1、 1Electronic Supplementary Information Sequential self-assembly for construction of Pt(II)-bridged 3rotaxanes on gold nanoparticles Liangliang Zhu,aHong Yan,aKim Truc Nguyen,aHe Tiancand Yanli Zhao*aba Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nany
2、ang Technological University, 21 Nanyang Link, Singapore 637371 b School of Materials Science and Engineering, Nanyang Technological University, Singapore 639798 c Key Laboratory for Advanced Materials and Institute of Fine Chemicals, East China University of Science found C 59.31, H 5.94, N 6.62. 3
3、: Compound 2 (0.5 g, 1.24 mmol) was added to an acetone solution (12 mL) containing 1,2-dibromoethane (2.4 g, 12.9 mmol). The mixture solution was then added K2CO3(355 mg, 2.57 mmol). The solution was stirred under refluxing for 8 h under Ar protection. After filtration, the filtrate was concentrate
4、d in vacuo and then purified through silica gel chromatography (petroleum ether : ethyl acetate = 9 : 2) to afford yellow compound 3 (0.395 g, 62.7%). m.p. 107 108 C. 1H NMR (400 MHz, CDCl3, 298 K, TMS): = 7.97 (d, J = 8.8 Hz, 2H), 7.90 (d, J = 8.8 Hz, 2H), 7.25 (d, J = 8.8 Hz, 2H), 7.04 (d, J = 8.8
5、 Hz, 2H), 4.40 (t, J = 6.0 Hz, 2H), 3.71 (t, J = 6.0 Hz, 2H), 3.65 (m, 1H), 3.22 (m, 1H), 3.16 (m, 1H), 2.64 (t, J = 7.2 Hz, 2H), 2.50 (m, 1H), 1.90 (m, 1H), 1.80 (m, 2H), 1.60 (m, 2H), 1.29 (m, 2H). 13C NMR (100 MHz, CDCl3, 298K, TMS): = 171.69, 152.73, 152.29, 150.14, 147.34, 124.83, 124.10, 122.2
6、3, 114.94, 68.04, 56.31, 40.26, 38.54, 34.62, 34.20, 28.81, 28.73, 24.61. HRMS (ESI): calcd for C22H26N2O3S2Br m/z = 509.0568, found m/z = 509.0565 (79Br), 511.0553 (81Br) 3 + H+. LNO3: An acetonitrile solution (20 mL) containing 3 (0.36 g, 0.71 mmol) and 4,4-bipyridine (1.1 g, 7.09 mmol) was stirre
7、d at 80C for 2 d. The solvent was removed in vacuo. The residue was dissolved in a small amount of acetonitrile and then purified through silica gel chromatography (dichloromethane : methanol = 50 : 5) to afford white compound LBr (0.33 g, 70.2%). m.p. 250 C. 1H NMR (400 MHz, CDCl3, 298K, TMS): = 9.
8、73 (d, J = 5.6 Hz, 2H), 8.85 (d, J = 5.2 Hz, 2H), 8.20 (d, J = 6.0 Hz, 2H), 7.83 (d, J = 8.4 Hz, 2H), 7.80 (d, J = 8.0 Hz, 2H), 7.57 (d, J = 5.6 Hz, 2H), 7.15 (d, J = 8.4 Hz, 2H), 6.93 (d, J = 8.8 Hz, 2H), 5.60 (m, 2H), 4.69 (m, 2H), 3.55 (m, 1H), 3.10 (m, 2H), 3.16 (m, 2H), 2.54 (t, J = 7.6 Hz, 2H)
9、, 2.41 (m, 1H), 1.88 (m, 1H), 1.74 (m, 2H), 1.54 (m, 2H), 1.25 (m, 2H). 13C NMR (100 MHz, DMSO-d6, Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is The Royal Society of Chemistry 20125298K, TMS): = 171.53, 160.12, 152.80, 152.29, 150.97, 149.51, 146.55, 146.01, 140.
10、78, 125.22, 124.56, 123.47, 122.84, 121.94, 115.33, 66.46, 59.39, 56.01, 38.11, 34.00, 33.28, 27.99, 24.00. HRMS (ESI): calcd for C32H33N4O3S2m/z = 585.1994, found m/z: 585.2042 M Br+. Elemental analysis: calcd C 57.74, H 5.00, N 8.42; found C 57.72, H 5.35, N 9.50. AgNO3(47 mg, 0.28 mmol) was then
11、added to a water solution (20 mL) containing LBr (180 mg, 0.27 mmol) and the mixture solution was stirred at 45 C in dark for 8 h. The solid formed was collected by filtration and the product was extracted with acetone (30 mL). After removing solvent and drying under reduced pressure, pure LNO3 was
12、obtained as a yellow solid (138 mg, 78.8%). Its proton resonances are almost the same as those of LBr. enPt: Ethylene diamine platinum chloride (60 mg, 0.18 mmol) was suspended in H2O (20 mL) at 50 C. AgNO3(64 mg, 0.38 mmol) was added to the suspension and the mixture solution was stirred for 2 h. W
13、hite AgCl solid was formed and then filtered off. The filtrate was evaporated in vacuo and the white solid product was directly used for the next step. Citrate-Stabilized AuNPs with an Average Diameter of 15 nm: It was prepared by following the synthetic procedure described in literature.S2 AuL(-CD)
14、NO3 and AuPt-2L(-CD)2NO34: Two of the hybrids were prepared by the ligand-exchange reaction. Typically, L(-CD)NO3 or Pt-2L(-CD)2NO34 aqueous solution (1 mL, 10 mM calculated by the azobenzene unit) was placed in a 4-mL cleaned vial. Citrate-stabilized AuNP solution (2 mL, 14.25 nM calculated by the
15、gold spheres) was dropwise added to the ligand solution with stirring. AuL(-CD)NO3 was formed immediately and deposited as black precipitates, whereas AuPt-2L(-CD)2NO34was generated stably and isolated by centrifugation. Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal
16、 is The Royal Society of Chemistry 20126Job Plot of Complexation between LNO3 and -CD 0.00.10.20.30.40.50.60.70.80.91.0510152025AmaxDifferenceL/L+alfa-CDFig. S1 Job plot showing 1:1 stoichiometry of the host-guest complex between LNO3 and -CD in H2O. The total concentration of the host and guest was
17、 kept at 1.0104M. Association Constant k between LNO3 and -CD The association constant k between LNO3 and -CD in aqueous solution was determined by following the UV-Vis absorption changes at 440 nm as shown in Fig. S2. The concentration of LNO3 maintains unchanged at 1.0 104M. Upon addition of -CD,
18、the absorption at 440 nm changes remarkably. With a 1:1 stoichiometry, the inclusion complexation between -CD and LNO3 is expressed by the following equation: We employed the double reciprocal plot in calculation of the association constant k according to the modified Hidebrand-Benesi equation:S3whe
19、re A denotes the absorbance difference before and after addition of -CD and denotes the difference of the molar extinction coefficient between the ligand and the complex at the same wavelength. Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is The Royal Society of Ch
20、emistry 20127The association constant k is calculated from the double reciprocal plot of 1/A versus 1/-CD, and the value calculated is 1830 95 M1 for the host-guest complex. 300 350 400 450 500 550 6000.000.150.300.450.600.75AbsorbanceWavelength/nmincreasing the concentration of alfa-CD1000 2000 300
21、0 4000 500068101214-+R-Square(COD) = 0.9984K = 1830 95 M-11/d A4401/alfa-CD/M-1Fig. S2 UV-Vis absorption changes (left) and double reciprocal plot (right) of LNO3 upon stepwise addition of -CD. The concentration of LNO3 maintains 1.0 104M. Fig. S3 Energy-minimized structure of L(-CD)NO3 (left) and T
22、EM image of AuL(-CD)NO3 (right). The distance between some of two adjacent nanoparticles has been highlighted by red ellipse, which is consistent with the length of L(-CD)NO3. Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is The Royal Society of Chemistry 20128Fig.
23、S4 Raman spectra of L(-CD)NO3 in H2O recorded immediately by mixed with (a) H2O, (b) enPt, (c) AuNPs, (d) AuNPs followed by enPt, and (e) enPt followed by AuNPs. The concentrations of L(-CD)NO3 and AuNPs maintaine 3.3 mM and 4.75 nM, respectively. The amount of enPt was adjusted to be half equiv of
24、L(-CD)NO3. The green and red dash lines denote the vibrations of azobenzene and aromatic units, respectively.S4 Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is The Royal Society of Chemistry 201291H NMR Titration Experiments Fig. S5 1H NMR spectra (400 MHz) of (A)
25、LNO3, (B) LNO3 + 0.15 equiv of enPt, and (C) LNO3 + 0.5 equiv of enPt in DMSO-d6at 298 K. The “*” stands for the methylene protons of the coordinated ethylene diamine group. Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is The Royal Society of Chemistry 201210Fig. S
26、6 1H NMR spectra (400 MHz) of (A) L(-CD)NO3, (B) L(-CD)NO3 + 0.05 equiv of enPt, (C) L(-CD)NO3 + 0.15 equiv of enPt, (D) L(-CD)NO3 + 0.35 equiv of enPt, (E) L(-CD)NO3 + 0.5 equiv of enPt, (F) L(-CD)NO3 + 0.7 equiv of enPt, and (G) L(-CD)NO3 + 1.0 equiv of enPt in D2O at 298 K. Some impurity peaks ma
27、rked with “X” emerged when more than 0.5 equiv of enPt was added, indicating that 0.5 equiv of enPt is sufficient for the quantitative formation of Pt-2L(-CD)2NO34. The “*” stands for the methylene protons of the coordinated ethylene diamine group. 1H NOESY NMR Spectra The NOE cross peaks between th
28、e azobenzene protons Hg-jand the internal protons H3/5of -CD are found in the 1H NOESY NMR spectra (Fig. S7 and S8), indicating the -CD ring dominantly encircles the azobenzene unit both in L(-CD)NO3 and Pt-2L(-CD)2NO34. Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal
29、 is The Royal Society of Chemistry 201211Fig. S7 1H NOESY NMR spectrum (400 MHz) of L(-CD)NO3 in D2O at 298 K. Fig. S8 1H NOESY NMR spectrum (400 MHz) of Pt-2L(-CD)2NO34in D2O at 298 K. Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is The Royal Society of Chemistry
30、201212Fig. S9 ESI-MS spectrum of L(-CD)NO3 in H2O. Fig. S10 ESI-MS spectrum of Pt-2L(-CD)2NO34in H2O. Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is The Royal Society of Chemistry 201213Fig. S11 Energy-minimized structure of Pt-2L(-CD)2NO34(left) and TEM image of
31、AuPt-2L(-CD)2NO34(right). The ellipses highlight the thickness of the outer layer around a nanoparticle, which is consistent with the height of L(-CD)NO3. 300 350 400 450 500 550-4-202468(A)edcbCD/mdegWavelength/nma300 350 400 450-2024(B)bCD/mdegWavelength/nmaFig. S12 (A) Induced circular dichroism
32、(ICD) spectra of LNO3 (curve a), L(-CD)NO3 (curve b), L(-CD)NO3 irradiated by 365 nm of UV light for 20 min (curve c), Pt-2L(-CD)2NO34 (curve d), and Pt-2L(-CD)2NO34 irradiated by 365 nm of UV light for 20 min (curve e) in H2O at 298 K. (B) Induced circular dichroism (ICD) spectra of AuPt-2L(-CD)2NO
33、34(curve a) and AuPt-2L(-CD)2NO34 irradiated by 365 nm of UV light for 20 min (curve b) in H2O at 298 K. Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is The Royal Society of Chemistry 201214Calculation of Coverage of Pt-2L(-CD)2NO34on AuNPs The coverage of Pt-2L(-C
34、D)2NO34on AuNPs was determined by UV-Vis spectroscopy and calculated from LambertBeer law. The initial solution of Pt-2L(-CD)2NO34 (the concentration is 10.0 mM calculated by the azobenzene unit) was diluted 60-fold with deionized water, and used for measurement of the UV-Vis absorbance. The absorba
35、nce A1at 350 nm, attributed to the electronic transition * of the azobenzene unit, is 2.029. A aqueous solution (2 mL) of AuNPs (14.25 nM) was added into the initial aqueous solution (1 mL) of Pt-2L(-CD)2NO34 (10.0 mM) and stirred for 1 h. The excess AuNPs were thoroughly removed by centrifugation (
36、13500 rpm for 15 min). The absorbance A2at 350 nm for the rest solution after diluted 60-fold with deionized water is 0.676. The relationship between the absorbance and the ligand concentration is reflected as the following equation: A1/A2 =Cinitial/60Cend/60(both the molar extinction coefficient an
37、d the cuvette length d are constant)According to the result (Cend= 3.331 mM), we can deduce that the ligand amount consumed by these AuNPs is 5.985 109mol. As one Pt-2L(-CD)2NO34molecule has two azobenzene units, the average molar ratio of Pt-2L(-CD)2NO34to AuNPs is 210:1. 1H NMR Spectra for Compoun
38、ds 2, 3 and LBr Fig. S13 1H NMR spectrum of the compound 2. Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is The Royal Society of Chemistry 201215Fig. S14 1H NMR spectrum of the compound 3. Fig. S15 1H NMR spectrum of the compound LBr. Electronic Supplementary Mater
39、ial (ESI) for Chemical CommunicationsThis journal is The Royal Society of Chemistry 20121613C NMR Spectra for Compounds 2, 3 and LBr Fig. S16 13C NMR spectrum of the compound 2. Fig. S17 13C NMR spectrum of the compound 3. Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journ
40、al is The Royal Society of Chemistry 201217Fig. S18 13C NMR spectrum of the compound LBr. Elemental Analysis Reports for Compounds 2 and LBr Fig. S19 Elemental analysis reports of the compounds 2 and LBr. Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is The Royal So
41、ciety of Chemistry 201218Elemental Composition Reports for Compounds 2, 3 and LBr Fig. S20 Single mass analysis of the compound 2. Fig. S21 Single mass analysis of the compound 3. Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is The Royal Society of Chemistry 201219
42、Fig. S22 Single mass analysis of the compound LBr. FT-IR Spectra for Compounds 1, 2, 3 and LBr Fig. S23 FT-IR spectrum of the compound 1. Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is The Royal Society of Chemistry 201220Fig. S24 FT-IR spectrum of the compound 2.
43、 Fig. S25 FT-IR spectrum of the compound 3. Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is The Royal Society of Chemistry 201221Fig. S26 FT-IR spectrum of the compound LBr. References: S1 X. Ma, Q. Wang, D. Qu, Y. Xu, F. Ji and H. Tian, Adv. Funct. Mater., 2007, 1
44、7, 829. S2 K. C. Grabar, R. G. Freeman, M. B. Hommer and M. J. Natan, Anal. Chem., 1995, 67, 735. S3 (a) H. A. Benesi and J. H. Hildebrand, J. Am. Chem. Soc., 1949, 71, 2703; (b) L. Zhu, D. Zhang, D. Qu, Q. Wang, X. Ma and H. Tian, Chem. Commun., 2010, 46, 2587. S4 (a) H.-Z. Yu, J. Zhang, H.-L. Zhang and Z.-F. Liu, Langmuir, 1999, 15, 16; (b) Q. Ye, J. Fang and L. Sun, J. Phys. Chem. B, 1997, 101, 8221. Electronic Supplementary Material (ESI) for Chemical CommunicationsThis journal is The Royal Society of Chemistry 2012
