Metallamacrocycle-Modified Gold Nanoparticles: A

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included below. N ... A 50 mL three-neck flask was charged with purified CuI (175 mg, 0.92 mmol), L-proline ( .... imidazole (1.19g, 17.5 mmol), K2CO3 (2.90 g, 21 mol), CuI (335 mg, 1.75 ... 8.4 Hz, 2H), 6.90 (d, J = 8.0 Hz, 2H), 4.01 (s, 6H), 3.60 (s, 6H), 3.46 (s, .... atoms including Au1', Au2' and C78 were refined isotropically.

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Supplementary Information

Metallamacrocycle-Modified Gold Nanoparticles: A New Pathway for Surface Functionalization Hai-Xia Liu, Xin He, and Liang Zhao*

Contribution from Key Laboratory of Bioorganic Phosphorus Chemistry & Chemical Biology (Ministry of Education), Department of Chemistry, Tsinghua University, Beijing 100084, P. R. China.

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6761;

E-mail: [email protected]

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Electronic Supplementary Material (ESI) for Chemical Communications This journal is © The Royal Society of Chemistry 2013

Synthesis of MMC-1-4: All commercially available chemicals were used without further purification. Compounds 2-5 were synthesized according to the literature method.[1] The 1H- and 13C-NMR spectra were included below. Br

NaH, THF

NH2Me

Br

Br 160-170 oC

N

1 MeI

N

96%

N H

N

N

N

N H

2

N

N

N

Ag N

N

N

N

N

N

N

N

N

Br

N

NH4PF6

2I

N

N

N

96%

AuCl(SMe2)

2(PF6 )

N

N

N

N

N

N

N

N

N

Br

Br

N

N H

3 H N

CuI ,L-Proline K2CO3

N

80%

N

NH4PF6 90%

N

N

N

N

N

N

N

N

N

N

N

N

N

N

87%

N

N

N

Ag2O/Bu4NPF6

2(PF6 )

N

N 2(PF6 )

Au N

N

N

N

N

N

N

N

10 MeNH2

N

N

N

6

8

9

Br

N

N

N N

Au

96%

N

N

CuI ,L-Proline K2CO3 95%

N

N

N

Ag

N

N

N

N

N

N

Br

3

7

N

N

reflux

N

N

N

N

H N

Br

N

N

N

N

N

N

N

N

N

N

N

N

11

N

N

N

N

N

N

4

N

N

N

N

N

N

N

N

N

N

Br NaH

N H

Br

N

N

N

N

Br

N

5 MeI 99%

N

2(PF6 )

N

Ag2O, Bu4NPF6 87%

N

N

N

N

N

N

N

N

N

N

N

12 N N N N N N N N N

2I N

N N N N Ag

Ag N N N N N N N N N

13

N

2(PF6 )

N N N N

14 N N N N N N N N N

AuCl(SMe2)

N N N N Au

Au

90%

N N N N N N N N N

2(PF6 )

N N N N

15

N N

N

N

N

6

N

N

N N

A 50 mL three-neck flask was charged with purified CuI (175 mg, 0.92 mmol), L-proline (212 mg, 1.84 mmol), K 2 CO 3 (2.376 g, 17.22 mmol), imidazole (859 mg, 12.63 mmol) and compound 3 (2.577 g, 5.74 mmol), evacuated and backfilled with argon. To this mixture 9 mL

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DMSO was added by syringe under argon and the mixture was heated to 90 oC for 22 h. After complete reaction, water was added in one portion to form a clear solution (20-40 mL). The reaction mixture was extracted with EtOAc (3 × 30 mL) and the organic layers were combined, washed with brine (20 mL), dried over MgSO 4 , and concentrated in vacuo. The residual oil was then purified via column chromatography with ethyl acetate as eluent to give pure 6 (2.31g, 95%) as a pale yellow solid: m.p. 155-156 °C; 1H-NMR (400 MHz, CDCl 3 , ppm): δ 8.35 (s, 2H), 7.62-7.57 (m, 5H), 7.18 (s, 2H), 7.12 (d, J = 8.4 Hz, 2H), 6.98 (d, J = 7.6 Hz, 2H), 6.84 (d, J = 7.6 Hz, 2H), 3.65 (s, 6H); 13C-NMR (100 MHz, CDCl 3 , ppm): δ 156.8, 156.0, 147.5, 139.6, 138.9, 135.1, 130.4, 116.2, 110.9, 109.6, 103.2, 36.0; IR (KBr, cm-1): 3126 (m), 1574 (s), 1446 (s), 1302 (m), 1172 (s), 1507 (s), 973 (m), 769 (m), 743 (m), 714 (m); MALDI-TOF MS: m/z = 424.0 ([M+H]+).

N

N

N

N

N

N

2I

N

N

N

7

Compound 6 (0.85 g, 2 mmol) was dissolved in 25 mL toluene in a sealed tube and MeI (2.5 mL, 40 mmol) was added by syringe. The mixture was heated to 90 oC for 6 h. The reaction mixture was cooled to room temperature and a yellow solid appeared. Recrystallize the solid by methanol /diethyl ether to produce pure 7 (1.36 g, 96%) as a yellow solid: m.p.: 180-181 °C; 1 H-NMR (400 MHz, DMSO-d 6 , ppm): δ 9.96 (s, 2H), 8.47 (t, J = 2 Hz, 2H), 7.97-7.92 (m, 4H), 7.86 (t, J = 8.0 Hz, 1H), 7.43 (d, J = 8.0 Hz, 2H), 7.39 (d, J = 8.4 Hz, 2H), 7.14 (d, J = 7.6 Hz, 2H), 3.99 (s, 6H), 3.61 (s, 6H); 13C-NMR (100 MHz, DMSO-d 6 , ppm): δ 156.0, 155.1, 144.5, 140.7, 140.5, 135.2, 124.7, 118.9, 113.8, 110.4, 104.5, 36.4, 36.1; IR (KBr, cm-1): 3082 (m), 1618 (s), 1432 (s), 1319 (m), 1220 (m), 1175 (m), 1088 (m), 950 (m), 793 (s); MALDI-TOF MS: m/z = 580.0 ([M-I]+).

N

N

N

N

N

N

N

2PF6

N N

8

In a 100 mL round-bottom flask were charged with 3 mL methanol solution of NH 4 PF 6 (489 mg, 3mmol) and 20 mL methanol solution of compound 7 (707 mg, 1 mmol). A yellow solid appeared immediately, which was filtered, washed by cool methanol and diethyl ether to yield pure 8 (713 mg, 96%) as a yellow solid: m.p.: 177-178 °C; 1H-NMR (400 MHz, DMSO-d 6 , ppm): δ 9.94 (s, 2H), 8.46 (s, 2H), 7.95-7.91 (m, 4H), 7.85 (t, J = 8.0 Hz, 1H), 7.42 (d, J = 7.6 Hz, 2H), 7.39 (d, J = 8.4 Hz, 2H), 7.14 (d, J = 8.0 Hz, 2H), 3.98 (s, 6H), 3.61 (s, 6H); 13C-NMR (100 MHz, DMSO-d 6 , ppm): δ 156.1, 155.1, 144.5, 140.7, 140.5, 135.2, 124.7, 118.9, 113.8, 110.4, 104.5, 36.4, 36.0; IR (KBr, cm-1): ν 3169 (m), 1622 (s), 1487 (s), 1326 (m), 1220 (s),

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1178 (m), 1093 (s), 955 (m), 843 (s), 784 (m), 736 (m), 558 (s); MALDI-TOF MS: m/z = 598.1 ([M-PF 6 ]+). N

N

N

N

N

N

N

N

Ag N

N 2PF6

Ag N

N

N

N

N

N

N

N

9 (MMC-1)

To a mixed solution of CH 2 Cl 2 (30 mL) and CH 3 CN (10 mL) were added compound 8 (500 mg, 0.67 mmol), Ag 2 O (232 mg, 1 mmol) and catalytic amounts of Bu 4 NPF 6 . After the reaction mixture was refluxed for 3 h in dark, NaOH solution (1 N, 5 mL) was added. The reaction mixture was refluxed for further 8 h. The resulting suspension was then filtered through celite and the resulting filtrate was concentrated in vacuo. Recrystallize by CH 3 CN/Et 2 O repeatedly to give pure 9 (411 mg, 87%) as an off-white powder: m.p.: 186-187 °C; 1H-NMR (400 MHz, CD 3 CN, ppm): δ 7.78 (s, 4H), 7.55 (t, J = 7.6 Hz, 4H), 7.40 (t, J = 8.0 Hz, 2H), 7.33 (s, 4H), 7.23 (d, J = 8.0 Hz, 4H), 7.09 (d, J = 8.4 Hz, 4H), 6.67 (d, J = 8.4 Hz, 4H), 3.88 (s, 12H), 3.28 (s, 12H); 13C-NMR (100 MHz, CD 3 CN, ppm): δ 157.1, 155.6, 149.6, 140.6, 139.9, 124.4, 120.4, 115.3, 107.3, 107.1, 40.3, 36.6; IR (KBr, cm-1): 3151 (w), 2951 (w), 1566 (m), 1429 (s), 1327 (m), 1237 (m), 1174 (m), 1117 (m), 954 (w), 842 (s), 788 (m), 740 (m), 559 (s); MALDI-TOF MS: m/z = 559.9 ([M-2PF 6 ]2+).

N

N

N

N

N

N

N

N

Au N

N 2PF6

Au N

N

N

N

N

N

N

N

10 (MMC-3)

To a 30 mL CH 2 Cl 2 solution of 9 (300 mg, 0.21 mmol) was added AuCl(SMe 2 ) (126 mg, 0.43 mmol). The mixture was stirred for 36 h at room temperature. The resulting suspension was then filtered through celite and the filtrate was concentrated in vacuo. Recrystallize by CH 3 CN/Et 2 O repeatedly to produce pure 10 (320 mg, 96%) as an off-white powder: m.p.: 192-193 °C; 1H-NMR (400 MHz, CD 3 CN, ppm): δ 7.70 (d, J = 2.0 Hz, 4H), 7.54 (t, J = 8.0 Hz, 2H), 7.44 (t, J = 8.0 Hz, 4H), 7.35 (d, J = 1.6 Hz, 4H), 7.28 (d, J = 7.6 Hz, 4H), 7.15 (d, J = 8.0 Hz, 4H), 6.84 (d, J = 8.4 Hz, 4H), 3.99 (s, 12H), 3.35 (s, 12H); 13C-NMR (100 MHz, CD 3 CN, ppm): δ 183.3, 157.2, 156.0, 149.4, 140.3, 124.5, 121.5, 114.4, 110.0, 108.9, 39.6, 36.5; IR

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(KBr): 3152 (w), 2951 (w), 1566 (m), 1429 (s), 1330 (m), 1239 (m), 1174 (m), 1121 (m), 955 (w), 842 (s), 789 (m), 741 (m), 559 (s); MALDI-TOF MS: m/z = 1441.0 ([M-PF 6 ]+). N

N

N

N

N

N

N

N

N

N

N

N

N

11

Compound 11 was prepared from 5 by a similar procedure to the synthesis of 6. Quantities: 5 (4.63 g, 7 mmol), imidazole (1.19g, 17.5 mmol), K 2 CO 3 (2.90 g, 21 mol), CuI (335 mg, 1.75 mmol), L-proline (403 mg, 3.5 mmol), DMSO (25 mL). The product 11 is a yellow solid (3.56 g, 80%): m.p.: 136-137 °C; 1H-NMR (400 MHz, CDCl 3 , ppm): δ 8.35 (s, 2H), 7.62 (s, 2H), 7.58 (t, J = 8.0 Hz, 2H), 7.49 (t, J = 8.0 Hz, 2H), 7.44 (t, J = 8.0 Hz, 1H), 7.18 (s, 2H), 7.14 (d, J = 8.4 Hz, 2H), 6.95 (d, J = 8.0 Hz, 2H), 6.84-6.79 (m, 6H), 3.65 (s, 6H), 3.60 (s, 6H); 13C-NMR (100 MHz, CDCl 3 , ppm): δ 157.0, 156.6, 156.4, 155.8, 147.5, 139.3, 138.4, 138.3, 135.1, 130.4, 116.2, 110.7, 108.4, 107.9, 107.4, 102.6, 36.0, 35.9; IR (KBr, cm-1): 3126 (w), 1573 (s), 1434 (s),1336 (m), 1312 (m), 1286 (m), 1175 (s), 1055 (m), 995 (m), 786 (m); MALDI-TOF MS: m/z = 636.1 ([M+H]+).

N

N

N

N

N

N

N

N

N

2I

N

N

N

N

12

Compound 12 was prepared from 11 by a similar procedure to the synthesis of 7. Quantities: 11 (1.91 g, 3 mmol), MeI (3.8 mL, 60 mmol), toluene (45 mL). The product is a yellow solid (2.73 g, 99%): mp 136-138 °C; 1H-NMR (400 MHz, DMSO-d 6 , 50 oC, ppm): δ 9.93 (s, 2H), 8.44 (s, 2H), 7.94 (s, 2H), 7.89 (t, J = 8.0 Hz, 2H), 7.70 (t, J = 8.0 Hz, 2H), 7.60 (t, J = 8.0 Hz, 1H),7.39-7.36 (m, 4H), 7.02 (d, J = 8.0 Hz, 2H), 6.92 (d, J = 8.0 Hz, 2H), 6.87 (d, J = 8.0 Hz, 2H), 4.00 (s, 6H), 3.61 (s, 6H), 3.48 (s, 6H); 13C-NMR (100 MHz, DMSO-d 6 , ppm): δ 156.2, 155.8, 155.5, 154.8, 144.5, 140.4, 139.5, 139.0, 135.2, 124.7, 118.9, 113.5, 108.9, 108.0, 107.5, 103.9, 36.4, 36.0, 35.7; IR (KBr, cm-1): 3058 (m), 1563 (s), 1418 (s), 1321 (w), 1220 (s), 1169 (s), 1088 (m), 980 (m), 785 (m), 733 (m); 616 (m); MALDI-TOF MS: m/z = 792.0 ([M-I]+).

N

N

N

N

N

N

N

N

N

2PF6

N

N

N

N

13

Compound 13 was prepared from 12 by a similar procedure to the synthesis of 8. Quantities: 12 (1.84 g, 2 mmol), NH 4 PF 6 (978 mg, 6 mmol), methonal (18 mL). The product was a yellow solid (1.72 g, 90%): m.p.: 202-204 °C; 1H-NMR (400 MHz, DMSO-d 6 , 50 °C, ppm): δ 9.86 (s, 2H), 8.40 (s, 2H), 7.92 (s, 2H), 7.80 (t, J = 8.0 Hz, 2H), 7.75 (t, J = 8.0 Hz, 1H), 7.63 (t, J = 8.0 Hz, 2H), 7.35 (d, J = 7.6 Hz, 2H), 7.29 (d, J = 8.4 Hz, 2H), 6.94 (d, J = 8.4 Hz, 2H), 6.91 (d, J = 8.4 Hz, 2H), 6.90 (d, J = 8.0 Hz, 2H), 4.01 (s, 6H), 3.60 (s, 6H), 3.46 (s, 6H); 13C-NMR (100

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MHz, DMSO-d 6 , ppm): δ156.2, 154.6, 154.5, 153.2, 144.8, 140.7, 140.4, 135.5, 125.2, 119.3, 114.4, 108.5, 108.2, 107.8, 104.5, 36.9, 36.8, 36.7; IR (KBr, cm-1): 3169 (m), 1589 (m), 1429 (s), 1345 (w), 1221 (m), 1173 (m), 1093 (m), 985 (m), 839 (s), 783 (m), 557 (s); MALDI-TOF MS: m/z = 810.1 ([M-PF 6 ]+).

N

N

N

N

N

N

N

N

N

N

N

N

Ag

Ag N

N

N

N

N

N

N

N

N

N

N

N

2PF6

N

N

14 (MMC-2)

Compound 14 was prepared from 13 by a similar procedure to the synthesis of 9. Quantities: 13 (1.15 g, 1.2 mmol), Ag 2 O (696 mg, 3 mmol), Catalytic amounts of Bu 4 NPF 6 , NaOH solution (1 N, 10 mL), CH 2 Cl 2 (60 mL) and CH 3 CN (15 mL). The product is a yellow solid (955 mg, 87%): mp 168-170 °C; 1H-NMR (400 MHz, CD 3 CN, 70 °C, ppm): δ 7.69 (d, J = 1.2 Hz, 4H), 7.50-7.43 (m, 8H), 7.37 (t, J = 8.0 Hz, 2H), 7.26 (d, J = 1.2 Hz, 4H), 7.13-7.10 (m, 8H), 6.71 (d, J = 8.4 Hz, 4H), 6.70 (d, J = 8.0 Hz, 4H), 6.67 (d, J = 7.6 Hz, 4H), 3.87 (s, 12H), 3.36 (s, 12H), 3.34 (s, 12H); 13C-NMR (100 MHz, CD 3 CN, ppm): δ 157.2, 156.8, 155.8, 149.7, 140.6, 139.8, 139.0, 124.2, 120.5, 113.8, 109.3, 107.7, 106.7, 40.1, 36.6; IR (KBr, cm-1): ν 3146 (w), 2948 (w), 1563 (s), 1419 (s), 1323 (w), 1237 (w), 1169 (m), 1114 (m), 983 (m), 841 (s), 786 (m), 732 (m), 558 (s); MALDI-TOF MS: m/z = 772.1 ([M-2PF 6 ]2+).

N

N

N

N

N

N

N

N

N

N

N

N

N

Au

Au N

N

N

N

N

N

N

N

N

N

N

N

2PF6

N

15 (MMC-4)

Compound 15 was prepared from 14 by a similar procedure to the synthesis of 10. Quantities: 14 (385 mg, 0.21 mmol), AuCl(SMe 2 ) (126 mg, 0.43 mmol ), CH 2 Cl 2 (30 mL). The product was a yellow solid (380 mg, 90%): m.p.: 185-187 °C; 1H-NMR (400 MHz, DMSO-d 6 , 150 °C, ppm): δ 7.91 (s, 4H), 7.75 (t, J = 8.0 Hz, 4H), 7.61 (s, 4H), 7.40-7.34 (m, 10H), 7.30 (d, J = 7.2 Hz, 4H), 6.82-6.80 (m, 8H), 6.68 (d, J = 8.4 Hz, 4H), 4.06 (s, 12H), 3.49 (s, 12H), 3.39( s, 12H); 13 C-NMR (100 MHz, DMSO-d 6 , 100 °C, ppm): δ 180.7, 156.3, 155.7, 155.4, 154.7, 147.4, 139.9, 138.4, 137.4, 123.5, 120.6, 113.6, 108.3, 107.5, 107.3, 106.9, 37.9, 36.0, 35.5; IR (KBr, cm-1): ν 3150 (w), 2951 (w), 1565 (s), 1422 (s), 1337 (w), 1240 (m), 1168 (m), 1120 (m), 985 (m), 843 (s), 789 (m), 740 (m), 557 (s); MALDI-TOF MS: m/z = 860.5 ([M-2PF 6 ] 2+). Preparation of MMC-Au NPs

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The Au NPs was prepared by the literature method.[2] The concentration of the Au NPs solution was described as 2.95 × 10-4 M based on HAuCl 3 . MMC (9.87 × 10-7 mol) in 0.5 mL DMF was added into Au NPs (2.95 × 10-6 mol, 10 mL aqueous solution) and stirred at room temperature for 2 hours. X-ray Crystallographic Analysis Data for MMC-1·CH 3 OCH 2 CH 2 OCH 3 was collected at 173 K with Mo-Kα radiation (λ = 0.71073 Å) with frames of oscillation range 0.5º. Data for [H 2 Au 2 (2) 2 (H 2 O) 2 ] (CF 3 SO 3 ) 4 ·H 2 O (a protonated MMC-4) was collected at 143 K with Cu-Kα radiation (λ = 1.54178 Å) with frames of oscillation range 1º. All structures were solved by direct methods, and non-hydrogen atoms were located from difference Fourier maps. All non-hydrogen atoms were subjected to anisotropic refinement by full-matrix least-squares on F2 by using the SHELXTL program unless otherwise noticed. All figures are drawn by using X-seed program.[3] Crystal data for compound MMC-1·CH 3 OCH 2 CH 2 OCH 3 : C 54 H 60 Ag 2 F 12 N 18 O 2 P 2 , M = 1498.88, triclinic, space group P1 (No. 1), a = 8.3519(17) Å, b = 12.047(2) Å, c = 15.107(3) Å, α = 98.79(3) °, β = 98.78(3) °, γ = 99.16(3) °, V = 1458.4(5) Å3, Z = 1, T = 173 K, D c = 1.707 g cm-3, Flack parameter = 0.55(6). The structure, refined on F2, converged for 7642 unique reflections (R int = 0.0715) and 6894 observed reflections with I > 2σ(I) to give R 1 = 0.0681 and wR 2 = 0.1667 and a goodness-of-fit = 1.062. Two oxygen atoms O1 and O2 is disordered at two positions with a refined site-occupancy ratio of 0.50:0.50. The whole CH 3 OCH 2 CH 2 OCH3 molecule is highly disordered. Therefore, total six non-hydrogen atoms (O1, O2, C51, C52, C53, C54) were refined isotropically. There are four A level alerts in the checkcif report, which are all due to the severe disorder of the solent molecule CH 3 OCH 2 CH 2 OCH 3 . Crystal data for compound [H 2 Au 2 (2) 2 (H 2 O) 2 ](CF 3 SO 3 ) 4 ·H 2 O (a protonated MMC-4): C 78 H 79 Au 2 F 12 N 26 O 15 S 4 , M = 2370.86, monoclinic, space group P2 1 /n (No. 14), a = 21.3858(9) Å, b = 13.9075(7) Å, c = 30.0241(13) Å, α = 90.00 °, β = 102.410(3) °, γ = 90.00 °, V = 8721.2(7) Å3, Z = 4, T = 143(2) K, D c = 1.801 g cm-3. The structure, refined on F2, converged for 16317 unique reflections (R int = 0.0872) and 14640 observed reflections with I > 2σ(I) to give R 1 = 0.0740 and wR 2 = 0.2043 and a goodness-of-fit = 1.047. Gold atoms Au1 and Au2 are disordered over two closely separated positions because of twin crystal. Several disordered atoms including Au1’, Au2’ and C78 were refined isotropically. There are three A level alerts in the checkcif report. The first A alert arising from the large Hirshfeld difference between F5 and C76 can be explained by the existence of disordered positions for this uncoordinated ligand. Due to twin crystal and low quality data, it is hard to split the CF 3 moiety into two sets of positions. The second A alert because of high Ueq of O2W compared with its neighboring gold atom can be explained by the large atomic difference between the oxygen and the gold. The third A alert because of the short intramolecular distance between H8A and H10A can be ascribed to the theoretical hydrogen addition. References [1] Zhang, E.-X.; Wang, D.-X.; Zheng, Q.-Y.; Wang, M.-X. Org. Lett. 2008, 10, 2565. [2] Frens, G. Nat. Phys. Sci. 1973, 241, 20. [3] (a) Barbour, L. J. J. Supramol. Chem. 2001, 1, 189. (b) Atwood, J. L.; Barbour, L. J. Cryst. Growth Des. 2003, 3, 3. S7

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CA-AuNPs 82.0 80

1013,80 868,81 1050,79 963,81 807,80 1160,79 983,81 1352,781262,78 1113,78

75

1561,76

616,78

1430,76 1401,75

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65 1638,65

%T

60

55

50

45 3449,42

42.0 4000.0

3600

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Figure S1. IR spectra of CA-AuNPs. S8

cm-1

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MMC-1 98.3 90 80

2169,94

1966,96

596,95 654,91 1004,87

3588,85 3661,82 3460,83

70

3149,74

2949,78

683,81

984,73 953,67

60

%T

621,88

1017,81

488,95 501,94 515,92 473,96

1078,63

713,61

1257,58

50

1290,48

40

1115,42 1172,41

1369,40

30

736,39 787,37

1236,34

557,29

20

1325,24

1604,22

10

1585,16 1566,15

1428,2

841,1

1.2 4000.0

3600

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Figure S2. IR spectra of MMC-1. S9

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84.6

MMC-1-AuNPs 733,84 696,83 502,83 674,83 618,83 559,82 797,82 852,81

82 80

868,80

78 1384,78 1543,77 1469,78

76 2852,76 2962,76 2921,75

%T 74

1219,78 1260,78 1158,78 1032,77 1089,76

1589,75 1430,74

72

1621,73

70 68 66 65.1 4000.0

3446,65

3600

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cm-1

Figure S3. IR spectra of MMC-1-AuNPs. S10

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MMC-2

100.0 95 90

920,96

3656,96 3588,97 3145,90

85

629,92 621,92

2946,88

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1003,82

75 70 %T

982,74

65 1235,67

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730,68 1112,65

556,69

784,65

1365,63 1284,64

55

1323,58

1168,56

50 1471,52

45 1563,46

40 35

1418,29

28.6 4000.0

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Figure S4. IR spectra of MMC-2. S11

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77.3

MMC-2-AuNPs

76

554,76 624,75 700,75 667,75 501,73

74 72

869,72

70

%T

801,71

68 66

1319,66

64

3280,64 2962,64

2085,65 2853,64

2923,63

62

1654,61 1618,61

60

1420,62 1384,63

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Figure S5. IR spectra of MMC-2-AuNPs.

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1258,61 1218,60 1108,61 1154,58

58.8 4000.0

1033,63

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MMC-3

96.6 90

3591,93 3659,91 3469,94 3150,86

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2949,88

621,92

1024,91 1007,91

1668,88

691,87

963,85 982,83 954,84

70 1118,70 737,68

60 %T

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1170,64 1238,62

788,63 557,58

1329,55

50 1606,52 1586,46 1565,45 1471,44

40

30 20

1428,16

842,14

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Figure S6. IR spectra of MMC-3. S13

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MMC-3-AuNPs

83.1 82 80

849,81 868,81 801,80

1732,81 1152,80 1195,79 1260,79

2853,80

78

2924,78

76

1303,77

1024,77 1072,76

1426,76 1383,76 1371,74

74 72

616,81 561,81

1496,73

70 %T 68 66

1617,66

64 62 60 58 56

3459,54

54.0 4000.0

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Figure S7. IR spectra of MMC-3-AuNPs. S14

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MMC-4 100.0

95

3650,98 3147,97

1024,97 1006,96

2949,96

918,98

621,97 691,95

1082,93

90

983,92 739,89 1285,88 1238,88

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1369,84 1325,85

1117,87

787,87

557,87

1168,84

%T 80 1585,79

75 1470,75 1565,74

70

65

1420,62

841,62

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Figure S8. IR spectra of MMC-4. S15

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MMC-4-AuNPs 90.7 2338,90

2087,90

925,90 838,90 901,90 868,89

88 1304,87

86 84

2959,84 2854,85

1384,84 1420,84

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%T

2924,81

80

726,89 667,88 584,88 622,88 521,88 565,88 502,88

800,88

1259,84 1237,83 1157,82 1113,83 1084,82

78 76 1620,76

74 72 70 69.2 4000.0

3445,69

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Figure S9. IR spectra of MMC-4-AuNPs. S16

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Figure S10. XPS spectra of CA-AuNPs, MMC-4 and the centrifuged MMC-4-AuNPs.

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General procedures for UV-Vis titration experiments UV-Vis spectroscopic titrations experiments were carried out using a UV-Vis spectrometer at 298 K. All spectra were collected using a quartz cuvette with 10 mm path length. For each spectrum acquired, the range of 290-800 nm was surveyed at a resolution of 1.0 nm and an integration time of 0.1s. The pH values for each titration were measured by a pH meter. AuNPs (pH = 4.17) AuNPs-HBF4(pH = 2.38) AuNPs-HBF4(pH = 2.08)

0.8 0.7 0.6

A

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wavelength (nm)

Figure S11. UV-Vis titration curves of CA-AuNPs and HBF 4 . The DMF/H 2 O (v/v = 1:20) solution of HBF 4 (c = 3.17 × 10-2 M) was added into 3 mL DMF/H 2 O (v/v = 1:20) solution of CA-AuNPs (c = 2.95 × 10-4 M based on HAuCl 3 ) at 25 °C. The volume of HBF 4 was 0, 60 μL, 120 μL from top to down. MMC-3-AuNPs (pH = 4.05) MMC-3-AuNPs-HBF4 (pH = 2.37) MMC-3-AuNPs-HBF4 (pH = 2.07) MMC-3-AuNPs-HBF4 (pH = 1.89) MMC-3-AuNPs-HBF4 (pH = 1.79) MMC-3-AuNPs-HBF4 (pH = 1.69) MMC-3-AuNPs-HBF4 (pH = 1.61) MMC-3-AuNPs-HBF4 (pH = 1.54)

1.4 1.2

A

1.0 0.8 0.6 0.4 0.2 0.0

300

400

500

600

700

800

wavelength (nm)

Figure S12. UV-Vis titration curves of MMC-3-AuNPs and HBF 4 . The DMF/H 2 O (v/v = 1:20) solution of HBF 4 (c = 3.17 × 10-2 M) was added into 3 mL DMF/H 2 O (v/v = 1:20) solution of S18

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MMC-3-AuNPs at 25 °C. The volume of HBF 4 was 0, 60 μL, 120 μL, 180 μL, 240 μL, 300 μL, 360 μL, 420 μL from top to down. MMC-4-AuNPs (pH = 4.07) MMC-4-AuNPs-HBF4 (pH = 2.40) MMC-4-AuNPs-HBF4 (pH = 2.10) MMC-4-AuNPs-HBF4 (pH = 1.91) MMC-4-AuNPs-HBF4 (pH = 1.82) MMC-4-AuNPs-HBF4 (pH = 1.70) MMC-4-AuNPs-HBF4 (pH = 1.63) MMC-4-AuNPs-HBF4 (pH = 1.56) MMC-4-AuNPs-HBF4 (pH = 1.52) MMC-4-AuNPs-HBF4 (pH = 1.45)

2.5

2.0

A

1.5

1.0

0.5

0.0

300

400

500

600

700

800

wavelength (nm) Figure S13. UV-Vis titration curves of MMC-4-AuNPs and HBF 4 . The DMF/H 2 O (v/v = 1:20) solution of HBF 4 (c = 3.17 × 10-2 M) was added into 3 mL DMF/H 2 O (v/v = 1:20) solution of MMC-4-AuNPs at 25 °C. The volume of HBF 4 was 0, 60 μL, 120μL, 180 μL, 240 μL, 300 μL, 360 μL, 420 μL, 480 μL, 540 μL from top to down.

Figure S14. UV-Vis spectra of CA-AuNPs and the mixed solution samples of MMC-3, MMC-4, MMC-3-AuNPs, MMC-4-AuNPs with Cu(MeCN) 4 PF 6 (1 µM) in 1:3 ratio.

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