2H), 4.09 (t, J = 6.0 Hz, 2H), 4.39 (t, J = 6.8 Hz, 2H), 5.17 (s, 2H), 6.71 (br, 2H), 7.08 (d, J = 8.8 Hz, 2H), 7.40 (d, J = 8.8 Hz, 2H), 7.87 (s, 1H), 13C NMR (100MHz, CDCl3) δ (ppm): 159.36, 143.08, 150.02, 131.74, 123.99, 122.92, 119.90, 115.21, 61.48, 51.01, 49.24, 28.89, 22.21, 19.13, 16.04, 10.12. HR-ESI-MS (C18H26F6N5OP): m/z calcd for [M-PF6

-]+ = 328.2132, found =328.2135, error 1 ppm.

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Fig. S15 1H NMR spectrum (400 MHz, CD3CN, 298 K) of compound AC

Fig. S16 13C NMR spectrum (100 MHz, CD3CN, 298 K) of compound AC

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Fig. S17 High-resolution electrospray ionization mass spectrum of compound AC

Synthesis of Compound M2Compound M1 (2.00g, 2.7mmol) and 3-Bromo-1-propyne (0.4 g, 3.3mmol) were

dissolved in DMF (80 mL) and heated at 65 ℃ under N2 atmosphere overnight. After

the reaction mixture was cooled to ambient temperature, the solvent was removed and the resulting residue was subjected to column chromatography with CH2Cl2 as eluent,

to give M2 (1.57g, 75 %) as a white solid. MP: 164.3-165.6℃. 1H NMR (400 MHz,

CDCl3, 298 K) δ (ppm): 1.85 (s, 1H), 3.67 (m, 24H), 3.71 (s, 3H), 3.77 (s, 10H), 4.41(s, 2H), 6.71 (s, 1H), 6.76 (m, 9H), 13C NMR (100 MHz, CDCl3) δ (ppm): 151.30, 150.77, 148.91, 129.00, 128.56, 128.40, 115.39, 114.24, 114.16, 114.05, 114.01, 113.96, 113.86, 79.14, 74.73, 56.39, 55.90, 52.75, 30.25, 29.71, 29.11. HR-ESI-MS (C47H50O10): m/z calcd for [M+Na]+ = 797.3302, found =797.3312, error 1.2 ppm.

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Fig. S18 1H NMR spectrum (400 MHz, CDCl3, 298 K) of compound M2

Fig. S19 13C NMR spectrum (100 MHz, CDCl3, 298 K) of compound M2

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Fig. S20 High-resolution electrospray ionization mass spectrum of compound M2

Synthesis of Compound D3

In a sealed tube, 80 mL of 20% Et3N in tetrahydrofuran was degassed vigorously for 30 minutes. The following compounds were then added in order: compound M2 (2.00g, 2.58mmol), compound M4 （0.27g, 0.68mmol, dichlorobis(triphenylphosphine)palladium(II) (0.091g, 0.13mmol) and CuI (0.024g,

0.13mmol). The dark mixture was stirred at 35 ℃ for 12 h. The organic solvent was

evaporated under reduced pressure and the residue was partitioned between dichloromethane (50 mL) and water (50 mL). The aqueous layer was further washed with dichloromethane (3 × 50 mL). The organic phases were combined and dried over anhydrous Na2SO4. After the solvent was removed, the brown residue was purified by column chromatography (CH2Cl2/CH3COOC2H5= 100:1), to afford D3 (0.50g, 30 %)

as a white solid. Mp: 233.5-235.2℃. 1HNMR (400 MHz, CDCl3) δ (ppm): 3.63–3.75

(m, 72H), 3.81 (s, 9H), 3.84–3.88 (m, 30H), 6.82-6.87 (m, 30H), 7.64 (s, 3H). 13C NMR (100MHz, CDCl3) δ (ppm): 151.78, 150.85, 149.02, 136.54, 128.44, 128.33,128.25, 128.20, 128.16, 122.86, 115.73, 114.06, 80.01, 75.62, 75.39, 70,43, 57.59, 55.84, 55.78, 55.73, 55.64, 30.01, 29.74, 29.59. MALDI-FT-ICR-MS: m/z calcd for [M + Na]+ = 2491.0143, found =2491.0142, error 0.1 ppm.

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Fig. S21 1H NMR spectrum (400 MHz, CDCl3, 298 K) of compound D3

Fig. S22 13C NMR spectrum (100 MHz, CDCl3, 298 K) of compound D3

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Fig. S23 High-resolution MALDI-FT-ICR-MS spectrum of compound D3

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