Isolation of atomically precise mixed ligand shell PdAu 24 clusters. Supporting Information

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1 Electronic Supplementary Material (ESI) for Nanoscale. This journal is The Royal Society of Chemistry 2016 Isolation of atomically precise mixed ligand shell PdAu 24 clusters - Supporting Information Annelies Sels, 1 Noelia Barrabés 2, Stefan Knoppe, 3 Thomas Bürgi 1* 1: Department of Physical Chemistry, University of Geneva, 30 Quai Ernest-Ansermet, 1211 Geneva 4, Switzerland 2: Institute of Materials Chemistry, Technical University of Vienna, Getreidemarkt 9/BC/01, 1060 Vienna, Austria 3: Molecular Imaging and Photonics, Department of Chemistry, KU Leuven, Celestijnenlaan 200D, 3001 Leuven, Belgium *: corresponding author, Thomas.Buergi@unige.ch S-1

2 Figure S1. MALDI-TOF mass spectra of the crude exchanged product after 72h reaction. The original PdAu 24 (2-PET) 18 and PdAu 24 (2-PET) 16 (R-BINAS) 1 are no longer observed, resulting in a higher amount of exchanged BINAS. Figure S2. CD spectra of PdAu 24 (2-PET) 18-2x (R-BINAS) x and PtAu 24 (2-PET) 18-2x (R- BINAS) x after 24h exchange reaction (left) and CD spectra of pure R-BINAS (right). The CD signal confirms the induced secondary level of chirality. S-2

3 All possible exchange isomers of PdAu 24 (2-PET) 14 (R-BINAS) 2 PdAu 24 (2-PET) 18 consists of six dimeric staples, containing one apex and two core sulphurs. Assuming an interstaple binding mode of dithiol ligands, BINAS binds from the apex S-atom in one staple to a core S-atom in another staple. Statistically, after one BINAS ligand is exchanged, five apex sulphurs remain available for the 2 nd BINAS, resulting in ten possible isomers of PdAu 24 (2-PET) 14 (R-BINAS) 2. However, repetition of isomers can occur considering the high symmetry of the cluster. Herein all ten configurations are identified and after rotation, matched to identical isomers. Isomers I3/I5 and I4/I6 are enantiomers concerning their adsorption pattern. Structure I1 Structure I2 S-3

4 Structure I3 Structure I4 Structure I5 S-4

5 Structure I6 Figure S3. Isomers of PdAu 24 (2-PET) 14 (R-BINAS) 2 S-5

6 All possible exchange isomers of PdAu 24 (2-PET) 12 (R-BINAS) 3 Statistically, 15 configurations of PdAu 24 (2-PET) 12 (R-BINAS) 3 are possible. However, due to the high relative energy of I5, eight structures can be excluded. Below the seven remaining isomers are shown. Structure 1 Structure 5 Structure 6 Structure 4 Structure 2 Structure 3 S-6

7 Structure 7 Figure S3. Isomers of PdAu 24 (2-PET) 12 (R-BINAS) 3 S-7

8 Coordinates of all optimized structures Coordinates of PdAu 24 (CH 3 ) 18 Au Au Au Au Au Au Au Au Au Au Au Au Au S S S S S S S S S S-8

9 C H H C H H C H H C H H C H H C H H C H H C H H C S-9

10 H H Au Au Au Au Au Au Au Au Au Au Au Au S S S S S S S S S C H S-10

11 H C H H C H H C H H C H H C H H C H H C H H C H H S-11

12 H H H H H H H H H H H H H H H H H H S-12

13 Coordinates of PdAu 24 (CH 3 ) 16 (S-BINAS) 1 Au Au Au Au Au Au Au Au Au Au Au Au Au S S S S S S S S S S-13

14 Au Au Au Au Au Au Au Au Au Au Au Au S S S S S S S S S C C C C S-14

15 C H C H C C C C C H C H C C C C H H H H C C C C H S-15

16 H H H C H H H C H H H C H H H C H H H C H H H C H S-16

17 H H C H H H C H H H C H H H C H H H C H H H C H H S-17

18 H C H H H C H H H C H H H C H H H S-18

19 Coordinates of PdAu 24 (CH 3 ) 14 (S-BINAS) 2 (Isomer 1) Au Au Au Au Au Au Au Au Au Au Au Au Au S S S S S S S S S Au S-19

20 Au Au Au Au Au Au Au Au Au Au Au S S S S S S S S S C C C C C S-20

21 H C H C C C C C H C H C C C C H H H H C C C C H H S-21

22 H H C H H H C H H H C H H H C H H H C H H H C H H S-22

23 H C H H H C H H H C H H H C H H H C H H H C H H H S-23

24 C H H H C H H H C C C C C H C C H C H C C H H H C S-24

25 C C C C C C H C C H C H H H H S-25

26 Coordinates of PdAu 24 (CH 3 ) 14 (S-BINAS) 2 (Isomer 2) Au Au Au Au Au Au Au Au Au Au Au Au Au S S S S S S S S S Au S-26

27 Au Au Au Au Au Au Au Au Au Au Au S S S S S S S S S C C C C C S-27

28 H C H C C C C C H C H C C C C H H H H C C C C H H S-28

29 H H C H H H C H H H C H H H C H H H C H H H C H H S-29

30 H C H H H C H H H C H H H C H H H C H H H C H H H S-30

31 C H H H C H H H C C C C C H C C H C H C C H H H C S-31

32 C C C C C C H C C H C H H H H S-32

33 Coordinates of PdAu 24 (CH 3 ) 14 (S-BINAS) 2 (Isomer 3) Au Au Au Au Au Au Au Au Au Au Au Au Au S S S S S S S S S Au S-33

34 Au Au Au Au Au Au Au Au Au Au Au S S S S S S S S C C C C C H S-34

35 C H C C C C C H C H C C C C H H H H C C C C H H H S-35

36 H C H H H C H H H C H H H C H H H C H H H C H H H S-36

37 C H H H C H H H C H H H C H H H C H H H C H H H C S-37

38 H H H C H H H C C C C H C C C H C H C C H H H C C S-38

39 C C C C C H C C H C H H H H S S-39

40 Coordinates of PdAu 24 (CH 3 ) 14 (S-BINAS) 2 (Isomer 4) Au Au Au Au Au Au Au Au Au Au Au Au Au S S S S S S S Au Au Au Au S-40

41 Au Au Au Au Au Au Au Au S S S S S S S S S C C C C C H C H S-41

42 C C C C C H C H C C C C H H H H C C C C H H H H C S-42

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