Supporting Information for A Janus-type Bis(maloNHC) and its Zwitterionic Gold and Silver Metal Complexes

Transcription

1 Supporting Information for A Janus-type Bis(maloNHC) and its Zwitterionic Gold and Silver Metal Complexes Ashley Carter, Alexander Mason, Michael A. Baker, Donald G. Bettler, Angelo Changas, Colin D. McMillen, and Daniela Tapu*, Department of Chemistry and Biochemistry, Kennesaw State University, 370 Paulding Avenue NW, Kennesaw, Georgia, 30144, United States Department of Chemistry, Clemson University, 379 Hunter Laboratories, Clemson, SC, 29634, United States dtapu@kennesaw.edu Contents NMR Spectra of 2, 3, 5-9 X-ray Crystallography of 6-9 Page S2 S11 S1

2 Figure S1. 1 H NMR spectrum of 2 (CDCl 3, 300 MHz) Figure S2. 13 C NMR spectrum of 2 (CDCl 3, 75.5 MHz) S2

3 Figure S3. 1 H NMR spectrum of 3 (DMSO-d 6, 300 MHz) Figure S4. 1 H NMR spectrum of 5 (CDCl 3, 300 MHz) S3

4 Figure S5. 13 C NMR spectrum of 5 (CDCl 3, 75.5 MHz) Figure S6. 1 H NMR spectrum of 6 (DMSO-d 6, 300 MHz) S4

5 Figure S7. 13 C NMR spectrum of 6 (CDCl 3, 75.5 MHz) Figure S8. 1 H NMR spectrum of 1 (DMSO-d 6, 300 MHz) S5

6 Figure S9. 13 C NMR spectrum of 1 (DMSO-d 6, 75.5 MHz) Figure S10. 1 H NMR spectrum of 7 (DMSO-d 6, 300 MHz) S6

7 Figure S C NMR spectrum of 7 (DMSO-d 6, 75.5 MHz) Figure S12. 1 H NMR spectrum of 8 (CDCl 3, 300 MHz) S7

8 Figure S C NMR spectrum of 8 (CD 2 Cl 2, 75.5 MHz) Figure S P NMR spectrum of 8 (CDCl 3, MHz) S8

9 Figure S15. 1 H NMR spectrum of 9 (CDCl 3, 300 MHz) Figure S C NMR spectrum of 9 (CD 2 Cl 2, 75.5 MHz) S9

10 Figure S P NMR spectrum of 9 (CDCl 3, MHz) S10

11 Crystal Structure Report for 6 (C74H82N4O4 xc7h8 (x ~3-4.5)) A specimen of C 95 H 106 N 4 O 4, approximate dimensions mm x mm x mm, was used for the X-ray crystallographic analysis. The X-ray intensity data were measured. The integration of the data using a monoclinic unit cell yielded a total of reflections to a maximum θ angle of (0.83 Å resolution), of which were independent (average redundancy , completeness = 99.9%, R int = 7.01%, R sig = 2.97%) and (80.02%) were greater than 2σ(F 2 ). The final cell constants of a = (12) Å, b = (14) Å, c = (14) Å, β = (2), volume = (10) Å 3, are based upon the refinement of the XYZ-centroids of reflections above 20 σ(i). The calculated minimum and maximum transmission coefficients (based on crystal size) are and The structure was solved and refined using the Bruker SHELXTL Software Package, using the space group P 1 21/n 1, with Z = 4 for the formula unit, C 95 H 106 N 4 O 4. The final anisotropic full-matrix least-squares refinement on F 2 with 949 variables converged at R1 = 6.33%, for the observed data and wr2 = 19.07% for all data. The goodness-of-fit was The largest peak in the final difference electron density synthesis was e - /Å 3 and the largest hole was e - /Å 3 with an RMS deviation of e - /Å 3. On the basis of the final model, the calculated density was g/cm 3 and F(000), 2944 e -. An additional 1.5 molecules of crystallized toluene solvent molecules per formula unit were modeled using the SQUEEZE algorithm of PLATON. Three crystallized solvent molecules per formula unit were modeled directly from the difference electron density map. Figure S18. Solid state molecular structure of 6 S11

12 Figure S19. Solid state packing diagram of 6 S12

13 Table S1. Sample and crystal data for 6 squeezed. Chemical formula C 95 H 106 N 4 O 4 Formula weight Temperature Wavelength Crystal size Crystal system g/mol 100(2) K Å x x mm monoclinic Space group P 1 21/n 1 Unit cell dimensions a = (12) Å α = 90 b = (14) Å β = (2) c = (14) Å γ = 90 Volume (10) Å 3 Z 4 Density (calculated) g/cm 3 Absorption coefficient mm -1 F(000) 2944 Table S2. Data collection and structure refinement for 6 squeezed. Theta range for data collection 2.10 to Index ranges -23 h 23, -24 k 24, -26 l 26 Reflections collected Independent reflections [R(int) = ] Max. and min. transmission and Structure solution technique direct methods Structure solution program SHELXT-2014 (Sheldrick 2014) Refinement method Full-matrix least-squares on F 2 Refinement program SHELXL-2014 (Sheldrick 2014) Function minimized 2 Σ w(f o - F c2 ) 2 S13

14 Data / restraints / parameters / 30 / 949 Goodness-of-fit on F Δ/σmax Final R indices data; I>2σ(I) R1 = , wr2 = all data R1 = , wr2 = Weighting scheme w=1/[σ 2 (F o2 )+(0.0962P) P] where P=(F o2 +2F c2 )/3 Largest diff. peak and hole and eå -3 R.M.S. deviation from mean eå -3 Table S3. Atomic coordinates and equivalent isotropic atomic displacement parameters (Å 2 ) for 6 squeezed. U(eq) is defined as one third of the trace of the orthogonalized U ij tensor. x/a y/b z/c U(eq) O (7) (7) (6) (3) O (8) (7) (7) (4) O (8) (7) (7) (3) O (8) (7) (7) (4) N (8) (8) (7) (3) N (8) (8) (7) (3) N (8) (8) (7) (3) N (8) (8) (7) (3) C (10) (10) (8) (4) C (10) (10) (8) (4) C (10) (10) (8) (4) C (10) (10) (9) (4) C (10) (10) (9) (4) C (10) (10) (9) (4) C (10) (10) (9) (4) C (10) (10) (9) (4) C (11) (10) (10) (5) S14

15 C (11) (10) (10) (5) C (10) (10) (9) (4) C (10) (10) (9) (4) C (10) (10) (9) (4) C (10) (10) (9) (4) C (11) (11) (9) (4) C (12) (12) (10) (5) C (12) (11) (10) (5) C (12) (11) (10) (5) C (11) (10) (9) (4) C (12) (12) (10) (5) C (13) (13) (11) (6) C (13) (14) (12) (6) C (11) (11) (10) (5) C (15) (15) (11) (7) C (12) (12) (11) (5) C (10) (10) (10) (4) C (12) (11) (10) (5) C (14) (13) (12) (6) C (13) (14) (14) (7) C (12) (13) (13) (6) C (11) (11) (10) (5) C (13) (12) (10) (5) C (17) (17) (12) (7) C (18) (14) (14) (7) C (11) (12) (10) (5) C (13) (14) (14) (7) C (16) (16) (13) (7) C (10) (10) (8) (4) S15

16 C (10) (10) (9) (4) C (10) (10) (9) (4) C (10) (10) (9) (4) C (10) (10) (9) (4) C (11) (10) (9) (4) C (11) (10) (9) (4) C (10) (10) (9) (4) C (11) (10) (9) (4) C (11) (10) (9) (4) C (10) (10) (8) (4) C (10) (10) (9) (4) C (10) (10) (9) (4) C (10) (10) (9) (4) C (12) (11) (10) (5) C (14) (12) (11) (6) C (14) (12) (12) (6) C (13) (11) (11) (5) C (11) (10) (9) (4) C (13) (12) (11) (5) C (14) (13) (13) (6) C (18) (2) (13) (10) C (12) (11) (10) (5) C (18) (15) (12) (8) C (14) (14) (16) (8) C (11) (10) (9) (4) C (11) (12) (10) (5) C (13) (15) (13) (7) C (16) (17) (14) (8) C (15) (15) (13) (7) S16

17 C (12) (12) (10) (5) C (12) (14) (11) (6) C (14) (17) (14) (8) C (16) (15) (14) (7) C (13) (13) (10) (5) C (16) (16) (12) (7) C (16) (16) (14) (8) C (13) (17) (12) (7) C (14) (16) (13) (7) C (15) (14) (14) (7) C (15) (14) (13) (6) C (16) (14) (13) (7) C (15) (15) (14) (7) C (2) (3) (16) (14) C (13) (16) (13) (7) C (13) (15) (12) (6) C (13) (14) (13) (6) C (13) (15) (12) (6) C (13) (15) (13) (7) C (13) (14) (14) (7) C (2) (3) (17) (14) C (3) (2) (3) (13) C (16) (2) (2) (11) C (2) (2) (2) (10) C (2) (19) (2) (12) C (16) (2) (19) (11) C (2) (3) (3) (14) C (4) (3) (3) 0.140(2) S17

18 Table S4. Bond lengths (Å) for 6 squeezed. O1-C (2) O2-C (2) O3-C (2) O4-C (3) N1-C (3) N1-C (2) N1-C (2) N2-C (3) N2-C (3) N2-C (2) N3-C (3) N3-C (3) N3-C (2) N4-C (3) N4-C (2) N4-C (3) C1-H C2-C (3) C3-C (3) C3-C (3) C5-C (3) C5-C (3) C6-C (3) C6-H C7-C (3) C7-H C8-C (3) C8-C (3) C9-C (3) C9-H C10-H C11-C (3) C11-C (3) C12-C (3) C12-H C13-C (3) C13-H C14-C (3) C14-C (3) C15-C (3) C15-C (3) C16-C (3) C16-H C17-C (3) C17-H C18-C (3) C18-H C19-C (3) C20-C (3) C20-C (3) C20-H C21-H21A 0.98 C21-H21B 0.98 C21-H21C 0.98 C22-H22A 0.98 C22-H22B 0.98 S18

19 C22-H22C 0.98 C23-C (3) C23-C (3) C23-H C24-H24A 0.98 C24-H24B 0.98 C24-H24C 0.98 C25-H25A 0.98 C25-H25B 0.98 C25-H25C 0.98 C26-C (3) C26-C (3) C27-C (3) C27-C (4) C28-C (4) C28-H C29-C (4) C29-H C30-C (3) C30-H C31-C (3) C32-C (3) C32-C (4) C32-H C33-H33A 0.98 C33-H33B 0.98 C33-H33C 0.98 C34-H34A 0.98 C34-H34B 0.98 C34-H34C 0.98 C35-C (4) C35-C (4) C35-H C36-H36A 0.98 C36-H36B 0.98 C36-H36C 0.98 C37-H37A 0.98 C37-H37B 0.98 C37-H37C 0.98 C38-H C39-C (3) C40-C (3) C40-C (3) C42-C (3) C42-C (3) C43-C (3) C43-H C44-C (3) C44-H C45-C (3) C45-C (3) C46-C (3) C46-H C47-H C48-C (3) C48-C (3) C49-C (3) C49-H S19

20 C50-C (3) C50-H C51-C (3) C51-C (3) C52-C (3) C52-C (3) C53-C (4) C53-H C54-C (4) C54-H C55-C (3) C55-H C56-C (3) C57-C (3) C57-C (4) C57-H C58-H58A 0.98 C58-H58B 0.98 C58-H58C 0.98 C59-H59A 0.98 C59-H59B 0.98 C59-H59C 0.98 C60-C (4) C60-C (4) C60-H C61-H61A 0.98 C61-H61B 0.98 C61-H61C 0.98 C62-H62A 0.98 C62-H62B 0.98 C62-H62C 0.98 C63-C (3) C63-C (3) C64-C (3) C64-C (3) C65-C (4) C65-H C66-C (4) C66-H C67-C (3) C67-H C68-C (3) C69-C (4) C69-C (3) C69-H C70-H70A 0.98 C70-H70B 0.98 C70-H70C 0.98 C71-H71A 0.98 C71-H71B 0.98 C71-H71C 0.98 C72-C (4) C72-C (4) C72-H C73-H73A 0.98 C73-H73B 0.98 C73-H73C 0.98 C74-H74A 0.98 S20

21 C74-H74B 0.98 C74-H74C 0.98 C75-C (4) C75-C (5) C75-C (4) C76-C (4) C76-H C77-C (4) C77-H C78-C (4) C78-H C79-C (4) C79-H C80-H C81-H81A 0.98 C81-H81B 0.98 C81-H81C 0.98 C82-C (4) C82-C (4) C82-C (4) C83-C (4) C83-H C84-C (4) C84-H C85-C (4) C85-H C86-C (4) C86-H C87-H C88-H88A 0.98 C88-H88B 0.98 C88-H88C 0.98 C89-C (7) C89-C (7) C89-C (8) C90-C (6) C90-H C91-C (7) C91-H C92-C (6) C92-H C93-C (6) C93-H C94-H C95-H95A 0.98 C95-H95B 0.98 C95-H95C 0.98 Table S5. Bond angles ( ) for 6 squeezed. C1-N1-C (16) C1-N1-C (16) C26-N1-C (16) C1-N2-C (16) C1-N2-C (16) C14-N2-C (15) S21

22 C38-N3-C (16) C38-N3-C (16) C63-N3-C (16) C38-N4-C (17) C38-N4-C (16) C39-N4-C (16) N2-C1-N (18) N2-C1-H N1-C1-H O1-C2-C (18) O1-C2-N (17) C3-C2-N (16) C4-C3-C (17) C4-C3-C (17) C2-C3-C (17) O2-C4-C (18) O2-C4-N (17) C3-C4-N (17) C10-C5-C (18) C10-C5-C (18) C6-C5-C (18) C7-C6-C (19) C7-C6-H C5-C6-H C6-C7-C (18) C6-C7-H C8-C7-H C9-C8-C (18) C9-C8-C (18) C7-C8-C (18) C10-C9-C (19) C10-C9-H C8-C9-H C9-C10-C (19) C9-C10-H C5-C10-H C12-C11-C (18) C12-C11-C (18) C13-C11-C (18) C13-C12-C (19) C13-C12-H C11-C12-H C12-C13-C (18) C12-C13-H C11-C13-H C15-C14-C (19) C15-C14-N (18) C19-C14-N (17) C16-C15-C (2) C16-C15-C (19) C14-C15-C (19) C17-C16-C (2) C17-C16-H C15-C16-H C16-C17-C (2) C16-C17-H C18-C17-H C17-C18-C (2) S22

23 C17-C18-H C19-C18-H C18-C19-C (19) C18-C19-C (19) C14-C19-C (18) C15-C20-C (2) C15-C20-C (19) C22-C20-C (19) C15-C20-H C22-C20-H C21-C20-H C20-C21-H21A C20-C21-H21B H21A-C21-H21B C20-C21-H21C H21A-C21-H21C H21B-C21-H21C C20-C22-H22A C20-C22-H22B H22A-C22-H22B C20-C22-H22C H22A-C22-H22C H22B-C22-H22C C19-C23-C (19) C19-C23-C (18) C24-C23-C (19) C19-C23-H C24-C23-H C25-C23-H C23-C24-H24A C23-C24-H24B H24A-C24-H24B C23-C24-H24C H24A-C24-H24C H24B-C24-H24C C23-C25-H25A C23-C25-H25B H25A-C25-H25B C23-C25-H25C H25A-C25-H25C H25B-C25-H25C C31-C26-C (19) C31-C26-N (19) C27-C26-N (19) C28-C27-C (2) C28-C27-C (2) C26-C27-C (19) C29-C28-C (2) C29-C28-H C27-C28-H C30-C29-C (2) C30-C29-H C28-C29-H C29-C30-C (2) C29-C30-H C31-C30-H C26-C31-C (2) C26-C31-C (19) S23

24 C30-C31-C (2) C27-C32-C (2) C27-C32-C (2) C33-C32-C (2) C27-C32-H C33-C32-H C34-C32-H C32-C33-H33A C32-C33-H33B H33A-C33-H33B C32-C33-H33C H33A-C33-H33C H33B-C33-H33C C32-C34-H34A C32-C34-H34B H34A-C34-H34B C32-C34-H34C H34A-C34-H34C H34B-C34-H34C C31-C35-C (2) C31-C35-C (2) C36-C35-C (2) C31-C35-H C36-C35-H C37-C35-H C35-C36-H36A C35-C36-H36B H36A-C36-H36B C35-C36-H36C H36A-C36-H36C H36B-C36-H36C C35-C37-H37A C35-C37-H37B H37A-C37-H37B C35-C37-H37C H37A-C37-H37C H37B-C37-H37C N4-C38-N (17) N4-C38-H N3-C38-H O3-C39-C (18) O3-C39-N (17) C40-C39-N (17) C39-C40-C (17) C39-C40-C (17) C41-C40-C (17) O4-C41-C (18) O4-C41-N (17) C40-C41-N (17) C47-C42-C (18) C47-C42-C (18) C43-C42-C (18) C44-C43-C (19) C44-C43-H C42-C43-H C43-C44-C (19) C43-C44-H C45-C44-H S24

25 C46-C45-C (18) C46-C45-C (18) C44-C45-C (18) C47-C46-C (19) C47-C46-H C45-C46-H C46-C47-C (19) C46-C47-H C42-C47-H C50-C48-C (18) C50-C48-C (18) C49-C48-C (18) C50-C49-C (19) C50-C49-H C48-C49-H C49-C50-C (19) C49-C50-H C48-C50-H C56-C51-C (19) C56-C51-N (18) C52-C51-N (18) C51-C52-C (2) C51-C52-C (2) C53-C52-C (2) C54-C53-C (2) C54-C53-H C52-C53-H C55-C54-C (2) C55-C54-H C53-C54-H C54-C55-C (2) C54-C55-H C56-C55-H C51-C56-C (2) C51-C56-C (19) C55-C56-C (19) C52-C57-C (2) C52-C57-C (2) C58-C57-C (2) C52-C57-H C58-C57-H C59-C57-H C57-C58-H58A C57-C58-H58B H58A-C58-H58B C57-C58-H58C H58A-C58-H58C H58B-C58-H58C C57-C59-H59A C57-C59-H59B H59A-C59-H59B C57-C59-H59C H59A-C59-H59C H59B-C59-H59C C56-C60-C (2) C56-C60-C (2) C62-C60-C (2) C56-C60-H S25

26 C62-C60-H C61-C60-H C60-C61-H61A C60-C61-H61B H61A-C61-H61B C60-C61-H61C H61A-C61-H61C H61B-C61-H61C C60-C62-H62A C60-C62-H62B H62A-C62-H62B C60-C62-H62C H62A-C62-H62C H62B-C62-H62C C68-C63-C (2) C68-C63-N (19) C64-C63-N (19) C65-C64-C (2) C65-C64-C (2) C63-C64-C (2) C66-C65-C (2) C66-C65-H C64-C65-H C65-C66-C (2) C65-C66-H C67-C66-H C66-C67-C (3) C66-C67-H C68-C67-H C63-C68-C (2) C63-C68-C (2) C67-C68-C (2) C71-C69-C (2) C71-C69-C (2) C64-C69-C (2) C71-C69-H C64-C69-H C70-C69-H C69-C70-H70A C69-C70-H70B H70A-C70-H70B C69-C70-H70C H70A-C70-H70C H70B-C70-H70C C69-C71-H71A C69-C71-H71B H71A-C71-H71B C69-C71-H71C H71A-C71-H71C H71B-C71-H71C C68-C72-C (2) C68-C72-C (2) C74-C72-C (2) C68-C72-H C74-C72-H C73-C72-H C72-C73-H73A C72-C73-H73B S26

27 H73A-C73-H73B C72-C73-H73C H73A-C73-H73C H73B-C73-H73C C72-C74-H74A C72-C74-H74B H74A-C74-H74B C72-C74-H74C H74A-C74-H74C H74B-C74-H74C C80-C75-C (3) C80-C75-C (3) C76-C75-C (3) C77-C76-C (3) C77-C76-H C75-C76-H C76-C77-C (3) C76-C77-H C78-C77-H C79-C78-C (3) C79-C78-H C77-C78-H C78-C79-C (3) C78-C79-H C80-C79-H C79-C80-C (3) C79-C80-H C75-C80-H C75-C81-H81A C75-C81-H81B H81A-C81-H81B C75-C81-H81C H81A-C81-H81C H81B-C81-H81C C83-C82-C (3) C83-C82-C (3) C87-C82-C (3) C84-C83-C (3) C84-C83-H C82-C83-H C83-C84-C (3) C83-C84-H C85-C84-H C86-C85-C (3) C86-C85-H C84-C85-H C85-C86-C (3) C85-C86-H C87-C86-H C86-C87-C (3) C86-C87-H C82-C87-H C82-C88-H88A C82-C88-H88B H88A-C88-H88B C82-C88-H88C H88A-C88-H88C H88B-C88-H88C S27

28 C94-C89-C (6) C94-C89-C (6) C90-C89-C (6) C89-C90-C (4) C89-C90-H C91-C90-H C90-C91-C (4) C90-C91-H C92-C91-H C93-C92-C (4) C93-C92-H C91-C92-H C94-C93-C (4) C94-C93-H C92-C93-H C89-C94-C (6) C89-C94-H C93-C94-H C89-C95-H95A C89-C95-H95B H95A-C95-H95B C89-C95-H95C H95A-C95-H95C H95B-C95-H95C Table S6. Anisotropic atomic displacement parameters (Å 2 ) for 6 squeezed. The anisotropic atomic displacement factor exponent takes the form: -2π 2 [ h 2 a *2 U h k a * b * U 12 ] U11 U22 U33 U23 U13 U12 O (7) (8) (8) (6) (6) (6) O (8) (8) (9) (7) (7) (6) O (8) (8) (8) (6) (7) (6) O (8) (8) (9) (6) (7) (6) N (8) (9) (8) (7) (6) (7) N (8) (8) (8) (6) (6) (6) N (8) (9) (8) (7) (6) (6) N (8) (8) (8) (6) (6) (6) C (9) (10) (9) (7) (7) (8) C (10) (10) (9) (7) (7) (8) C (9) (10) (9) (7) (7) (8) C (10) (10) (10) (8) (8) (8) C (9) (10) (9) (8) (7) (8) S28

29 C (10) (10) (9) (8) (8) (8) C (10) (10) (9) (8) (8) (8) C (10) (10) (9) (8) (8) (8) C (12) (10) (11) (8) (9) (8) C (11) (11) (11) (8) (9) (9) C (10) (10) (9) (7) (7) (8) C (10) (10) (9) (8) (8) (8) C (9) (10) (10) (8) (8) (8) C (9) (10) (9) (8) (8) (8) C (10) (11) (10) (8) (8) (8) C (11) (12) (11) (9) (9) (9) C (13) (11) (12) (9) (10) (9) C (12) (11) (11) (9) (9) (9) C (10) (11) (10) (8) (8) (8) C (12) (12) (11) (9) (9) (9) C (14) (14) (12) (10) (10) (11) C (13) (16) (13) (11) (10) (11) C (11) (11) (11) (8) (9) (9) C (15) (18) (12) (11) (11) (13) C (12) (13) (13) (10) (10) (10) C (10) (10) (11) (8) (8) (8) C (12) (11) (12) (9) (10) (9) C (15) (14) (14) (11) (12) (11) C (13) (16) (18) (13) (12) (11) C (11) (14) (16) (12) (11) (10) C (10) (11) (12) (9) (9) (9) C (14) (13) (12) (10) (10) (10) C (19) (19) (14) (13) (13) (15) C (2) (16) (18) (13) (15) (14) S29

30 C (10) (13) (12) (10) (9) (9) C (13) (16) (17) (13) (12) (12) C (16) (18) (15) (13) (12) (14) C (9) (10) (9) (7) (7) (8) C (9) (10) (9) (8) (7) (8) C (9) (10) (9) (8) (7) (8) C (9) (11) (10) (8) (8) (8) C (9) (10) (9) (8) (7) (8) C (10) (10) (10) (8) (8) (8) C (10) (11) (9) (8) (8) (8) C (9) (10) (9) (8) (7) (8) C (11) (10) (10) (8) (8) (8) C (11) (11) (10) (8) (8) (9) C (9) (10) (9) (7) (7) (8) C (9) (11) (9) (8) (7) (8) C (10) (10) (9) (8) (8) (8) C (10) (10) (10) (8) (8) (8) C (11) (11) (11) (9) (9) (9) C (14) (12) (13) (10) (11) (10) C (15) (11) (15) (10) (12) (10) C (12) (12) (13) (10) (10) (10) C (11) (11) (11) (8) (8) (8) C (14) (12) (12) (10) (10) (10) C (14) (14) (15) (11) (12) (11) C (2) 0.098(3) (14) (16) (13) (19) C (12) (11) (12) (9) (9) (9) C (2) (15) (14) (12) (14) (15) C (14) (15) 0.082(2) (15) (14) (11) C (10) (11) (10) (8) (8) (8) S30

31 C (11) (13) (12) (10) (9) (9) C (12) (18) (16) (13) (11) (12) C (16) 0.066(2) (18) (15) (14) (15) C (16) (18) (15) (13) (12) (13) C (12) (12) (12) (9) (9) (10) C (11) (16) (12) (11) (9) (11) C (13) 0.070(2) (17) (15) (12) (13) C (16) (18) (17) (14) (13) (14) C (13) (14) (12) (10) (10) (10) C (17) (18) (13) (12) (12) (14) C (17) (19) (17) (14) (13) (15) C (13) 0.074(2) (14) (14) (11) (13) C (13) 0.060(2) (15) (14) (11) (13) C (15) (14) (19) (13) (13) (12) C (15) (15) (15) (12) (12) (12) C (17) (15) (15) (12) (13) (13) C (17) (15) (18) (13) (14) (12) C (2) 0.147(4) 0.047(2) (2) (17) (2) C (13) (19) (15) (13) (11) (12) C (12) (18) (14) (13) (11) (12) C (12) (15) (16) (12) (11) (11) C (13) (17) (14) (12) (11) (12) C (12) (18) (15) (13) (11) (12) C (12) (16) (18) (13) (12) (11) C (2) 0.137(4) 0.063(2) 0.050(3) (18) 0.006(2) C (2) 0.082(3) 0.112(3) (2) 0.030(2) 0.018(2) C (15) 0.076(2) 0.112(3) (2) (17) (15) C (13) (13) (13) (9) (9) (9) C (2) 0.057(2) 0.116(3) (19) 0.051(2) (16) S31

32 C (16) 0.097(3) 0.081(3) (2) (16) (18) C (2) 0.104(4) 0.121(4) 0.014(3) 0.008(2) 0.018(2) C (5) 0.135(5) 0.140(5) 0.010(4) 0.056(4) 0.028(4) Table S7. Hydrogen atomic coordinates and isotropic atomic displacement parameters (Å 2 ) for 6 squeezed. x/a y/b z/c U(eq) H H H H H H H H H H H H21A H21B H21C H22A H22B H22C H H24A H24B H24C H25A H25B S32

33 H25C H H H H H33A H33B H33C H34A H34B H34C H H36A H36B H36C H37A H37B H37C H H H H H H H H H H H S33

34 H58A H58B H58C H59A H59B H59C H H61A H61B H61C H62A H62B H62C H H H H H70A H70B H70C H71A H71B H71C H H73A H73B H73C H74A H74B S34

35 H74C H H H H H H81A H81B H81C H H H H H H88A H88B H88C H H H H H H95A H95B H95C S35

36 Crystal Structure Report for 7 2 C2H3N A specimen of C 80 H 89 K 2 N 7 O 4 S 2, approximate dimensions mm x mm x mm, was used for the X-ray crystallographic analysis. The X-ray intensity data were measured. The integration of the data using a monoclinic unit cell yielded a total of reflections to a maximum θ angle of (0.79 Å resolution), of which 8620 were independent (average redundancy , completeness = 99.7%, R int = 4.79%, R sig = 2.11%) and 6977 (80.94%) were greater than 2σ(F 2 ). The final cell constants of a = (10) Å, b = (16) Å, c = (16) Å, β = (3), volume = (6) Å 3, are based upon the refinement of the XYZ-centroids of reflections above 20 σ(i). The calculated minimum and maximum transmission coefficients (based on crystal size) are and The structure was solved and refined using the Bruker SHELXTL Software Package, using the space group P 1 21/c 1, with Z = 2 for the formula unit, C 80 H 89 K 2 N 7 O 4 S 2. The final anisotropic full-matrix least-squares refinement on F 2 with 425 variables converged at R1 = 5.61%, for the observed data and wr2 = 19.79% for all data. The goodness-of-fit was The largest peak in the final difference electron density synthesis was e - /Å 3 and the largest hole was e - /Å 3 with an RMS deviation of e - /Å 3. On the basis of the final model, the calculated density was g/cm 3 and F(000), 1440 e -. Figure S20. Solid state molecular structure of 7 S36

37 Figure S21. Solid state packing diagram of 7 Table S8. Sample and crystal data for 7. Chemical formula C 80 H 89 K 2 N 7 O 4 S 2 Formula weight Temperature Wavelength Crystal size Crystal system g/mol 100(2) K Å x x mm monoclinic Space group P 1 21/c 1 Unit cell dimensions a = (10) Å α = 90 b = (16) Å β = (3) c = (16) Å γ = 90 Volume (6) Å 3 Z 2 Density (calculated) g/cm 3 Absorption coefficient mm -1 F(000) 1440 S37

38 Table S9. Data collection and structure refinement for 7. Theta range for data collection 2.06 to Index ranges -14 h 15, -23 k 23, -23 l 23 Reflections collected Independent reflections 8620 [R(int) = ] Max. and min. transmission and Structure solution technique direct methods Structure solution program SHELXT-2014 (Sheldrick 2014) Refinement method Full-matrix least-squares on F 2 Refinement program SHELXL-2014 (Sheldrick 2014) Function minimized 2 Σ w(f o - F c2 ) 2 Data / restraints / parameters 8620 / 6 / 425 Goodness-of-fit on F Δ/σmax Final R indices 6977 data; I>2σ(I) R1 = , wr2 = all data R1 = , wr2 = Weighting scheme w=1/[σ 2 (F o2 )+(0.1153P) P] where P=(F o2 +2F c2 )/3 Largest diff. peak and hole and eå -3 R.M.S. deviation from mean eå -3 Table S10. Atomic coordinates and equivalent isotropic atomic displacement parameters (Å 2 ) for 7. U(eq) is defined as one third of the trace of the orthogonalized U ij tensor. x/a y/b z/c U(eq) K (5) (3) (3) (17) S (5) (3) (3) (17) O (14) (9) (9) (4) O (16) (9) (9) (4) N (16) (10) (10) (4) S38

39 N (16) (10) (10) (4) C (19) (12) (12) (4) C (19) (11) (12) (4) C (19) (11) (12) (4) C (19) (12) (12) (5) C (19) (12) (12) (4) C (2) (12) (13) (5) C (19) (12) (12) (5) C (18) (12) (12) (4) C (19) (12) (12) (5) C (19) (12) (12) (5) C (18) (11) (12) (4) C (19) (12) (13) (5) C (19) (12) (13) (5) C (2) (13) (13) (5) C (2) (15) (15) (6) C (3) (19) (17) (8) C (3) (2) (19) (10) C (3) (17) (17) (8) C (2) (14) (15) (6) C (2) (16) (17) (6) C (3) (18) (2) (8) C (3) (2) (2) (9) C (3) (15) (17) (7) C (4) (2) (2) (10) C (4) (19) (2) (9) C (2) (12) (12) (5) C (2) (14) (14) (5) C (3) (16) (14) (7) S39

40 C (3) (15) (15) (7) C (2) (15) (16) (6) C (2) (13) (14) (5) C (2) (16) (16) (6) C (3) (2) (3) (10) C (3) (18) (2) (8) C (2) (14) (16) (6) C (3) (17) (2) (9) C (3) (2) (2) (8) N (5) (3) (4) (16) C (5) (4) (5) (18) C (5) (5) (4) 0.065(2) Table S11. Bond lengths (Å) for 7. K1-O (16) K1-O (17) K1-N (5) K1-C (2) K1-C (3) K1-C (2) K1-C (3) K1-C (2) K1-C (3) K1-C (2) K1-C (6) S1-C (2) O1-C (3) O2-C (3) O2-K (17) N1-C (3) N1-C (3) N1-C (3) N2-C (3) N2-C (3) N2-C (3) C2-C (3) C3-C (3) C3-C (3) C5-C (3) C5-C (3) C6-C (3) C6-H C7-C (3) C7-H S40

41 C8-C (3) C8-C (3) C9-C (3) C9-H C10-H C11-C (3) C11-C (3) C12-C (3) C12-H C13-C (3) C13-H C14-C (4) C14-C (4) C15-C (4) C15-C (4) C16-C (5) C16-H C17-C (5) C17-H C18-C (4) C18-H C19-C (4) C20-C (4) C20-C (4) C20-H C21-H21A 0.98 C21-H21B 0.98 C21-H21C 0.98 C22-H22A 0.98 C22-H22B 0.98 C22-H22C 0.98 C23-C (5) C23-C (4) C23-H C24-H24A 0.98 C24-H24B 0.98 C24-H24C 0.98 C25-H25A 0.98 C25-H25B 0.98 C25-H25C 0.98 C26-C (4) C26-C (4) C26-K (2) C27-C (3) C27-C (4) C27-K (2) C28-C (4) C28-K (3) C28-H C29-C (4) C29-K (3) C29-H C30-C (3) C30-K (3) C30-H C31-C (4) C31-K (2) C32-C (4) S41

42 C32-C (4) C32-H C33-H33A 0.98 C33-H33B 0.98 C33-H33C 0.98 C34-H34A 0.98 C34-H34B 0.98 C34-H34C 0.98 C35-C (4) C35-C (4) C35-H C36-H36A 0.98 C36-H36B 0.98 C36-H36C 0.98 C37-H37A 0.98 C37-H37B 0.98 C37-H37C 0.98 N3-C (10) C38-C (11) C39-H39A 0.98 C39-H39B 0.98 C39-H39C 0.98 Table S12. Bond angles ( ) for 7. O1-K1-O (6) O1-K1-N (16) O2-K1-N (15) O1-K1-C (6) O2-K1-C (6) N3-K1-C (16) O1-K1-C (6) O2-K1-C (6) N3-K1-C (16) C27-K1-C (6) O1-K1-C (6) O2-K1-C (5) N3-K1-C (16) C27-K1-C (6) C28-K1-C (6) O1-K1-C (7) O2-K1-C (6) N3-K1-C (16) C27-K1-C (7) C28-K1-C (8) C26-K1-C (6) O1-K1-C (5) O2-K1-C (6) N3-K1-C (15) C27-K1-C (6) C28-K1-C (7) C26-K1-C (6) C29-K1-C (6) O1-K1-C (7) O2-K1-C (6) S42

43 N3-K1-C (16) C27-K1-C (7) C28-K1-C (8) C26-K1-C (6) C29-K1-C (8) C6-K1-C (6) O1-K1-C (6) O2-K1-C (6) N3-K1-C (16) C27-K1-C (7) C28-K1-C (7) C26-K1-C (6) C29-K1-C (6) C6-K1-C (6) C30-K1-C (6) O1-K1-C (14) O2-K1-C (13) N3-K1-C (19) C27-K1-C (14) C28-K1-C (14) C26-K1-C (14) C29-K1-C (14) C6-K1-C (13) C30-K1-C (14) C31-K1-C (14) C2-O1-K (15) C4-O2-K (14) C1-N1-C (18) C1-N1-C (17) C4-N1-C (17) C1-N2-C (18) C1-N2-C (18) C2-N2-C (17) N2-C1-N (18) N2-C1-S (17) N1-C1-S (16) O1-C2-C (2) O1-C2-N (19) C3-C2-N (18) C4-C3-C (19) C4-C3-C (19) C2-C3-C (19) O2-C4-C (2) O2-C4-N (19) C3-C4-N (19) C10-C5-C (19) C10-C5-C (2) C6-C5-C (2) C7-C6-C (2) C7-C6-K (14) C5-C6-K (15) C7-C6-H C5-C6-H K1-C6-H C6-C7-C (2) C6-C7-H C8-C7-H C9-C8-C (19) S43

44 C9-C8-C (2) C7-C8-C (19) C10-C9-C (2) C10-C9-H C8-C9-H C9-C10-C (2) C9-C10-H C5-C10-H C13-C11-C (19) C13-C11-C (19) C12-C11-C (2) C13-C12-C (2) C13-C12-H C11-C12-H C12-C13-C (2) C12-C13-H C11-C13-H C19-C14-C (2) C19-C14-N (2) C15-C14-N (2) C16-C15-C (3) C16-C15-C (3) C14-C15-C (2) C17-C16-C (3) C17-C16-H C15-C16-H C18-C17-C (3) C18-C17-H C16-C17-H C17-C18-C (3) C17-C18-H C19-C18-H C14-C19-C (3) C14-C19-C (2) C18-C19-C (3) C15-C20-C (3) C15-C20-C (2) C22-C20-C (3) C15-C20-H C22-C20-H C21-C20-H C20-C21-H21A C20-C21-H21B H21A-C21-H21B C20-C21-H21C H21A-C21-H21C H21B-C21-H21C C20-C22-H22A C20-C22-H22B H22A-C22-H22B C20-C22-H22C H22A-C22-H22C H22B-C22-H22C C19-C23-C (3) C19-C23-C (3) C25-C23-C (3) C19-C23-H C25-C23-H S44

45 C24-C23-H C23-C24-H24A C23-C24-H24B H24A-C24-H24B C23-C24-H24C H24A-C24-H24C H24B-C24-H24C C23-C25-H25A C23-C25-H25B H25A-C25-H25B C23-C25-H25C H25A-C25-H25C H25B-C25-H25C C31-C26-C (2) C31-C26-N (2) C27-C26-N (2) C31-C26-K (13) C27-C26-K (13) N1-C26-K (13) C28-C27-C (3) C28-C27-C (2) C26-C27-C (2) C28-C27-K (15) C26-C27-K (14) C32-C27-K (16) C29-C28-C (3) C29-C28-K (16) C27-C28-K (14) C29-C28-H C27-C28-H K1-C28-H C30-C29-C (2) C30-C29-K (15) C28-C29-K (15) C30-C29-H C28-C29-H K1-C29-H C29-C30-C (3) C29-C30-K (16) C31-C30-K (14) C29-C30-H C31-C30-H K1-C30-H C26-C31-C (2) C26-C31-C (2) C30-C31-C (2) C26-C31-K (13) C30-C31-K (15) C35-C31-K (15) C27-C32-C (3) C27-C32-C (2) C33-C32-C (3) C27-C32-H C33-C32-H C34-C32-H C32-C33-H33A C32-C33-H33B H33A-C33-H33B S45

46 C32-C33-H33C H33A-C33-H33C H33B-C33-H33C C32-C34-H34A C32-C34-H34B H34A-C34-H34B C32-C34-H34C H34A-C34-H34C H34B-C34-H34C C31-C35-C (2) C31-C35-C (2) C37-C35-C (3) C31-C35-H C37-C35-H C36-C35-H C35-C36-H36A C35-C36-H36B H36A-C36-H36B C35-C36-H36C H36A-C36-H36C H36B-C36-H36C C35-C37-H37A C35-C37-H37B H37A-C37-H37B C35-C37-H37C H37A-C37-H37C H37B-C37-H37C C38-N3-K (5) N3-C38-C (8) N3-C38-K1 42.6(3) C39-C38-K (5) C38-C39-H39A C38-C39-H39B H39A-C39-H39B C38-C39-H39C H39A-C39-H39C H39B-C39-H39C Table S13. Anisotropic atomic displacement parameters (Å 2 ) for 7. The anisotropic atomic displacement factor exponent takes the form: -2π 2 [ h 2 a *2 U h k a * b * U 12 ] U11 U22 U33 U23 U13 U12 K (3) (3) (3) (2) (2) (2) S (3) (3) (3) (2) (2) (2) O (9) (9) (7) (6) (7) (7) O (10) (9) (8) (7) (7) (8) N (10) (9) (9) (7) (7) (8) N (9) (9) (9) (7) (7) (7) C (11) (11) (10) (8) (8) (8) S46

47 C (11) (10) (10) (8) (8) (8) C (11) (10) (10) (8) (8) (8) C (11) (11) (10) (8) (9) (9) C (10) (11) (10) (8) (8) (8) C (11) (10) (11) (8) (9) (8) C (11) (11) (10) (8) (8) (8) C (10) (10) (10) (8) (8) (8) C (11) (10) (10) (8) (9) (8) C (11) (11) (10) (8) (8) (9) C (10) (10) (10) (8) (8) (8) C (10) (10) (11) (9) (9) (8) C (10) (11) (11) (9) (8) (8) C (13) (12) (11) (9) (9) (10) C (13) (15) (13) (11) (11) (11) C (16) 0.065(2) (16) (15) (13) (15) C (2) 0.067(2) (17) (16) (17) (19) C (2) (16) (15) (13) (15) (16) C (16) (13) (12) (10) (11) (12) C (13) (17) (15) (13) (11) (12) C (16) (18) 0.063(2) (16) (15) (14) C (16) 0.076(2) 0.058(2) (18) (14) (15) C (18) (14) (15) (11) (13) (13) C (2) 0.054(2) (18) (15) (17) (18) C (2) 0.050(2) 0.055(2) (16) (18) (17) C (12) (11) (10) (8) (9) (9) C (13) (13) (11) (9) (10) (10) C (16) (16) (12) (11) (11) (13) C (18) (16) (12) (11) (12) (13) C (15) (14) (14) (11) (12) (12) S47

48 C (13) (12) (12) (9) (10) (10) C (15) (16) (13) (11) (11) (12) C (17) 0.066(2) 0.092(3) 0.001(2) (18) (16) C (2) (17) 0.067(2) (16) (17) (15) C (13) (13) (14) (11) (11) (11) C (2) (16) 0.077(2) (16) (18) (15) C (16) 0.066(2) 0.059(2) (17) (14) (15) N (2) 0.071(3) 0.075(3) (3) 0.011(2) (2) C (2) 0.060(4) 0.089(5) (4) 0.014(3) (2) C (3) 0.115(7) 0.047(4) (4) 0.022(3) 0.021(4) Table S14. Hydrogen atomic coordinates and isotropic atomic displacement parameters (Å 2 ) for 7. x/a y/b z/c U(eq) H H H H H H H H H H H21A H21B H21C H22A H22B H22C S48

49 H H24A H24B H24C H25A H25B H25C H H H H H33A H33B H33C H34A H34B H34C H H36A H36B H36C H37A H37B H37C H39A H39B H39C S49

50 Crystal Structure Report for 8 (C110H110Au2N4O4P2 C7H8) A specimen of C 117 H 118 Au 2 N 4 O 4 P 2, approximate dimensions mm x mm x mm, was used for the X-ray crystallographic analysis. The X-ray intensity data were measured. The integration of the data using a monoclinic unit cell yielded a total of reflections to a maximum θ angle of (0.78 Å resolution), of which were independent (average redundancy 6.206, completeness = 99.9%, R int = 5.26%, R sig = 3.62%) and 9290 (81.44%) were greater than 2σ(F 2 ). The final cell constants of a = (14) Å, b = (6) Å, c = (10) Å, β = (10), volume = (7) Å 3, are based upon the refinement of the XYZ-centroids of reflections above 20 σ(i). The calculated minimum and maximum transmission coefficients (based on crystal size) are and The structure was solved and refined using the Bruker SHELXTL Software Package, using the space group C 1 2/c 1, with Z = 4 for the formula unit, C 117 H 118 Au 2 N 4 O 4 P 2. The final anisotropic full-matrix least-squares refinement on F 2 with 622 variables converged at R1 = 3.87%, for the observed data and wr2 = 12.28% for all data. The goodness-of-fit was The largest peak in the final difference electron density synthesis was e - /Å 3 and the largest hole was e - /Å 3 with an RMS deviation of e - /Å 3. On the basis of the final model, the calculated density was g/cm 3 and F(000), 4272 e -. Figure S22. Solid state molecular structure of 8 Table S15. Sample and crystal data for 8 (C 110 H 110 Au 2 N 4 O 4 P 2 C 7 H 8 ) Chemical formula C 117 H 118 Au 2 N 4 O 4 P 2 Formula weight Temperature Wavelength Crystal size Crystal system g/mol 100(2) K Å x x mm monoclinic Space group C 1 2/c 1 S50

51 Unit cell dimensions a = (14) Å α = 90 b = (6) Å β = (10) c = (10) Å γ = 90 Volume (7) Å 3 Z 4 Density (calculated) g/cm 3 Absorption coefficient mm -1 F(000) 4272 Table S16. Data collection and structure refinement for 8. Theta range for data collection 2.04 to Index ranges -42 h 42, -18 k 18, -33 l 28 Reflections collected Independent reflections [R(int) = ] Max. and min. transmission and Structure solution technique direct methods Structure solution program SHELXT-2014 (Sheldrick 2014) Refinement method Full-matrix least-squares on F 2 Refinement program SHELXL-2014 (Sheldrick 2014) Function minimized 2 Σ w(f o - F c2 ) 2 Data / restraints / parameters / 44 / 622 Goodness-of-fit on F Δ/σmax Final R indices 9290 data; I>2σ(I) R1 = , wr2 = all data R1 = , wr2 = Weighting scheme w=1/[σ 2 (F o2 )+(0.0608P) P] where P=(F o2 +2F c2 )/3 Largest diff. peak and hole and eå -3 R.M.S. deviation from mean eå -3 S51

52 Table S17. Atomic coordinates and equivalent isotropic atomic displacement parameters (Å 2 ) for 8. U(eq) is defined as one third of the trace of the orthogonalized U ij tensor. x/a y/b z/c U(eq) Au (2) (2) (2) (7) P (5) (9) (6) (3) O (15) (4) (19) (11) O (14) (3) (18) (9) N (14) (3) (19) (8) N (15) (3) (19) (8) C (18) (3) (2) (10) C (19) (4) (2) (10) C (18) (3) (2) (10) C (18) (3) (2) (10) C (18) (3) (2) (10) C (2) (4) (3) (11) C (2) (4) (3) (11) C (19) (4) (3) (11) C (19) (4) (3) (11) C (2) (4) (3) (11) C (19) (3) (3) (11) C (19) (4) (3) (11) C (19) (4) (3) (11) C (19) (4) (2) (10) C (19) (4) (2) (11) C (2) (5) (3) (13) C (2) (5) (3) (15) C (2) (5) (3) (13) C (19) (4) (2) (11) C (2) (4) (3) (13) C (3) (5) (3) (18) S52

53 C (3) (5) (3) (16) C (2) (4) (3) (13) C (3) (5) (3) (17) C (3) (6) (4) 0.058(2) C (18) (4) (2) (11) C (2) (4) (3) (12) C (2) (5) (3) (15) C (2) (6) (3) (17) C (2) (5) (3) (15) C (2) (4) (3) (12) C (3) (4) (3) (15) C (3) (6) (5) 0.068(2) C (3) (6) (4) 0.065(2) C (3) (5) (3) (17) C (3) (6) (4) 0.066(2) C (3) (5) (4) 0.064(2) C (2) (4) (2) (11) C (2) (4) (3) (14) C (3) (5) (3) (19) C (3) (5) (3) 0.051(2) C (3) (6) (3) 0.054(2) C (3) (5) (3) (16) C (18) (3) (2) (10) C (2) (4) (3) (11) C (2) (4) (3) (14) C (2) (4) (3) (13) C (2) (4) (3) (13) C (2) (4) (3) (12) C (19) (4) (2) (10) S53

54 C (2) (4) (3) (12) C (2) (5) (3) (14) C (2) (5) (3) (16) C (3) (4) (3) (16) C (2) (4) (3) (13) C (6) (14) (9) 0.071(4) C (4) (12) (8) 0.052(3) C (6) (12) (8) 0.073(4) C (6) (12) (8) 0.072(4) C (6) (10) (8) 0.066(4) C (6) (12) (9) 0.069(4) C (8) (17) (8) 0.090(6) Table S18. Bond lengths (Å) for 8. Au1-C (5) Au1-P (13) P1-C (5) P1-C (5) P1-C (5) O1-C (7) O2-C (6) N1-C (6) N1-C (6) N1-C (6) N2-C (6) N2-C (6) N2-C (6) C2-C (7) C3-C (7) C3-C (7) C5-C (8) C5-C (8) C6-C (7) C6-H C7-C (8) C7-H C8-C (8) C8-C (7) C9-C (7) C9-H C10-H C11-C (8) C11-C (8) C12-C (7) S54

55 C12-H C13-C (7) C13-H C14-C (8) C14-C (8) C15-C (8) C15-C (8) C16-C (10) C16-H C17-C (9) C17-H C18-C (8) C18-H C19-C (8) C20-C (9) C20-C (8) C20-H C21-H21A 0.98 C21-H21B 0.98 C21-H21C 0.98 C22-H22A 0.98 C22-H22B 0.98 C22-H22C 0.98 C23-C (9) C23-C (9) C23-H C24-H24A 0.98 C24-H24B 0.98 C24-H24C 0.98 C25-H25A 0.98 C25-H25B 0.98 C25-H25C 0.98 C26-C (8) C26-C (8) C27-C (8) C27-C (9) C28-C (10) C28-H C29-C (10) C29-H C30-C (8) C30-H C31-C (9) C32-C (11) C32-C (10) C32-H C33-H33A 0.98 C33-H33B 0.98 C33-H33C 0.98 C34-H34A 0.98 C34-H34B 0.98 C34-H34C 0.98 C35-C (11) C35-C (11) C35-H C36-H36A 0.98 C36-H36B 0.98 C36-H36C 0.98 S55

56 C37-H37A 0.98 C37-H37B 0.98 C37-H37C 0.98 C38-C (9) C38-C (9) C39-C (9) C39-H C40-C (12) C40-H C41-C (12) C41-H C42-C (9) C42-H C43-H C44-C (7) C44-C (7) C45-C (8) C45-H C46-C (9) C46-H C47-C (9) C47-H C48-C (8) C48-H C49-H C50-C (8) C50-C (7) C51-C (8) C51-H C52-C (10) C52-H C53-C (10) C53-H C54-C (9) C54-H C55-H C56-C (2) C56-C (2) C56-C (2) C57-C (2) C57-H C58-C (16) C58-H C59-C (16) C59-H C60-C (3) C60-H C61-H C62-H62A 0.98 C62-H62B 0.98 C62-H62C 0.98 S56

57 Table S19. Bond angles ( ) for 8. C1-Au1-P (13) C44-P1-C (2) C44-P1-C (2) C50-P1-C (3) C44-P1-Au (16) C50-P1-Au (18) C38-P1-Au (2) C1-N1-C (4) C1-N1-C (4) C4-N1-C (4) C1-N2-C (4) C1-N2-C (4) C2-N2-C (4) N1-C1-N (4) N1-C1-Au (3) N2-C1-Au (4) O1-C2-C (5) O1-C2-N (5) C3-C2-N (4) C2-C3-C (4) C2-C3-C (5) C4-C3-C (4) O2-C4-C (5) O2-C4-N (4) C3-C4-N (4) C6-C5-C (5) C6-C5-C (5) C10-C5-C (5) C7-C6-C (5) C7-C6-H C5-C6-H C8-C7-C (5) C8-C7-H C6-C7-H C7-C8-C (5) C7-C8-C (5) C9-C8-C (5) C10-C9-C (5) C10-C9-H C8-C9-H C9-C10-C (5) C9-C10-H C5-C10-H C13-C11-C (5) C13-C11-C (5) C12-C11-C (5) C13-C12-C (5) C13-C12-H C11-C12-H C11-C13-C (5) C11-C13-H C12-C13-H C15-C14-C (5) C15-C14-N (5) C19-C14-N (5) C14-C15-C (5) S57

58 C14-C15-C (5) C16-C15-C (5) C17-C16-C (6) C17-C16-H C15-C16-H C16-C17-C (5) C16-C17-H C18-C17-H C17-C18-C (6) C17-C18-H C19-C18-H C18-C19-C (5) C18-C19-C (5) C14-C19-C (5) C15-C20-C (5) C15-C20-C (5) C21-C20-C (5) C15-C20-H C21-C20-H C22-C20-H C20-C21-H21A C20-C21-H21B H21A-C21-H21B C20-C21-H21C H21A-C21-H21C H21B-C21-H21C C20-C22-H22A C20-C22-H22B H22A-C22-H22B C20-C22-H22C H22A-C22-H22C H22B-C22-H22C C24-C23-C (6) C24-C23-C (5) C25-C23-C (6) C24-C23-H C25-C23-H C19-C23-H C23-C24-H24A C23-C24-H24B H24A-C24-H24B C23-C24-H24C H24A-C24-H24C H24B-C24-H24C C23-C25-H25A C23-C25-H25B H25A-C25-H25B C23-C25-H25C H25A-C25-H25C H25B-C25-H25C C31-C26-C (5) C31-C26-N (5) C27-C26-N (5) C28-C27-C (6) C28-C27-C (6) C26-C27-C (5) C29-C28-C (6) C29-C28-H S58

59 C27-C28-H C28-C29-C (6) C28-C29-H C30-C29-H C29-C30-C (6) C29-C30-H C31-C30-H C26-C31-C (5) C26-C31-C (5) C30-C31-C (6) C34-C32-C (6) C34-C32-C (6) C27-C32-C (6) C34-C32-H C27-C32-H C33-C32-H C32-C33-H33A C32-C33-H33B H33A-C33-H33B C32-C33-H33C H33A-C33-H33C H33B-C33-H33C C32-C34-H34A C32-C34-H34B H34A-C34-H34B C32-C34-H34C H34A-C34-H34C H34B-C34-H34C C31-C35-C (6) C31-C35-C (7) C37-C35-C (6) C31-C35-H C37-C35-H C36-C35-H C35-C36-H36A C35-C36-H36B H36A-C36-H36B C35-C36-H36C H36A-C36-H36C H36B-C36-H36C C35-C37-H37A C35-C37-H37B H37A-C37-H37B C35-C37-H37C H37A-C37-H37C H37B-C37-H37C C43-C38-C (5) C43-C38-P (5) C39-C38-P (4) C40-C39-C (7) C40-C39-H C38-C39-H C41-C40-C (7) C41-C40-H C39-C40-H C42-C41-C (6) C42-C41-H C40-C41-H S59

60 C41-C42-C (7) C41-C42-H C43-C42-H C38-C43-C (7) C38-C43-H C42-C43-H C45-C44-C (5) C45-C44-P (4) C49-C44-P (4) C44-C45-C (5) C44-C45-H C46-C45-H C47-C46-C (5) C47-C46-H C45-C46-H C46-C47-C (5) C46-C47-H C48-C47-H C47-C48-C (6) C47-C48-H C49-C48-H C48-C49-C (5) C48-C49-H C44-C49-H C55-C50-C (5) C55-C50-P (4) C51-C50-P (4) C52-C51-C (6) C52-C51-H C50-C51-H C53-C52-C (6) C53-C52-H C51-C52-H C52-C53-C (6) C52-C53-H C54-C53-H C53-C54-C (6) C53-C54-H C55-C54-H C50-C55-C (6) C50-C55-H C54-C55-H C62-C56-C (2) C62-C56-C (2) C61-C56-C (18) C58-C57-C (18) C58-C57-H C56-C57-H C57-C58-C (2) C57-C58-H C59-C58-H C60-C59-C (18) C60-C59-H C58-C59-H C59-C60-C (16) C59-C60-H C61-C60-H C56-C61-C (17) S60

61 C56-C61-H C60-C61-H C56-C62-H62A C56-C62-H62B H62A-C62-H62B C56-C62-H62C H62A-C62-H62C H62B-C62-H62C Table S20. Anisotropic atomic displacement parameters (Å 2 ) for 8. The anisotropic atomic displacement factor exponent takes the form: -2π 2 [ h 2 a *2 U h k a * b * U 12 ] U11 U22 U33 U23 U13 U12 Au (11) (11) (11) (7) (8) (7) P (6) (6) (6) (5) (5) (5) O (2) 0.078(3) 0.024(2) (2) (18) (2) O (19) 0.049(3) 0.029(2) (18) (17) (17) N (19) 0.020(2) 0.018(2) (16) (17) (16) N (19) 0.022(2) 0.020(2) (16) (17) (16) C (2) 0.016(2) 0.021(2) (19) 0.016(2) (19) C (2) 0.030(3) 0.023(3) (2) 0.017(2) (2) C (2) 0.020(2) 0.025(3) (19) 0.014(2) (19) C (2) 0.020(2) 0.026(3) (2) 0.015(2) (19) C (2) 0.020(2) 0.027(3) (2) 0.015(2) (19) C (3) 0.028(3) 0.032(3) 0.004(2) 0.019(2) 0.004(2) C (3) 0.026(3) 0.032(3) 0.001(2) 0.021(2) 0.001(2) C (3) 0.021(2) 0.033(3) (2) 0.021(2) (2) C (2) 0.023(3) 0.036(3) (2) 0.019(2) (2) C (3) 0.024(3) 0.032(3) 0.002(2) 0.020(2) (2) C (3) 0.015(2) 0.041(3) (2) 0.024(2) (19) C (3) 0.023(3) 0.030(3) 0.002(2) 0.018(2) 0.001(2) C (2) 0.022(3) 0.036(3) (2) 0.018(2) (2) C (2) 0.033(3) 0.019(2) (2) 0.016(2) 0.000(2) C (3) 0.035(3) 0.025(3) 0.004(2) 0.016(2) 0.004(2) C (3) 0.051(4) 0.028(3) 0.012(3) 0.013(2) 0.008(3) S61

62 C (3) 0.066(4) 0.027(3) (3) 0.010(2) (3) C (3) 0.043(3) 0.031(3) (3) 0.018(3) (3) C (3) 0.038(3) 0.026(3) (2) 0.018(2) (2) C (3) 0.031(3) 0.034(3) 0.007(2) 0.018(3) 0.006(2) C (5) 0.036(4) 0.054(4) 0.009(3) 0.043(4) 0.012(4) C (4) 0.037(3) 0.054(4) 0.011(3) 0.039(4) 0.003(3) C (3) 0.025(3) 0.046(3) (3) 0.024(3) (2) C (4) 0.036(4) 0.060(4) 0.006(3) 0.038(4) 0.013(3) C (5) 0.052(4) 0.073(5) (4) 0.047(5) 0.005(4) C (2) 0.034(3) 0.017(2) (2) 0.010(2) (2) C (3) 0.038(3) 0.033(3) (3) 0.017(2) (2) C (3) 0.052(4) 0.036(3) (3) 0.023(3) (3) C (3) 0.079(5) 0.021(3) (3) 0.015(3) 0.001(3) C (3) 0.048(4) 0.026(3) 0.013(3) 0.009(3) 0.009(3) C (3) 0.042(3) 0.022(3) 0.002(2) 0.010(2) 0.004(2) C (4) 0.026(3) 0.047(4) (3) 0.036(3) (3) C (6) 0.051(5) 0.093(7) (5) 0.054(5) (4) C (5) 0.045(4) 0.084(6) 0.008(4) 0.037(5) 0.001(4) C (5) 0.034(3) 0.039(4) 0.011(3) 0.028(3) 0.013(3) C (6) 0.064(5) 0.065(5) 0.027(4) 0.053(5) 0.039(5) C (6) 0.038(4) 0.069(5) 0.008(4) 0.043(5) (4) C (3) 0.023(3) 0.024(3) (2) 0.021(2) (2) C (3) 0.036(3) 0.022(3) 0.002(2) 0.011(3) (3) C (5) 0.039(4) 0.026(3) (3) 0.012(3) (3) C (6) 0.041(4) 0.021(3) (3) 0.024(4) (4) C (6) 0.066(5) 0.038(4) (3) 0.046(4) (4) C (4) 0.057(4) 0.029(3) (3) 0.028(3) (3) C (2) 0.020(2) 0.030(3) (2) 0.018(2) 0.002(2) C (3) 0.022(3) 0.033(3) 0.002(2) 0.020(2) (2) S62

63 C (3) 0.021(3) 0.050(4) 0.002(3) 0.029(3) (2) C (3) 0.025(3) 0.046(4) (3) 0.019(3) (2) C (3) 0.033(3) 0.032(3) (2) 0.017(3) (3) C (3) 0.024(3) 0.031(3) (2) 0.019(2) (2) C (2) 0.025(3) 0.026(3) (2) 0.016(2) 0.001(2) C (3) 0.033(3) 0.036(3) (2) 0.020(3) (2) C (3) 0.042(4) 0.046(4) (3) 0.025(3) 0.005(3) C (4) 0.041(4) 0.048(4) (3) 0.022(3) 0.013(3) C (4) 0.025(3) 0.055(4) (3) 0.028(4) 0.006(3) C (3) 0.025(3) 0.040(3) (2) 0.019(3) (2) C (6) 0.074(7) 0.081(7) (6) 0.023(6) 0.004(6) C (5) 0.056(7) 0.073(7) 0.023(6) 0.019(5) (5) C (6) 0.066(7) 0.073(8) 0.023(6) 0.011(6) 0.001(6) C (7) 0.062(7) 0.072(7) 0.006(6) 0.016(6) 0.016(6) C (6) 0.028(6) 0.083(7) (6) 0.012(6) 0.000(5) C (6) 0.057(7) 0.102(8) (6) 0.044(6) (6) C (12) 0.127(14) 0.034(8) (9) 0.027(8) (11) Table S21. Hydrogen atomic coordinates and isotropic atomic displacement parameters (Å 2 ) for 8. x/a y/b z/c U(eq) H H H H H H H H S63

64 H H H21A H21B H21C H22A H22B H22C H H24A H24B H24C H25A H25B H25C H H H H H33A H33B H33C H34A H34B H34C H H36A H36B H36C S64

65 H37A H37B H37C H H H H H H H H H H H H H H H H H H H H H62A H62B H62C S65

66 Crystal Structure Report for 9 (C110H110Ag2N4O4P2 C7H8) A specimen of C 117 H 118 Ag 2 N 4 O 4 P 2, approximate dimensions mm x mm x mm, was used for the X-ray crystallographic analysis. The X-ray intensity data were measured. The integration of the data using a monoclinic unit cell yielded a total of reflections to a maximum θ angle of (0.80 Å resolution), of which were independent (average redundancy , completeness = 99.6%, R int = 6.89%, R sig = 2.47%) and 8892 (82.11%) were greater than 2σ(F 2 ). The final cell constants of a = (5) Å, b = (2) Å, c = (4) Å, β = (11), volume = (3) Å 3, are based upon the refinement of the XYZ-centroids of reflections above 20 σ(i). The calculated minimum and maximum transmission coefficients (based on crystal size) are and The structure was solved and refined using the Bruker SHELXTL Software Package, using the space group C 1 2/c 1, with Z = 4 for the formula unit, C 117 H 118 Ag 2 N 4 O 4 P 2. The final anisotropic full-matrix least-squares refinement on F 2 with 622 variables converged at R1 = 6.09%, for the observed data and wr2 = 20.45% for all data. The goodness-of-fit was The largest peak in the final difference electron density synthesis was e - /Å 3 and the largest hole was e - /Å 3 with an RMS deviation of e - /Å 3. On the basis of the final model, the calculated density was g/cm 3 and F(000), 4016 e -. Figure S23. Solid state molecular structure of 9 S66

67 Figure S24. Solid state packing diagram of 9 Table S22. Sample and crystal data for 9. Chemical formula C 117 H 118 Ag 2 N 4 O 4 P 2 Formula weight Temperature Wavelength Crystal size Crystal system g/mol 100(2) K Å x x mm monoclinic Space group C 1 2/c 1 Unit cell dimensions a = (5) Å α = 90 b = (2) Å β = (11) S67