supplementary materials for - science advances · supplementary materials for thiacalix[4]arene:...
TRANSCRIPT
advances.sciencemag.org/cgi/content/full/2/8/e1600323/DC1
Supplementary Materials for
Thiacalix[4]arene: New protection for metal nanoclusters
Zong-Jie Guan, Jiu-Lian Zeng, Zi-Ang Nan, Xian-Kai Wan, Yu-Mei Lin, Quan-Ming Wang
Published 12 August 2016, Sci. Adv. 2, e1600323 (2016)
DOI: 10.1126/sciadv.1600323
The PDF file includes:
Supplementary Materials and Methods
table S1. Crystal data and structure refinement for 1.
fig. S1. The experimental and simulated PXRD spectra of 1.
fig. S2. Infrared spectrum of 1.
fig. S3. EDX analysis of 1.
fig. S4. 1H nuclear magnetic resonance spectrum of 1 (CD3COCD3).
fig. S5. The coordination modes of alkynyl ligands in 1.
fig. S6. The main frontier orbitals of Ag34, Ag35, and Ag36 clusters.
fig. S7. The experimental absorption spectra in comparison with calculated
spectra of Ag34 (left) and Ag36 (right).
Other Supplementary Material for this manuscript includes the following:
(available at advances.sciencemag.org/cgi/content/full/2/8/e1600323/DC1)
CIF files
Supplementary Materials
Supplementary Materials and Methods:
Chemicals. 3,3-Dimethyl-1-butyne (HC≡CBut, 98%) was purchased from J&K,
p-tert-Butylthiacalix[4]arene (H4L) was purchased from TCI, sodium borohydride
(NaBH4, 98%) and other reagents were purchased from Sinopharm Chemical
ReagentCo. Ltd. (Shanghai, China).
Instruments. ESI-MS was performed on an Agilent Technologies ESI-TOF-MS.
UV-Vis absorption spectra were recorded on Cary 5000. FTIR spectra were recorded
on Nicolet Avatar 380 with samples prepared as KBr pellets. Energy-dispersive X-ray
spectroscopy (EDX) analysis was performed on a Hitachi S-4800 microscope
operated at 20kV. Inductively coupled plasma-atomic emission spectrometry
(ICP-AES) measurements were performed using a Thermo Electron IRIS Intrepid II
XSP spectrometer. X-ray powder diffractometry study of the 1 was performed on a
Panalytical X-Pert pro diffractometer with Cu Kα radiation. The transmission electron
microscopy (TEM) image was obtained using a Tecnai F30 microscopy. The operating
voltage was 300 kV. NMR data were recorded on a Bruker Avance II spectrometer
(500 MHz). Intensity data of 1 were collected on an Agilent SuperNova Dual system
(Mo K). Absorption corrections were applied by using the program CrysAlis
(multi-scan). The structure was solved by direct methods, and non-hydrogen atoms
except for solvent molecules and the disordered SbF6 ions were refined
anisotropically by least-squares on F2 using the SHELXTL program. One A level alert
in CIFCheck report (VERY LARGE Solvent Accessible VOID(S) in
Structure) is due to the existence of unresolved solvent molecules.
Synthesis of [Ag35(H2L)2(L)(C≡CBut)16](SbF6)3 (1). To 3.0 mL methanol mixture of
AgC≡CBut (0.1 mmol) and AgSbF6 (0.1 mmol), a freshly prepared solution of NaBH4
(0.02 mmol in 1 mL of ethanol) was added dropwise under vigorous stirring. The
solution color changed from colorless to pale brown and finally to dark brown. Then
3.0 mL CHCl3 solution containing H4L (0.02 mmol) was added to the mixture and
followed by addition of triethylamine (10 uL). Then the reaction continued for 20 h at
room temperature in air in the dark. The mixture was evaporated to dryness to give a
dark solid. This solid was suspended in 8 mL n-pentane, and centrifuged for 2 min at
10000 r/min, then the supernatant was removed. The residue solid was dissolved in a
mixture of toluene (2 mL) and methylene chloride (0.5 mL), and the solution was
centrifuged for 3 min at10000 r/min. The supernatant was collected and transferred to
a test tube of 1 cm diameter, then ca. 8 mL n-pentane was layered on to the solution.
After the solution was stored at 4 °C for about one week, and sheet-like dark crystals
deposited in 11% yield (5.1 mg, based on Ag). Elemental analysis (EDX) for 1, calcd
(%): Ag, 70.0; Sb, 6.0; S, 24.0; found: Ag, 69.1; Sb, 6.0; S, 24.9. IR: 2012 cm-1
(C≡CBut); 1631, 434, 261, 1238, 727, 830 cm-1 (H4L).
Experimental procedure for cluster transformation from Ag35 to Ag34 or Ag36
species:The sample of [Ag35(H2L)2(L)(C≡CBut)16](SbF6)3 (1) (0.6 mg) was dissolved
in 1 mL of methylene chloride, and divided into four parts (A to D). Each part was
treated by the following procedures and monitored by ESI-MS spectrometry
immediately. (A) Pure solution of 1 (Fig. 4A); (B) Addition of 2 equiv NEt3 and 1
equiv AgSbF6 salt (Fig.4B). (C) Addition of 2 equiv NEt3 (Fig. 4C). (D) Addition of 2
equiv HBF4 (Fig. 4D).
Theoretical calculations.
Density functional theory (DFT) calculations were performed with the quantum
chemistry program Turbomole V6.4. To save computational time, we replaced tBu on
BTCA with H, tBu on tBuC≡C with CH3. The def2-SV(P) basis sets were used for C,
H, O, S, Ag. Geometry optimization and time-dependent DFT calculation of the
UV-vis absorption spectra were done with the functional of Becke, Perdew 86.
Supplementary Table and Figures
table S1. Crystal data and structure refinement for 1.
Empirical formula C226H4Ag35Cl6F18O12S12Sb3
Formula weight 7990.39
T, K 101(2)
Wavelength(Å) 0.71073
Crystal system Triclinic
Space group P-1
Unit cell dimensions a = 21.7517(3) Å α = 91.3037(12)°
b = 22.6953(4) Å β = 101.9766(12)°
c = 34.1752(4) Å γ = 118.0381(17)°
Volume 14424.7(4) Å3
Z 2
Density (calculated) 1.840 g/cm3
Absorption coefficient 2.785 mm-1
F(000) 7420.0
Theta range for data collection 3.30 to 25.12°
Index ranges -23<=h<=25
-26<=k<=27
-40<=l<=40
Reflections collected 109699
Independent reflections 51338 [R(int) = 0.0406]
Absorption correction multi-scan
Data / restraints/parameters 51338 / 606 / 2850
Goodness-of-fit on F2 1.026
Final Rindices[I>2sigma(I)] R1 = 0.0720, wR2 = 0.2080
R indices (all data) R1 = 0.0988, wR2 = 0.2366
Largest diff. peak, hole 3.497 and -3.608 eÅ3
fig. S1. The experimental and simulated PXRD spectra of 1.
fig. S2. Infrared spectrum of 1.
fig. S3. EDX analysis of 1.
fig. S4. 1H nuclear magnetic resonance spectrum of 1 (CD3COCD3).
fig. S5. The coordination modes of alkynyl ligands in 1, three in μ4-η1,η1,η1,η2 (red), four in
μ4-η1,η1,η2,η2 (yellow), six in μ3-η1 (blue), two in μ3-η1,η1,η2 (orange) and one in μ3-η1,η2,η2 (sky
blue). All hydrogen atoms are omitted for clarity.
fig. S6. The main frontier orbitals of Ag34, Ag35, and Ag36 clusters.
fig. S7. The experimental absorption spectra in comparison with calculated spectra of Ag34
(left) and Ag36 (right).