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1 Supporting Information A Unique Pair: Ag 40 and Ag 46 Nanoclusters with the Same Surface but Different Cores for Structure-Property Correlation Jinsong Chai, Sha Yang, Ying Lv, Tao Chen, Shuxin Wang, Haizhu Yu,* Manzhou Zhu* Department of Chemistry and Centre for Atomic Engineering of Advanced Materials, Anhui Province Key Laboratory of Chemistry for Inorganic/Organic Hybrid Functionalized Materials, Anhui University, Hefei, Anhui, , China. 1. Materials. All reagents and solvents were commercially available and used without further purification. The silver p-toluenesulfonate (C 7 H 7 AgO 3 S, 98%, metal basis), triphenylphosphine (Ph 3 P, 99%), 2,4-dimethylbenzenethiol (HSPhMe 2, 99%), 2,5-dimethylbenzenethiol (HSPhMe 2, 99%), and sodium cyanoborohydride (NaBH 3 CN, 98%) were received from Aldrich (Shanghai, China). All solvents in the experiment are chromatographically pure and were purchased from Aldrich (Shanghai, China). Pure water was purchased from Wahaha Co. Ltd. All glassware was thoroughly cleaned with aqua regia (HCl: HNO 3 = 3:1, v:v), rinsed with copious pure water. 2. Synthesis of Ag 40 and Ag 46 nanoclusters. Ag 40 has the similar synthetic method as Ag 46. Herein, the synthetic method for Ag 40 is used as an example. 58 mg silver p-toluenesulfonate (0.2 mmol) was mixed with 167 mg PPh 3 (0.64 mmol) and dissolved in 14 ml ethanol. The solution was stirred for 10 mins. Then, 20 μl 2,4-dimethylbenzenethiol was added, 20 mins later, 50 mg NaBH 3 CN was added to the above solution and then the solution was continued to be stirred for 4 hours. The product was collected by centrifugation (Ag 40 nanoclusters are insoluble in ethanol) with the yield of ~1% based on the initial Ag atom. The synthesis of the Ag 46 nanocluster was achieved with the substitution of 2,5-dimethylbenzenethiol by 2,4-dimethylbenzenethiol, and the yield of Ag 46 is 3% based on the initial Ag atom. 3. Conversion from Ag 40 to Ag 46 nanoclusters and the Synthesis of Ag mg Ag 40 nanocluster was dissolved in the mixture solvent (5 ml CH 2 Cl 2 and 5 ml methanol). Then, 50 μl 2,5-dimethylbenzenethiol was added into the above solution, stirring under the room temperature for about 15 minutes. The product is the mixture of Ag 46 nanocluster and Ag 43 nanocluster. These two nanoclusters were separated by acetonitrile (Ag 46 nanocluster can be dissolved in acetonitrile). 4. X-ray Crystallographic Determination of Ag 40, Ag 46 and Ag 43 nanoclusters. The diffraction data of the single crystals were collected on Bruker APEX-II CCD diffractometer using Mo Kα radiation (λ= Å) for these three nanoclusters. The crystal structures were determined by direct methods and refined by using the full-matrix least-squares methods within the ShelXT-2016/6 program (Sheldrick, 2016, for Ag 40 ), helxt program (Sheldrick, 2015, for Ag 46 ) and shelxl program (Sheldrick, 2015, for Ag 43 ). 5. Characterization. Ultraviolet-visible (UV-vis) absorption spectra were recorded on an Agilent 8453 spectrophotometer with CH 2 Cl 2 as solvent. Electrospray ionization mass spectra (ESI-MS) were recorded using a Bruker Q-TOF S1

2 mass spectrometer. The source temperature maintained at 80 o C. The sample was directly infused into the chamber at 5 μl/min. ESI sample was prepared by dissolving it in dichloromethane (0.1 mg/ml). Thermal gravimetric analysis (TGA) was conducted on samples of about 10 mg, under an atmosphere of anhydrous N 2 (flow rate 50 ml/min), using a TG/DTA 6300 analyzer (Seiko Instruments, Inc), with a heating rate of 10 o C/min. 6. Computational method. We performed density functional theory (DFT) and time-dependent DFT (TD-DFT) calculations with BP/TZP method (include scalar relativistic effect) to optimize the geometric structure and simulate the UV/vis spectra of the Ag 40 and Ag To save computing cost, in Ag 40, 2,4-DMBT and PPh 3 were simplified to SMe and PMe 3 ; in Ag 46, 2,5-DMBT and PPh 3 were simplified to SMe and PMe excited singlet states were used in the TD-DFT calculations, and the numerical quality is set to be good. The continuous computational spectra are the sums of Gaussian smoothed individual transitions (width of 0.15 ev), and a correction of 0.2 ev is used to compensate the systematic underestimation of the theoretical calculations on transition energy (compared to the experimental one). All calculations were carried out on ADF software. 4 Figure S1. ESI-MS of the Ag 40 nanocluster. Inset: the measured (black trace) and simulated (green trace) isotopic patterns of [Ag 40 (SPhMe 2 ) 23 (PPh 3 ) 8 KAg] 3+. S2

3 Figure S2. ESI-MS of the Ag 46 nanocluster. Inset: the measured (black trace) and simulated (green trace) isotopic patterns of [Ag 46 (SPhMe 2 ) 24 (PPh 3 ) 8 ] 2+. Figure S3. TGA of the Ag 46 nanocluster. Figure S4. TGA of the Ag 40 nanocluster. S3

4 Figure S5. Full structures of Ag 40 (a) and Ag 46 (b) nanoclusters (Color labels: magenta/cyan/green = Ag, red = S, yellow = P, gray stick = C, and white stick = H). Figure S6. The crystal analysis of Ag 32 (SPhMe 2 ) 24 (PPh 3 ) 8 shell. (a) framework; (b) inner layer; (c) outer layer (d)-(f) the linkage between the inner and outer layer (color labels: light green = Ag in the inner layer, magenta = Ag in the outer layer, yellow = P, red = S; no C or H atoms are shown). S4

5 Figure S7. The Ag-Ag bond lengths distribution in the Ag 40 nanocluster. (Color labels: magenta/cyan = Ag, red = S, yellow = P). Figure S8. The Ag-L bond lengths distribution in the Ag 40 nanocluster. (L=S/P) (Color labels: magenta/cyan = Ag, red = S, yellow = P). S5

6 Figure S9. The Ag-Ag bond lengths distribution in the Ag 46 nanocluster. (Color labels: magenta/green = Ag, red = S, yellow = P). Figure S10. The Ag-L bond lengths distribution in the Ag 46 nanocluster. (L=S/P) (Color labels: magenta/green = Ag, red = S, yellow = P). Figure S11. The frontier orbitals of Ag 46 interpreted with the particle-in-a-box-like jellium states (the numbers denote the number of nodes along the x, y and z dimensions). S6

7 Figure S12. Frontier orbits of singlet Ag 40 (a), triplet Ag 40 (a) and Ag 46 (b) clusters mainly involved in the peaks discussed in paper. Figure S13. Ag 8 kernel and Ag 14 kernel. S7

8 Figure S14. The time-dependent UV-vis spectra of the Ag 40 converting to Ag 46. Figure S15. ESI-MS spectrum of stable product after Ag 40 reaction with 2,5-dimethylbenzenethiol. S8

9 Figure S16. The UV-vis spectra of the converting from Ag 40 to Ag 46. Figure S17. The UV-vis spectrum of Ag 43. S9

10 Figure S18. TGA of the Ag 43 nanocluster. Figure S19. Full structure of Ag 43 nanocluster (Color labels: magenta = Ag, red = S, yellow = P, gray stick = C, and white stick = H). S10

11 Figure S20. The Ag-Ag bond lengths distribution in the Ag 43 nanocluster. (Color labels: gray/magenta/cyan = Ag, red = S, yellow = P). Figure S21. The Ag-L bond lengths distribution in the Ag 43 nanocluster. (L=S/P) (Color labels: gray/magenta/cyan = Ag, red = S, yellow = P). Table S1. The coordination numbers of Ag atoms in different sites of the Ag 40 nanocluster. sites Ag coordinate number Core 5 Shell-inner 6 Shell-outer 4 S11

12 Table S2. The coordination numbers of Ag atoms in different sites of the Ag 46 nanocluster. Sites Ag coordinate number Core(corner) 9 Core (face) 12 Shell-inner 8 Shell-outer 4 S12

13 Table S3. Crystal Data and Structure Refinement for the Ag 40 (2,4-DMBT) 24 (PPh 3 ) 8 nanocluster. Identification code Ag 40 (SC 8 H 9 ) 24 (PC 18 H 15 ) 8 Empirical formula C 336 H 336 Ag 40 P 8 S 24 Formula weight g/mol Temperature 153 K Wavelength Å Crystal system trigonal Space group R 3 _ Unit cell dimensions a= (12) Å α= 90 b= (12) Å β= 90 c= (2) Å γ= 120 Volume 32050(3) Å 3 Z 3 Density (calculated) Mg/m 3 Absorption coefficient mm -1 F(000) Theta range for data collection to Index ranges Reflections collected <=h<=45-45<=k<=45-37<=l<=34 Independent reflections [R(int) = ] Completeness to theta = % Absorption correction Multi scan Data / restraints / parameters / 0 / 615 Goodness-of-fit on F Final R indices [I>2sigma(I)] R1=0.0538, wr2= R indices (all data) R1= , wr2= Largest diff. peak and hole and e.å-3 S13

14 Table S4. Crystal Data and Structure Refinement for the Ag 46 (2,5-DMBT) 24 (PPh 3 ) 8 nanocluster. Identification code Ag 46 (SC 8 H 9 ) 24 (PC 18 H 15 ) 8 Empirical formula C 352 H 354 Ag Cl 4 O 6 P 8 S 26 Formula weight g/mol Temperature K Wavelength Å Crystal system triclinic Space group P 1 _ Unit cell dimensions a= (8) Å α= (2) b= (8) Å β= (2) c= (8) Å γ= (2) Volume (6) Å 3 Z 1 Density (calculated) Mg/m 3 Absorption coefficient mm -1 F(000) 5279 Theta range for data collection to Index ranges -29<=h<=29-29<=k<=29-29<=l<=30 Reflections collected Independent reflections [R(int) = ] Completeness to theta = % Absorption correction Multi scan Data / restraints / parameters / 3821 / 1728 Goodness-of-fit on F Final R indices [I>2sigma(I)] R1=0.0820, wr2= R indices (all data) R1= , wr2= Largest diff. peak and hole and e.å-3 S14

15 Table S5. Crystal Data and Structure Refinement for the Ag 43 (2,5-DMBT) 25 (PPh 3 ) 4 nanocluster. Identification code Ag 43 (SC 8 H 9 ) 25 (PC 18 H 15 ) 4 Empirical formula C 272 H 279 Ag 43 P 4 S 25 Formula weight g/mol Temperature 170 K Wavelength Å Crystal system monoclinic Space group P 2 _ ybc Unit cell dimensions a= (3) Å α= 90 b= (3) Å β= (6) c= (8) Å γ= 90 Volume 35079(8) Å 3 Z 4 Density (calculated) Mg/m 3 Absorption coefficient mm -1 F(000) Theta range for data collection 2.25 to Index ranges -32<=h<=33-20<=k<=26-74<=l<=74 Reflections collected Independent reflections [R(int) = 0.295] Completeness to theta = % Absorption correction Multi scan Data / restraints / parameters / 5 / 3161 Goodness-of-fit on F Final R indices [I>2sigma(I)] R1=0.0781, wr2= R indices (all data) R1= , wr2= Largest diff. peak and hole and e.å Andreas, D. Chem. Rev. 2005, 105, Perdew, J. P.; Burke, K.; Ernzerhof, M. Phys. Rev. Lett. 1996, 77, Jochen, A. J. Chem. Phys. 2012, 136, Velde, G.; Bickelhaupt, F. M.; Baerends, E. J.; Guerra, C. F.; Gisbergen, S. J. A.; Snijders, J. G.; Ziegler, T. J. Comput. Chem. 2001, 22, S15