Buckycatchers. Supporting Information

Transcription

1 Coinage Metal Pyrazolates [(3,5-(CF3)2Pz)M]3 (M = Au, Ag, Cu) as Buckycatchers Naleen B. Jayaratna, a Marilyn M. Olmstead, b Boris I. Kharisov, c and H. V. Rasika Dias, *,a a Department of Chemistry and Biochemistry, The University of Texas at Arlington, Arlington, TX , USA b Department of Chemistry, University of California, One Shields Ave., Davis, CA c Universidad Autónoma de Nuevo León, Ciudad Universitaria, San Nicolás de los Garza, N.L., Mexico Supporting Information Experimental All manipulations were carried out under an atmosphere of purified nitrogen using standard Schlenk techniques or in a MBRAUN LABMaster glovebox equipped with a -10 C refrigerator. Solvents were purchased from commercial sources, and purified by conventional methods prior to use. Glassware was oven-dried at 150 C overnight. NMR spectra were recorded at 23 C (unless specified) on a JEOL Eclipse 500 spectrometer ( 1 H, MHz; 13 C, MHz, 19 F, ). Proton and carbon chemical shifts are reported in ppm, and referenced using the residual proton or carbon S1

2 signals of the deuterated solvent. 19 F NMR values were referenced to external CFCl3. Elemental analyses were performed at Intertek QTI laboratory (Whitehouse, NJ). Melting points were obtained on a Mel-Temp II apparatus. C60 was purchased from Sigma Aldrich. [(3,5-(CF3)2Pz)Cu]3 [Cu3], [(3,5-(CF3)2Pz)Ag]3 [Ag3], [(3,5-(CF3)2Pz)Au]3 [Au3] were prepared as reported previously. 1,2 Thermo gravimetric analysis was performed in a Shimadzu TGA-51 analyzer using a platinum crucible. Prior to the experiments, the thermo gravimetric equipment was calibrated using the process described in the Shimadzu Instruction Manual. {C60[Cu3]4} : [(3,5-(CF3)2Pz)Cu]3 ([Cu3], 200 mg, 0.25 mmol) was dissolved in 10 ml of carbon disulfide and transferred to a C60 solution (48 mg, mmol dissolved in 35 ml of carbon disulfide) using a cannula. The resulting mixture was covered with aluminum foil to protect from light, stirred for 1 hour, warmed slightly to redissolve minor precipitate, and kept at room temperature overnight to obtain dark purple (almost black to naked eye), X-ray quality crystals of {C60[Cu3]4}. The supernatant was collected and the solvent was reduced to half the original volume and the mixture was kept at room temperature to get the second crop of crystals of the product. This process could be repeated once more to get a third crop. The combined product was dried under reduced pressure to get 225 mg of {C60[Cu3]4} (92% yield based on [Cu3]). Mp: decomposition started ca. 280 C and completely decomposed ca 315 C (Metallic copper deposition observed). Anal. Calc. for C120H12N24F72Cu12: C, 36.77; H, 0.31; N, Found: C, 36.46; H, 0.19; N, H NMR (CS2/CDCl3, 2:1): δ 7.01 (s). 19 F NMR S2

3 (CS2/CDCl3, 2:1): δ (s). 13 C{ 1 H} NMR (CS2/CDCl3, 2:1): δ (s, CH), (q, 1 J(C,F) = Hz, CF3), (s, C60) (m, CCF3). {C60[Ag3]4} : [(3,5-(CF3)2Pz)Ag]3 ([Ag3], 93 mg, 0.10 mmol) was dissolved in 4 ml of carbon disulfide and transferred to a C60 solution (18 mg, mmol dissolved in 8 ml of carbon disulfide) using a cannula. This mixture was covered with aluminum foil to protect from light and stirred for 2 hours. The resulting mixture was warmed slightly to dissolve minor precipitate and kept at room temperature to obtain X-ray quality dark purple (almost black to naked eye) crystals of {C60[Ag3]4}. Crystals were separated and the solution was concentrated under reduced pressure (~ half the original volume) and kept at room temperature to collect the second crop of crystals. A third crop of the crystals was obtained following a similar process (combined crops: 100 mg. 90% yield based on [Ag3]). Mp: decomposition started ca. 270 C and decomposed completely ~280ºC. Anal. Calc. for C120H12N24F72Ag12: C, 32.37; H, 0.27; N, Found: C, 32.15; H, 0.19; N, H NMR (CS2/CDCl3, 2:1): δ 7.03 (s), 19 F NMR (CS2/CDCl3, 2:1): δ (s). 13 C{ 1 H} NMR (CS2/CDCl3, 2:1): δ (s, CH), (q, 1 J(C,F) = Hz, CF3), (s, C60) (q, 2 J(C,F) = 36.9 Hz, CCF3). S3

4 1 H NMR of {C60[Ag3]4} in 2:1 mixture of CS2:CDCl3 S4

5 19 F NMR of {C60[Ag3]4} in 2:1 mixture of CS2:CDCl3 S5

6 13 C NMR of {C60[Ag3]4} in 2:1 mixture of CS2:CDCl3 {C60[Au3]4} : [(3,5-(CF3)2Pz)Au]3 ([Au3], 120 mg, 0.10 mmol) was dissolved in 25 ml of benzene and transferred to a C60 solution (18 mg, mmol dissolved in 4 ml of carbon disulfide) using a cannula. The resulting solution was covered with aluminum foil to protect from light, stirred for 1 hour, and then concentrated to ca. 5 ml and kept overnight at room temperature to obtain dark purple crystalline solid of {C60[Au3]4} (115 mg. 83% yield based on [Au3]). X-ray quality crystals (reddish - dark purple but S6

7 almost black to naked eye) were obtained from 1:20 carbon disulfide/benzene solution at 5 C. Mp: decomposition started ca 270 C and a gold mirror was formed inside the capillary tube ca 280 C preventing further analysis. Anal. Calc. for C120H12N24F72Au12: C, 26.11; H, 0.22; N, Found: C, 26.19; H, 0.39; N, H NMR (C6D6): δ 6.49 (s), 19 F NMR (C6D6): δ (s). 13 C{ 1 H} NMR (C6D6): only selected signals (still weak) were observed due to low solubility, δ (s, CH), (s, C60). X-ray crystallographic data: A suitable crystal covered with a layer of hydrocarbon/paratone-n oil was selected and mounted on a Cryo-loop, and immediately placed in the low temperature nitrogen stream. The X-ray intensity data for {C60[M3]4} were measured at 100(2) K on a Bruker D8 Quest with a Photon 100 CMOS detector equipped with an Oxford Cryosystems 700 series cooler, a Triumph monochromator, and a Mo Kα fine-focus sealed tube (λ = Å). Intensity data were processed using the Bruker ApexII program suite. All the calculations for the structure determination were carried out using the SHELXTL package (version 6.14). Initial atomic positions were located by direct methods using XS, and the structures of the compounds were refined by the leastsquares method using SHELXL. 3 Absorption corrections were applied by using SADABS. All the non-hydrogen atoms were refined anisotropically. X-ray structural figures were generated using Olex2. 4 Further details are given in cif files. All three {C60[M3]4} adducts involving copper, silver and gold crystallize in cubic, Fd3 c space group (No. 228). The {C60[Cu3]4}, {C60[Ag3]4}, and {C60[Au3]4} are iso- S7

8 morphous and have cell dimensions consistent with the sizes of their covalent radii (i.e., Cu<Au<Ag in which silver is the largest member of the coinage metal family and has the largest unit cell volume). The C60 cage of {C60[M3]4} resides on a crystallographic special position of 23 symmetry (Wyckoff site symmetry a in origin choice 2). Five C atoms were located in the Fourier map. Subsequently, a C60 group taken from a previous structure 5 was mapped to these atoms and refinement proceeded with the C60 as a rigid group with occupancy of 1/12 and PART -1. A restraint was applied to the isotropic thermal parameters of the 60 cage C atoms (SIMU 0.004) due to the correlation effects of the close C C positions at this high symmetry. The moiety formula was chosen to emphasize the 1:4 ratio of C60 to the pyrazolate trimer [M3] in {C60[M3]4}. The dimer of trimer units of [(3,5-(CF3)2Pz)M]3 [M3] also sits on a special position. The asymmetric unit contains (3,5-(CF3)2Pz)M fragment and the hexanuclear [M3]2 is generated by applying mutually perpendicular 3-fold and 2-fold rotation operations. One of the CF3 groups was disordered into two orientations in the copper and silver adducts. S8

9 Table S1. Crystal data and structure refinement for {C60[Cu3]4}. Identification code rad232_0m Empirical formula Formula weight Temperature/K 100(2) Crystal system Space group C120H12Cu12F72N24 cubic Fd-3c a/å (3) b/å (3) c/å (3) α/ 90 β/ 90 γ/ 90 Volume/Å (12) Z 16 ρcalcg/cm μ/mm F(000) Crystal size/mm Radiation MoKα (λ = ) 2Θ range for data collection/ to Index ranges -44 h 44, -44 k 44, -44 l 44 Reflections collected Independent reflections 1975 [Rint = , Rsigma = ] Data/restraints/parameters 1975/606/521 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 /-0.69 Table S2. Bond Lengths for {C60[Cu3]4}. Atom Atom Length/Å Atom Atom Length/Å Cu1 N (6) C20 C Cu1 N (6) C21 C Cu1 Cu (17) C22 C Cu1 Cu (15) C22 C S9

10 Cu1 Cu (15) C23 C F1 C (8) C23 C F2 C (8) C24 C F3 C (8) C25 C F1A C (8) C25 C F2A C (8) C26 C F3A C (7) C27 C F4 C (9) C27 C F5 C (9) C28 C F6 C (9) C29 C N1 C (8) C29 C N1 N (8) C30 C N2 C (9) C31 C N2 Cu (6) C31 C C61 C (11) C32 C C61 C (11) C33 C C62 C (10) C33 C C63 C (10) C34 C C1 C C35 C C1 C C35 C C1 C C36 C C2 C C37 C C2 C C37 C C3 C C38 C C3 C C39 C C4 C C40 C C4 C C40 C C5 C C41 C C5 C C41 C C6 C C42 C C7 C C43 C C7 C C44 C C8 C C44 C C8 C C45 C C9 C C46 C C10 C C46 C S10

11 C10 C C47 C C11 C C48 C C11 C C49 C C12 C C49 C C13 C C50 C C13 C C51 C C14 C C51 C C15 C C52 C C15 C C53 C C16 C C54 C C16 C C55 C C17 C C55 C C18 C C56 C C18 C C57 C C19 C C58 C C20 C C59 C /2+Y,1/4-Z,3/4-X; 2 1/4+Z,-Y,-1/4+X; 3 3/4-Z,-1/2+X,1/4-Y Table S3. Bond Angles for {C60[Cu3]4}. Atom Atom Atom Angle/ Atom Atom Atom Angle/ N1 Cu1 N (3) C8 C24 C N1 Cu1 Cu (17) C25 C24 C N2 1 Cu1 Cu (19) C26 C25 C N1 Cu1 Cu (18) C26 C25 C N2 1 Cu1 Cu (17) C24 C25 C Cu1 2 Cu1 Cu (2) C25 C26 C N1 Cu1 Cu (18) C25 C26 C N2 1 Cu1 Cu (17) C27 C26 C Cu1 2 Cu1 Cu (5) C45 C27 C Cu1 3 Cu1 Cu C45 C27 C C63 N1 N (6) C28 C27 C C63 N1 Cu (5) C29 C28 C N2 N1 Cu (4) C29 C28 C C61 N2 N (6) C27 C28 C S11

12 C61 N2 Cu (5) C28 C29 C N1 N2 Cu (4) C28 C29 C N2 C61 C (7) C30 C29 C N2 C61 C (6) C13 C30 C C62 C61 C (6) C13 C30 C C63 C62 C (6) C31 C30 C N1 C63 C (6) C32 C31 C N1 C63 C (6) C32 C31 C C62 C63 C (7) C30 C31 C F1 C64 F (10) C31 C32 C F2A C64 F3A 108.2(8) C31 C32 C F2A C64 F1A 106.6(8) C33 C32 C F3A C64 F1A 105.6(8) C50 C33 C F1 C64 F (10) C50 C33 C F3 C64 F (9) C34 C33 C F1 C64 C (10) C35 C34 C F2A C64 C (8) C35 C34 C F3 C64 C (10) C33 C34 C F3A C64 C (7) C34 C35 C F1A C64 C (7) C34 C35 C F2 C64 C (9) C52 C35 C F5 C65 F (7) C18 C36 C F5 C65 F (7) C18 C36 C F4 C65 F (7) C37 C36 C F5 C65 C (6) C38 C37 C F4 C65 C (6) C38 C37 C F6 C65 C (6) C36 C37 C C2 C1 C C37 C38 C C2 C1 C C37 C38 C C9 C1 C C20 C38 C C1 C2 C C40 C39 C C1 C2 C C40 C39 C C12 C2 C C38 C39 C C4 C3 C C39 C40 C C4 C3 C C39 C40 C C2 C3 C C54 C40 C S12

13 C3 C4 C C42 C41 C C3 C4 C C42 C41 C C5 C4 C C56 C41 C C6 C5 C C41 C42 C C6 C5 C C41 C42 C C4 C5 C C23 C42 C C5 C6 C C44 C43 C C5 C6 C C44 C43 C C7 C6 C C25 C43 C C21 C7 C C43 C44 C C21 C7 C C43 C44 C C6 C7 C C57 C44 C C24 C8 C C27 C45 C C24 C8 C C27 C45 C C7 C8 C C46 C45 C C10 C9 C C47 C46 C C10 C9 C C47 C46 C C1 C9 C C45 C46 C C9 C10 C C46 C47 C C9 C10 C C46 C47 C C11 C10 C C48 C47 C C12 C11 C C49 C48 C C12 C11 C C49 C48 C C10 C11 C C47 C48 C C11 C12 C C48 C49 C C11 C12 C C48 C49 C C2 C12 C C50 C49 C C30 C13 C C33 C50 C C30 C13 C C33 C50 C C14 C13 C C49 C50 C C15 C14 C C52 C51 C C15 C14 C C52 C51 C C13 C14 C C60 C51 C C14 C15 C C51 C52 C C14 C15 C C51 C52 C C16 C15 C C35 C52 C S13

14 C17 C16 C C54 C53 C C17 C16 C C54 C53 C C15 C16 C C37 C53 C C16 C17 C C53 C54 C C16 C17 C C53 C54 C C18 C17 C C40 C54 C C36 C18 C C60 C55 C C36 C18 C C60 C55 C C17 C18 C C56 C55 C C20 C19 C C57 C56 C C20 C19 C C57 C56 C C5 C19 C C41 C56 C C19 C20 C C56 C57 C C19 C20 C C56 C57 C C21 C20 C C58 C57 C C7 C21 C C59 C58 C C7 C21 C C59 C58 C C20 C21 C C57 C58 C C23 C22 C C58 C59 C C23 C22 C C58 C59 C C21 C22 C C49 C59 C C22 C23 C C55 C60 C C22 C23 C C55 C60 C C42 C23 C C51 C60 C C8 C24 C /2+Y,1/4-Z,3/4-X; 2 1/4+Z,-Y,-1/4+X; 3 3/4-Z,-1/2+X,1/4-Y S14

15 Figure S1. Atom labeling scheme of {C60[Cu3]4} Figure S2. X-ray structures of {C60[Cu3]4} showing the basic stoichiometry and tetrahedrally encapsulated C60 by four [Cu3] S15

16 Figure S3. Symmetry generated dimer of [Cu3] S16

17 Figure S4. A view showing part of the supramolecular structure of {C60[Cu3]4} S17

18 Figure S5. Part of {C60[Cu3]4} showing cuprophilic interactions and C60 sandwiched [Cu3]2 dimer Figure S6. A view of Space-filling diagram {C60[Cu3]4} showing how [Cu3] moieties encircle C60 (C60 in yellow) S18

19 Table S4. Crystal data and structure refinement {C60[Ag3]4}. Identification code rad217_0m Empirical formula Formula weight Temperature/K 100(2) Crystal system Space group C120H12Ag12F72N24 cubic Fd-3c a/å (3) b/å (3) c/å (3) α/ 90 β/ 90 γ/ 90 Volume/Å (12) Z 16 ρcalcg/cm μ/mm F(000) Crystal size/mm Radiation MoKα (λ = ) 2Θ range for data collection/ 5.4 to Index ranges -47 h 47, -47 k 47, -47 l 47 Reflections collected Independent reflections 2300 [Rint = , Rsigma = ] Data/restraints/parameters 2300/606/521 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 /-0.54 Table S5. Bond Lengths for {C60[Ag3]4}. Atom Atom Length/Å Atom Atom Length/Å Ag1 N (4) C20 C Ag1 N (4) C21 C Ag1 Ag (7) C22 C Ag1 Ag (7) C22 C S19

20 Ag1 Ag (6) C23 C F1 C (7) C23 C F2 C (7) C24 C F3 C (7) C25 C F1A C (7) C25 C F2A C (7) C26 C F3A C (6) C27 C F4 C (6) C27 C F5 C (6) C28 C F6 C (6) C29 C N1 C (6) C29 C N1 N (5) C30 C N2 C (6) C31 C N2 Ag (4) C31 C C61 C (7) C32 C C61 C (7) C33 C C62 C (6) C33 C C63 C (7) C34 C C1 C C35 C C1 C C35 C C1 C C36 C C2 C C37 C C2 C C37 C C3 C C38 C C3 C C39 C C4 C C40 C C4 C C40 C C5 C C41 C C5 C C41 C C6 C C42 C C7 C C43 C C7 C C44 C C8 C C44 C C8 C C45 C C9 C C46 C C10 C C46 C S20

21 C10 C C47 C C11 C C48 C C11 C C49 C C12 C C49 C C13 C C50 C C13 C C51 C C14 C C51 C C15 C C52 C C15 C C53 C C16 C C54 C C16 C C55 C C17 C C55 C C18 C C56 C C18 C C57 C C19 C C58 C C20 C C59 C /2+Y,1/4-Z,3/4-X; 2 1/4+Z,-Y,-1/4+X; 3 3/4-Z,-1/2+X,1/4-Y Table S6. Bond Angles for {C60[Ag3]4}. Atom Atom Atom Angle/ Atom Atom Atom Angle/ N1 Ag1 N (15) C8 C24 C N1 Ag1 Ag (10) C25 C24 C N2 1 Ag1 Ag (11) C26 C25 C N1 Ag1 Ag (10) C26 C25 C N2 1 Ag1 Ag (10) C24 C25 C Ag1 2 Ag1 Ag (9) C25 C26 C N1 Ag1 Ag (10) C25 C26 C N2 1 Ag1 Ag (10) C27 C26 C Ag1 2 Ag1 Ag (2) C45 C27 C Ag1 3 Ag1 Ag C45 C27 C C63 N1 N (3) C28 C27 C C63 N1 Ag (3) C29 C28 C N2 N1 Ag (3) C29 C28 C C61 N2 N (4) C27 C28 C S21

22 C61 N2 Ag (3) C28 C29 C N1 N2 Ag (3) C28 C29 C N2 C61 C (4) C30 C29 C N2 C61 C (4) C13 C30 C C62 C61 C (4) C13 C30 C C61 C62 C (4) C31 C30 C N1 C63 C (4) C32 C31 C N1 C63 C (4) C32 C31 C C62 C63 C (4) C30 C31 C F3 C64 F (8) C31 C32 C F2A C64 F1A 107.2(7) C31 C32 C F2A C64 F3A 106.1(6) C33 C32 C F1A C64 F3A 105.9(7) C50 C33 C F3 C64 F (7) C50 C33 C F1 C64 F (7) C34 C33 C F3 C64 C (7) C35 C34 C F2A C64 C (6) C35 C34 C F1 C64 C (6) C33 C34 C F1A C64 C (6) C34 C35 C F3A C64 C (6) C34 C35 C F2 C64 C (6) C52 C35 C F4 C65 F (4) C18 C36 C F4 C65 F (5) C18 C36 C F5 C65 F (5) C37 C36 C F4 C65 C (5) C38 C37 C F5 C65 C (4) C38 C37 C F6 C65 C (4) C36 C37 C C2 C1 C C37 C38 C C2 C1 C C37 C38 C C9 C1 C C20 C38 C C1 C2 C C40 C39 C C1 C2 C C40 C39 C C12 C2 C C38 C39 C C4 C3 C C39 C40 C C4 C3 C C39 C40 C C2 C3 C C54 C40 C S22

23 C3 C4 C C42 C41 C C3 C4 C C42 C41 C C5 C4 C C56 C41 C C6 C5 C C41 C42 C C6 C5 C C41 C42 C C4 C5 C C23 C42 C C5 C6 C C44 C43 C C5 C6 C C44 C43 C C7 C6 C C25 C43 C C21 C7 C C43 C44 C C21 C7 C C43 C44 C C6 C7 C C57 C44 C C24 C8 C C27 C45 C C24 C8 C C27 C45 C C7 C8 C C46 C45 C C10 C9 C C47 C46 C C10 C9 C C47 C46 C C1 C9 C C45 C46 C C9 C10 C C46 C47 C C9 C10 C C46 C47 C C11 C10 C C48 C47 C C12 C11 C C49 C48 C C12 C11 C C49 C48 C C10 C11 C C47 C48 C C11 C12 C C48 C49 C C11 C12 C C48 C49 C C2 C12 C C50 C49 C C30 C13 C C33 C50 C C30 C13 C C33 C50 C C14 C13 C C49 C50 C C15 C14 C C52 C51 C C15 C14 C C52 C51 C C13 C14 C C60 C51 C C14 C15 C C51 C52 C C14 C15 C C51 C52 C C16 C15 C C35 C52 C S23

24 C17 C16 C C54 C53 C C17 C16 C C54 C53 C C15 C16 C C37 C53 C C16 C17 C C53 C54 C C16 C17 C C53 C54 C C18 C17 C C40 C54 C C36 C18 C C60 C55 C C36 C18 C C60 C55 C C17 C18 C C56 C55 C C20 C19 C C57 C56 C C20 C19 C C57 C56 C C5 C19 C C41 C56 C C19 C20 C C56 C57 C C19 C20 C C56 C57 C C21 C20 C C58 C57 C C7 C21 C C59 C58 C C7 C21 C C59 C58 C C20 C21 C C57 C58 C C23 C22 C C58 C59 C C23 C22 C C58 C59 C C21 C22 C C49 C59 C C22 C23 C C55 C60 C C22 C23 C C55 C60 C C42 C23 C C51 C60 C C8 C24 C /2+Y,1/4-Z,3/4-X; 2 1/4+Z,-Y,-1/4+X; 3 3/4-Z,-1/2+X,1/4-Y S24

25 Figure S7. Atom labeling scheme of {C60[Ag3]4} Figure S8. X-ray structures of {C60[Ag3]4} showing the basic stoichiometry and tetrahedrally encapsulated C60 by four [Ag3] S25

26 Figure S9. Part of {C60[Ag3]4} showing argentophilic interactions and C60 sandwiched [Ag3]2 dimer S26

27 Table S7. Crystal data and structure refinement for {C60[Au3]4}. Identification code rad248_0m Empirical formula Formula weight Temperature/K 100(2) Crystal system Space group C120H12Au12F72N24 cubic Fd-3c a/å (6) b/å (6) c/å (6) α/ 90 β/ 90 γ/ 90 Volume/Å (23) Z 16 ρcalcg/cm μ/mm F(000) Crystal size/mm Radiation MoKα (λ = ) 2Θ range for data collection/ to Index ranges -47 h 47, -47 k 47, -47 l 47 Reflections collected Independent reflections 2281 [Rint = , Rsigma = ] Data/restraints/parameters 2281/540/493 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 /-1.27 Table S8. Bond Lengths for {C60[Au3]4}. Atom Atom Length/Å Atom Atom Length/Å Au1 N (5) C22 C Au1 N (5) C22 C Au1 Au (7) C23 C Au1 Au (7) C23 C S27

28 Au1 Au (7) C24 C F1 C (8) C25 C F2 C (9) C25 C F3 C (8) C26 C F4 C (8) C27 C F5 C (8) C27 C F6 C (8) C28 C N1 C (8) C29 C N1 N (7) C29 C N2 C (9) C30 C N2 Au (5) C31 C C61 C (9) C31 C C61 C (9) C32 C C62 C (10) C33 C C63 C (10) C33 C C1 C C34 C C1 C C35 C C1 C C35 C C2 C C36 C C2 C C37 C C3 C C37 C C3 C C38 C C4 C C39 C C4 C C40 C C5 C C40 C C5 C C41 C C6 C C41 C C7 C C42 C C7 C C43 C C8 C C44 C C8 C C44 C C9 C C45 C C10 C C46 C C10 C C46 C C11 C C47 C C11 C C48 C S28

29 C12 C C49 C C13 C C49 C C13 C C50 C C14 C C51 C C15 C C51 C C15 C C52 C C16 C C53 C C16 C C54 C C17 C C55 C C18 C C55 C C18 C C56 C C19 C C57 C C20 C C58 C C20 C C59 C C21 C /2+Y,1/4-Z,3/4-X; 2 1/4+Z,-Y,-1/4+X; 3 3/4-Z,-1/2+X,1/4-Y Table S9. Bond Angles for {C60[Au3]4}. Atom Atom Atom Angle/ Atom Atom Atom Angle/ N1 Au1 N (2) C26 C25 C N1 Au1 Au (15) C24 C25 C N2 1 Au1 Au (16) C25 C26 C N1 Au1 Au (15) C25 C26 C N2 1 Au1 Au (16) C27 C26 C Au1 2 Au1 Au (1) C45 C27 C N1 Au1 Au (15) C45 C27 C N2 1 Au1 Au (16) C28 C27 C Au1 2 Au1 Au (7) C29 C28 C Au1 1 Au1 Au (1) C29 C28 C C63 N1 N (5) C27 C28 C C63 N1 Au (5) C28 C29 C N2 N1 Au (4) C28 C29 C C61 N2 N (5) C30 C29 C C61 N2 Au (5) C13 C30 C S29

30 N1 N2 Au (4) C13 C30 C N2 C61 C (6) C31 C30 C N2 C61 C (6) C32 C31 C C62 C61 C (6) C32 C31 C C61 C62 C (6) C30 C31 C N1 C63 C (6) C31 C32 C N1 C63 C (6) C31 C32 C C62 C63 C (6) C33 C32 C F1 C64 F (6) C50 C33 C F1 C64 F (6) C50 C33 C F3 C64 F (6) C34 C33 C F1 C64 C (6) C35 C34 C F3 C64 C (6) C35 C34 C F2 C64 C (6) C33 C34 C F4 C65 F (6) C34 C35 C F4 C65 F (6) C34 C35 C F5 C65 F (6) C52 C35 C F4 C65 C (6) C18 C36 C F5 C65 C (6) C18 C36 C F6 C65 C (6) C37 C36 C C2 C1 C C38 C37 C C2 C1 C C38 C37 C C9 C1 C C36 C37 C C1 C2 C C37 C38 C C1 C2 C C37 C38 C C12 C2 C C20 C38 C C4 C3 C C40 C39 C C4 C3 C C40 C39 C C2 C3 C C38 C39 C C3 C4 C C39 C40 C C3 C4 C C39 C40 C C5 C4 C C54 C40 C C6 C5 C C42 C41 C C6 C5 C C42 C41 C C4 C5 C C56 C41 C C5 C6 C C41 C42 C S30

31 C5 C6 C C41 C42 C C7 C6 C C23 C42 C C21 C7 C C44 C43 C C21 C7 C C44 C43 C C6 C7 C C25 C43 C C24 C8 C C43 C44 C C24 C8 C C43 C44 C C7 C8 C C57 C44 C C10 C9 C C27 C45 C C10 C9 C C27 C45 C C1 C9 C C46 C45 C C9 C10 C C47 C46 C C9 C10 C C47 C46 C C11 C10 C C45 C46 C C12 C11 C C46 C47 C C12 C11 C C46 C47 C C10 C11 C C48 C47 C C11 C12 C C49 C48 C C11 C12 C C49 C48 C C2 C12 C C47 C48 C C30 C13 C C48 C49 C C30 C13 C C48 C49 C C14 C13 C C50 C49 C C15 C14 C C33 C50 C C15 C14 C C33 C50 C C13 C14 C C49 C50 C C14 C15 C C52 C51 C C14 C15 C C52 C51 C C16 C15 C C60 C51 C C17 C16 C C51 C52 C C17 C16 C C51 C52 C C15 C16 C C35 C52 C C16 C17 C C54 C53 C C16 C17 C C54 C53 C C18 C17 C C37 C53 C C36 C18 C C53 C54 C S31

32 C36 C18 C C53 C54 C C17 C18 C C40 C54 C C20 C19 C C60 C55 C C20 C19 C C60 C55 C C5 C19 C C56 C55 C C19 C20 C C57 C56 C C19 C20 C C57 C56 C C21 C20 C C41 C56 C C7 C21 C C56 C57 C C7 C21 C C56 C57 C C20 C21 C C58 C57 C C23 C22 C C59 C58 C C23 C22 C C59 C58 C C21 C22 C C57 C58 C C22 C23 C C58 C59 C C22 C23 C C58 C59 C C42 C23 C C49 C59 C C8 C24 C C55 C60 C C8 C24 C C55 C60 C C25 C24 C C51 C60 C C26 C25 C /2+Y,1/4-Z,3/4-X; 2 1/4+Z,-Y,-1/4+X; 3 3/4-Z,-1/2+X,1/4-Y S32

33 Figure S10. Atom labeling scheme of {C60[Au3]4} S33

34 Figure S11. Estimated twist angles of {C60[M3]4} showing the distortion of hexanuclear M6 core from ideal trigonal-pyramidal geometry. S34

35 Table S10. Calculated [Cu3] weight percentages and observed weight loss by the thermogravimetric (TGA) analysis. Complex [M3] weight % Combined weight loss (1 st +2 nd ) % {C60[Cu3]4} {C60[Ag3]4} {C60[Au3]4} {C60[Cu3]4} complex S35

36 {C60[Ag3]4} complex {C60[Au3]4} complex All three {C60[M3]4} complexes decompose by releasing the metal-pyrazolate, leaving only C60. For example, C60[Cu3]4 starts it decomposition at 175 C and lose 80.4% of its total weight by 309 C in which mass content of metal-pyrazolate [Cu3] is equal to S36

37 81.6%. The two values are close enough to attribute the weight loss to metalpyrazolate. Interestingly, this weight lose occur in two steps in all three adducts. We could not find reasonable molecular fragments corresponding to the stepwise loss in copper and silver adducts. The first part of the weight loss in C60[Au3]4 (60.6%) match reasonably well to the loss of three [Au3] molecules from the complex and the second weight loss may be assigned to lose of the fourth [Au3] unit (after the experiment some gold plating was observed on the pan and the hang-down wire. This might be the reason for the observed difference of calculated and experimental total weight loses). References: (1) Dias, H. V. R.; Polach, S. A.; Wang, Z., Coinage metal complexes of 3,5- bis(trifluoromethyl)pyrazolate ligand. Synthesis and characterization of {[3,5- (CF3)2Pz]Cu}3 and {[3,5-(CF3)2Pz]Ag}3. J. Fluor. Chem. 2000, 103, (2) Omary, M. A.; Rawashdeh-Omary, M. A.; Gonser, M. W. A.; Elbjeirami, O.; Grimes, T.; Cundari, T. R.; Diyabalanage, H. V. K.; Gamage, C. S. P.; Dias, H. V. R., Metal Effect on the Supramolecular Structure, Photophysics, and Acid-Base Character of Trinuclear Pyrazolato Coinage Metal Complexes. Inorg. Chem. 2005, 44, (3) Sheldrick, G., Crystal structure refinement with SHELXL. Acta Crystallographica Section C 2015, 71, 3-8. (4) Dolomanov, O. V.; Bourhis, L. J.; Gildea, R. J.; Howard, J. A. K.; Puschmann, H., OLEX2: a complete structure solution, refinement and analysis program. J. Appl. Crystallogr. 2009, 42, (5) Ghiassi, K. B.; Chen, S. Y.; Wescott, J.; Balch, A. L.; Olmstead, M. M., New Insights into the Structural Complexity of C60 2S8: Two Crystal Morphologies, Two Phase Changes, Four Polymorphs. Cryst. Growth Des. 2015, 15, S37