Embryonic Growth of Face Center Cubic Silver Nanoclusters Shaped in Nearly Perfect Half Cubes and Cubes

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1 Supporting Information for Embryonic Growth of Face Center Cubic Silver Nanoclusters Shaped in Nearly Perfect Half Cubes and Cubes Huayan Yang,, Juanzhu Yan,, Yu Wang, Haifeng Su, Lars Gell, Xiaojing Zhao, Chaofa Xu, Boon K. Teo, *, Hannu Häkkinen, *, Nanfeng Zheng *, State Key Laboratory for Physical Chemistry of Solid Surfaces, Collaborative Innovation Center of Chemistry for Energy Materials, and Engineering Research Center for Nano-Preparation Technology of Fujian Province, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen , China Departments of Physics and Chemistry, Nanoscience Center, University of Jyväskylä, FI Jyväskylä, Finland H. Y. Y and J. Z. Y contributed equally to this work. Experimental Details Reagents: 3,4-Difluorothiophenol (HSPhF2, purity 96%), triphenylphosphine (PPh3, purity 98%), tributylphosphine (P n Bu3, purity 99%), tetrabutylammonium tetraphenylborate (PPh4Br, purity 99%), and tetrabutylammonium tetraphenylborate ( n Bu4N BPh4, purity 98%) were purchased from J&K Scientific Ltd. (Beijing, China), Silver tetrafluoroborate (AgBF4, purity 99%), Sodium borohydride (NaBH4, purity 98%), dichloromethane (CH2Cl2, A.R.), and methanol (CH3OH, A.R.) were purchased from Sinopharm Chemical Reagent Co. Ltd. (Shanghai, China). The water used in all experiments was ultrapure. All reagents were used as received without further purification. Synthesis of [Ag38(SPhF2)26(P n Bu3)8]: 40 mg silver tetrafluoroborate (AgBF4) was dissolved in a mixed solvent of dichloromethane and methanol. After the solution was cooled to 0 C in an ice bath, 16 μl tributylphosphine (P n Bu3) and 16 μl 3,4- difluorothiophenol (HSPhF2) were then added to the solution. After 20-min stiring, 2 ml NaBH4 aqueous solution (80 mg/ml) and 100 μl triethylamine were added quickly S1

2 under vigorous stirring. The reaction was aged for 12 h at 0 C. The aqueous phase was then removed and the organic phase was washed several times with water. Black block crystals were crystallized from CH2Cl2/hexane after 6 days at 4 C. Based on the single crystals separated from the reaction, the yield was estimated to be 6 % based on Ag. Synthesis of [Ag38(SPhF2)26(PPh3)8]: 40 mg silver tetrafluoroborate (AgBF4) was dissolved in a mixed solvent of dichloromethane and methanol. After the solution was cooled to 0 C in an ice bath, 20 mg triphenylphosphine and 16 μl 3,4-difluorothiophenol (HSPhF2) were then added to the solution. After 20-min stirring, 2 ml NaBH4 aqueous solution (80 mg/ml) and 100 μl triethylamine were added quickly under vigorous stirring. The reaction was aged for 12 h at 0 C. The aqueous phase was then removed and the organic phase was washed several times with water. Black block crystals were crystallized from CH2Cl2/hexane after after 6 days at 4 C. Based on the single crystals separated from the reaction, the yield was estimated to be 4 % based on Ag. Elemental Analysis Calcd (found) for C300H198F52P8S26Ag38 (fw = ): C, (38.7); H, 2.00 (3.0); F, 9.91; P, 2.49; S, 8.36; Ag, Synthesis of [Ag63(SPhF2)36(P n Bu3)8](BPh4): 40 mg silver tetrafluoroborate (AgBF4) was dissolved in a mixed solvent of dichloromethane and methanol. After the solution was cooled to 0 C in an ice bath, 10 μl tributyl phosphine (P n Bu3), 20 mg tetrabutylammonium tetraphenylborate ( n Bu4B PPh4), and 16 μl 3,4-difluorothiophenol (HSPhF2) were then added to the solution. After 20-min stirring, 2 ml NaBH4 aqueous solution (80 mg/ml) and 100 μl triethylamine were added quickly under vigorous stirring. The reaction was aged for 12 h at 0 C. The aqueous phase was then removed and organic phase was washed several times with water. The solution was centrifuged for 5 min at rpm. The brown supernatant was subjected to cryopreservation in the dark at 4 C. Black block crystals were obtained after 1 day. Based on the single crystals separated from the reaction, the yield was estimated to be 14 % based on Ag. Elemental Analysis Calcd (found) for C336BH344F72P8S36Ag63 (fw = ): C, (26.9); B, 0.077, H, 2.48 (3.4); F, 9.80; P, 1.76; S, 8.27; Ag, Similarly, crystals of [Ag63(SPhF2)36(PPh3)8]Br can be obtained following the same procedure except that P n Bu3 and n Bu4B PPh4 were substituted by PPh3 and PPh4Br, respectively. S2

3 Characterizations: The UV-Vis spectra were collected by Shimadzu UV-2550 Spectrophotometer with dichloromethane or 1,2-dichloroethane as solvent. Elemental analysis was performed on a Vario EL III (Germany). X-ray single-crystal analysis: The diffraction data of the single crystals grown from the solutions of [Ag38(SPhF2)26(P n Bu3)8], [Ag38(SPhF2)26(PPh3)8] and [Ag63(SPhF2)36(P n Bu3)8](BPh4) and [Ag63(SPhCF3)36(PPh3)8]Br nanoclusters were collected on an Agilent Technologies SuperNova system X-ray single-crystal diffractometer with Mo (λ = Å) and Cu Kα radiation (λ = Å) at 100 K. The data were processed using CrysAlisPro. 1 The structure was solved and refined using Full-matrix least-squares based on F 2 using ShelXT, 2 ShelXL 3 in Olex2, 4 and Shelxle. 5 Detailed crystal data and structure refinements for both compounds are given in Table S1-S4. Computational Methods: We used density-functional theory (DFT) with projector augmented waves (PAW) as implemented in the real-space grid code-package GPAW. 6-8 Scalar relativistic effects for silver were included in the used PAW setup. Total energy calculation and structure optimization was carried out by using the Perdew-Burke- Ernzerhof (PBE) 9 exchange-correlation functional, real space grid spacing of 0.2 Å, and 0.05 ev/ Å convergence criteria for the residual forces acting on atoms. Angular momentum resolved projected density of state analysis (PDOS) was performed by projecting the Kohn-Sham orbitals to the center of mass of the full cluster. 10 The optical absorption spectrum for the optimized structures were calculated by using the linear response time-dependent DFT (LR-TDDFT) as implemented in GPAW. 11 The GLLB (Gritsenko van Leeuwen van Lenthe Baerends) functional 12 was used for the exchange-correlation kernel, and the spacing in the real space grid was 0.25 Å. The plotted continuous absorption spectra are sums of the individual absorption lines folded with a Gaussian broadening of 0.05 ev. S3

4 Table S1 Crystal data and structure refinement for [Ag38(SPhF2)26(P n Bu3)8]. Identification code [Ag38(SPhF2)26(P n Bu3)8] Empirical formula C256H294Ag38Cl8F52P8S26 Formula weight Temperature/K (10) Crystal system monoclinic Space group P21/n a/å (2) b/å (2) c/å (3) α/ 90 β/ (9) γ/ 90 Volume/Å (3) Z 2 ρcalc g/cm μ/mm F(000) Crystal size/mm Radiation Cu Kα (λ = Å) 2 range for data collection/ to Index ranges -20 h 26, -24 k 24, -34 l 34 Reflections collected Independent reflections [Rint = , Rsigma = ] Data/restraints/parameters 23785/123/1686 Goodness-of-fit on F Final R indexes [I>=2σ (I)] R1 = , wr2 = Final R indexes [all data] R1 = , wr2 = Largest diff. peak/hole / e Å /-3.61 S4

5 Table S2 Crystal data and structure refinement for [Ag38(SPhF2)26(PPh3)8]. Identification code [Ag38(SPhF2)26(PPh3)8] Empirical formula Ag38S26C208F52H214P8Cl16 Formula weight Temperature/K Crystal system triclinic Space group P-1 a/å b/å c/å α/ β/ γ/ Volume/Å Z 1 ρcalcg/cm μ/mm F(000) Crystal size/mm Radiation Mo Kα (λ = Å) 2 range for data collection/ to Index ranges -28 h 25, -28 k 28, -29 l 29 Reflections collected Independent reflections [Rint = , Rsigma = ] Data/restraints/parameters 38392/0/1832 Goodness-of-fit on F Final R indexes [I>=2σ (I)] R1 = , wr2 = Final R indexes [all data] R1 = , wr2 = Largest diff. peak/hole / e Å /-1.79 S5

6 Table S3 Crystal data and structure refinement for [Ag63(SPhF2)36(P n Bu3)8]Br. Identification code [Ag63(SPhF2)36(P n Bu3)8]Br Empirical formula C315Ag63BrF72P8S36 Formula weight Temperature/K (10) Crystal system Trigonal Space group R-3 a/å (4) b/å (4) c/å (2) α/ 90 β/ 90 γ/ 120 Volume/Å (3) Z 6 ρcalcg/cm μ/mm F(000) Crystal size/mm Radiation Cu Kα (λ = Å) 2 range for data collection/ to Index ranges -28 h 28, -23 k 28, -130 l 130 Reflections collected Independent reflections [Rint = , Rsigma = ] Data/restraints/parameters 21696/54/1399 Goodness-of-fit on F Final R indexes [I>=2σ (I)] R1 = , wr2 = Final R indexes [all data] R1 = , wr2 = Largest diff. peak/hole / e Å /-3.09 S6

7 Table S4 Crystal data and structure refinement for [Ag63(SPhF2)36(P n Bu3)8](BPh4). Identification code [Ag63(SPhF2)36(P n Bu3)8](BPh4) Empirical formula C379H345Ag63BCl6F71.48P8S36 Formula weight Temperature/K (10) Crystal system trigonal Space group R-3 a/å (5) b/å (5) c/å (17) α/ 90 β/ 90 γ/ 120 Volume/Å (3) Z 6 ρcalcg/cm μ/mm F(000) Crystal size/mm Radiation Cu Kα (λ = Å) 2Θ range for data collection/ to Index ranges -21 h 26, -21 k 31, -142 l 131 Reflections collected Independent reflections [Rint = , Rsigma = ] Data/restraints/parameters 28186/27/1562 Goodness-of-fit on F Final R indexes [I>=2σ (I)] R1 = , wr2 = Final R indexes [all data] R1 = , wr2 = Largest diff. peak/hole / e Å /-2.38 S7

8 Table S5 A summary of average bond lengths of important bonds in 1, 2 2, 2 3. Cluster Bond Length(Å) # Ag(C)-Ag(SS) Ag(SS)-Ag(SS) Ag(SS)-Ag(S) Ag(S)-Ag(S) Ag(S)-Ag(P) Ag-S Ag-P Ag(P) refers to Ag atoms at the eight corners of each cube Ag(S) refers to surface Ag atoms that are capped by thiolates Ag(SS) refers to sub-surface Ag atoms that are next to surface Ag atoms Ag(C) refers to the central Ag atom Neither coordination of thiolate or phosphine is revealed on Ag(C) and Ag(SS). The bond lengths in the table are defined as follows: Ag P bond length between Ag and phosphine Ag S bond length between Ag and thiolate Ag(S)-Ag(P) bond length between phosphine-terminated Ag and its adjacent Ag Ag(S)-Ag(S) bond length between surface Ag atoms that are capped by thiolates Ag(SS)-Ag(S) bond length between surface Ag and Ag atoms at the subsurface shell Ag(SS)-Ag(SS) bond length between subsurface Ag atoms Ag(C)-Ag(SS) bong length between the central Ag and the subsurface Ag atoms All data are summarized from the single-crystal structures of [Ag14(SPhF2)12(PPh3)8] (1), [Ag38(SPhF2)26(P n Bu3)8] (2 2 ) and [Ag63(SPhF2)36(P n Bu3)8](BPh4) (2 3 ). S8

9 Figure S1. The UV-Vis spectra of as-prepared Ag38 and Ag63 in CH2Cl2 solution. Figure S2. The overall structure of the [Ag14(SPhF2)12(PPh3)8] cluster. Color codes: blue sphere, Ag; yellow sphere, S; red sphere, P; cyan sphere, F; grey stick/sphere, C; white sphere, H. The picture is produced from the CIF file published in Ref. 42. S9

10 Figure S3. The overall structure of the [Ag38(SPhF2)26(P n Bu3)8] cluster. Color codes: blue sphere, Ag; yellow sphere, S; red sphere, P; cyan sphere, F; grey stick/sphere, C; white sphere, H. Figure S4. The overall structure of the [Ag63(SPhF2)36(P n Bu3)8] + cluster. Color codes: blue sphere, Ag; yellow sphere, S; red sphere, P; cyan sphere, F; grey stick/sphere, C; white sphere, H. S10

11 Figure S5. The overall structure of the [Ag38(SPhF2)26(PPh3)8] cluster. Color codes: blue sphere, Ag; yellow sphere, S; red sphere, P; cyan sphere, F; grey stick/sphere, C. S. All hydrogen atoms are omitted for clarify. Figure S6. The overall structure of the yet-unknown Rubik s cube, predicted to have the formulation of [Ag172(SR)72(PR 3)8]. Color codes: blue sphere, Ag; yellow sphere, S; red sphere, P. All fluorine, carbon and hydrogen atoms are omitted for clarify. S11

12 Figure S7. Projected local density of states (PDOS) for the [Ag38(SPhF2)26(P n Bu3)8] cluster. The colours denoted various angular momentum components in the spherical decomposition of the Kohn-Sham states. The HOMO-LUMO energy gap (0.67 ev) is centered around zero. Figure S8. Same analysis as in Fig. S7 but for the [Ag63(SPhF2)36(P n Bu3)8] + cluster. Note the tiny (0.07 ev) HOMO-LUMO energy gap, centered around zero energy. S12

13 Figure S9. UV-Vis spectra of 1,2-dichloroethane solutions of (a) [Ag38(SPhF2)26(PPh3)8], (b) [Ag38(SPhF2)26(P n Bu3)8], and (c) [Ag63(SPhF2)36(P n Bu3)8] + heated in air at 50 C for different time periods. (d) The relative changes of the absorbance at 510 nm for Ag38 and 471 nm for Ag63 with heating time. S13

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