SUPPORTING INFORMATION

Transcription

1 SUPPORTING INFORMATION Silylium-Arene Adducts: An Experimental And Theoretical Study Muhammad Farooq Ibad, Peter Langer, Axel Schulz* and Alexander Villinger* This file includes: 1. Experimental p Structure elucidation p General procedure for the synthesis of trimethylsilicenium-arene salts p IR spectra of trimethylsilylium-arene-adducts p Raman and IR data of arenes p Computational details p References p.136 1

2 1. Experimental General Information. All manipulations were carried out under oxygen- and moisture-free conditions under argon using standard Schlenk or drybox techniques. Benzene (99.7, Sigma-Aldrich), toluene (99.7, Sigma-Aldrich), ethyl benzene (VEB Berlin, Berlin Adlershof), n-propylbenzene (98%, Aldrich), iso-propylbenzene (97%, Ferak Chemikalien, Berlin), tert.-butylbenzene (97%, Fluka), m-xylene (97%, Reachim) and p- xylene (97%, VEB Teerdestilation und Chemische Fabrik, Erkner), o-xylene (97%, VEB Petrolchemisches Kombinat Schwedt, BT Erkner), 1,2,3-trimethyl benzene (95%, Fluka), 1,2,4 trimethyl benzene (techn., VEB Teerdestilation und Chemische Fabrik, Erkner), and 1,3,5-trimethyl benzene (98%, Merck), were dried over Na/benzophenone and freshly distilled prior to use. N-heptane was freshly distilled prior to use. Bis(trimethylsilyl)hydronium tetrakis(pentafluorophenyl)borate [Me 3 Si-H-SiMe 3 ][B(C 6 F 5 ) 4 ] was prepared as previously reported. [1] NMR: 13 C{ 1 H}, 13 C DEPT, and 1 H NMR spectra were obtained on a Bruker AVANCE 300 spectrometer and were referenced internally to the deuterated solvent ( 13 C, CDCl 3 : δ reference = 77 ppm) or to protic impurities in the deuterated solvent ( 1 H, CHCl 3 : δ reference = 7.26 ppm). CDCl 3 was dried over P 4 O 10 and freshly distilled prior to use. IR: Nicolet 6700 FT-IR spectrometer with a Smart Endurance ATR device was used. Raman: Bruker VERTEX 70 FT-IR with RAM II FT-Raman module, equipped with a Nd:YAG laser (1064 nm) was used. CHN analyses: C/H/N/S-Mikronalysator TruSpec-932 from Leco was used. DSC: DSC 823e from Mettler-Toledo (Heating-rate 5 C/min) was used. 2

3 2. Structure elucidation X-ray Structure Determination: X-ray quality crystals of [Me 3 Si benzene][b(c 6 F 5 ) 4 ] (A1), [Me 3 Si benzene][b(c 6 F 5 ) 4 ] (A2), [Me 3 Si benzene/sime 3 FSiMe 3 ][B(C 6 F 5 ) 4 ] (A3), [Me 3 Si toluene][b(c 6 F 5 ) 4 ] (B1), [Me 3 Si toluene/sime 3 FSiMe 3 ][B(C 6 F 5 ) 4 ] (B2), [Me 3 Si ethylbenzene][b(c 6 F 5 ) 4 ] (C), [Me 3 Si n-propylbenzene][b(c 6 F 5 ) 4 ] (D), [Me 3 Si ipropylbenzene][b(c 6 F 5 ) 4 ] (E), [Me 3 Si o-xylene][b(c 6 F 5 ) 4 ] (F), [Me 3 Si m-xylene][b(c 6 F 5 ) 4 ] (G), [Me 3 Si p-xylene][b(c 6 F 5 ) 4 ] (H), [Me 3 Si 1,2,3-trimethylbenzene][B(C 6 F 5 ) 4 ] (I), [Me 3 Si 1,2,4-trimethylbenzene][B(C 6 F 5 ) 4 ] (J), [Me 3 Si 1,3,5-trimethylbenzene][B(C 6 F 5 ) 4 ] (K), 1,4-di-tert.-butylbenzene (L) and C 6 F 4 CS 2 -B(C 6 F 5 ) 3 (M) were selected in Fomblin YR-1800 perfluoroether (Alfa Aesar) at ambient temperatures. All samples were cooled to 173(2) K during measurement. The data were collected on a Bruker Apex Kappa-II or Bruker-Nonius Apex-X8 CCD diffractometer using graphite monochromated Mo Kα radiation (λ = ). The structures were solved by direct methods (SHELXS-97or SIR2004) [2,3] and refined by fullmatrix least squares procedures (SHELXL-97). [4] Semi-empirical absorption corrections were applied (SADABS). [5] All non hydrogen atoms were refined anisotropically, hydrogen atoms were included in the refinement at calculated positions using a riding model. The position of one [Me 3 Si-benzene] cation in A3 was found to be partially occupied by a [Me 3 Si-F-SiMe 3 ] cation. The occupancy of each part was refined freely (0.525(2)/0.475(2)). The position of the 1,2,3-trimethylbenzene molecule in the[me 3 Si-1,2,3-trimethylbenzene] cation in I was found to be disordered, and was split in two parts. The occupancy of each part was refined freely (0.667(3)/0.333(3)). The position of the free 1,2,3-trimethylbenzene molecule in I was found to be disordered, and was split in two parts. The occupancy of each part was refined freely (0.524(7)/0.476(7)). The position of the [Me 3 Si-1,2,4-trimethylbenzene] cation in J was found to be disordered, and was split in two parts. The occupancy of each part was refined freely (0.856(2)/0.144(2)). The position of the free 1,2,4-trimethylbenzene molecule in J was found to be disordered, and was split in two parts. The occupancy of each part was refined freely (0.524(8)/0.476(8)). The position of one [Me 3 Si-1,3,5-trimethylbenzene] cation in K was found to be disordered, and was split in two parts. The occupancy of each part was refined freely (0.685(4)/0.315(4)). 3

4 Table S1. Crystallographic Details of A1, A2 and A3. A1 A2 A3 benzene benzene benzene/fluoronium Chem. Formula C 33 H 15 BF 20 Si C 33 H 15 BF 20 Si C H BF Si 1.24 Form. Wght. [g mol -1 ] Colour Colourless Colourless Colourless Cryst. system Monoclinic Monoclinic Monoclinic Space group P2/c P2/c P2 1 /c a [Å] b [Å] c [Å] α [ ] [ ] [ ] (5) (2) (5) (10) (8) (3) (9) (2) (2) (10) (4) (10) V [Å 3 ] (14) (2) (3) Z calc. [g cm -3 ] [mm -1 ] λ MoKα [Å] T [K] 173(2) 173(2) 173(2) Measured reflections Independent reflections Reflections with I > 2σ(I) R int F(000) R 1 (R [F 2 > 2σ(F 2 )]) wr 2 (F 2 ) GooF Parameters CCDC #

5 Table S2. Crystallographic Details of B1, B2 and C. B1 B2 C toluene toluene/fluoronium ethylbenzene Chem. Formula C 34 H 17 BF 20 Si C H BF Si 1.08 C 43 H 29 BF 20 Si Form. Wght. [g mol -1 ] Colour Colourless Colourless Colourless Cryst. system Orthorhombic Orthorhombic Monoclinic Space group Pbca Pbca P2 1 /n a [Å] b [Å] c [Å] α [ ] [ ] [ ] (11) (12) (14) (4) (5) (5) (5) (7) (6) (2) V [Å 3 ] (8) (3) (3) Z calc. [g cm -3 ] [mm -1 ] λ MoKα [Å] T [K] 173(2) 173(2) 173(2) Measured reflections Independent reflections Reflections with I > 2σ(I) R int F(000) R 1 (R [F 2 > 2σ(F 2 )]) wr 2 (F 2 ) GooF Parameters CCDC #

6 Table S3. Crystallographic Details of D, E and F. D E F n-propylbenzene i-propylbenzene o-xylene Chem. Formula C 36 H 21 BF 20 Si C 36 H 21 BF 20 Si C 35 H 19 BF 20 Si Form. Wght. [g mol -1 ] Colour Colourless Colourless Colourless Cryst. system Monoclinic Monoclinic Monoclinic Space group P2 1 /c P2 1 /c P2 1 /n a [Å] b [Å] c [Å] α [ ] [ ] [ ] (7) (5) (6) (10) (3) (7) (5) (2) (6) (4) (10) (10) V [Å 3 ] (4) (19) (4) Z calc. [g cm -3 ] [mm -1 ] λ MoKα [Å] T [K] 173(2) 173(2) 173(2) Measured reflections Independent reflections Reflections with I > 2σ(I) R int F(000) R 1 (R [F 2 > 2σ(F 2 )]) wr 2 (F 2 ) GooF Parameters CCDC #

7 Table S4. Crystallographic Details of G, H and I. G H I m-xylene p-xylene 1,2,3-trimethylbenzene Chem. Formula C 43 H 29 BF 20 Si C 43 H 29 BF 20 Si C 45 H 33 BF 20 Si Form. Wght. [g mol -1 ] Colour Colourless Colourless Colourless Cryst. system Monoclinic Orthorhombic Monoclinic Space group P2 1 /c Pbca P2 1 /c a [Å] b [Å] c [Å] α [ ] [ ] [ ] (7) (9) (8) (10) (11) (11) (15) (7) (10) (8) (2) V [Å 3 ] (3) (9) (4) Z calc. [g cm -3 ] [mm -1 ] λ MoKα [Å] T [K] 173(2) 173(2) 173(2) Measured reflections Independent reflections Reflections with I > 2σ(I) R int F(000) R 1 (R [F 2 > 2σ(F 2 )]) wr 2 (F 2 ) GooF Parameters CCDC #

8 Table S5. Crystallographic Details of J, K, and L. J K L 1,2,4-trimethylbenzene 1,3,5-trimethylbenzene Chem. Formula C 45 H 33 BF 20 Si C H 30 BF 20 Si C 14 H 22 Form. Wght. [g mol -1 ] Colour Colourless Colourless Colourless Cryst. system Monoclinic Triclinic Monoclinic Space group P2 1 /c P-1 P2 1 /n a [Å] b [Å] c [Å] α [ ] [ ] [ ] (11) (13) (11) (4) (3) (5) (6) (10) (10) (10) 1,4-di-tert-butylbenzene (4) (6) (6) (4) V [Å 3 ] (5) (2) (7) Z calc. [g cm -3 ] [mm -1 ] λ MoKα [Å] T [K] 173(2) 173(2) 173(2) Measured reflections Independent reflections Reflections with I > 2σ(I) R int F(000) R 1 (R [F 2 > 2σ(F 2 )]) wr 2 (F 2 ) GooF Parameters CCDC #

9 Table S6. Crystallographic Details of C 6 F 4 CS 2 -B(C 6 F 5 ) 3 (M). M C 6 F 4 CS 2 -B(C 6 F 5 ) 3 Chem. Formula C 25 BF 19 S 2 Form. Wght. [g mol -1 ] Colour Colourless Cryst. system Monoclinic Space group P2 1 /n a [Å] b [Å] c [Å] α [ ] [ ] [ ] (5) (6) (5) (10) V [Å 3 ] (3) Z 8 calc. [g cm -3 ] [mm -1 ] λ MoKα [Å] T [K] 173(2) Measured reflections Independent reflections Reflections with I > 2σ(I) 9605 R int F(000) 2864 R 1 (R [F 2 > 2σ(F 2 )]) wr 2 (F 2 ) GooF Parameters 847 CCDC # - 9

10 10 Scheme S1. Numbering scheme of A1. Si C1 C2 C3 (1) B C10 C11 C12 C13 C14 C15 F2 F3 F4 F5 F6 F7 F8 F9 F10 C21 C10' C11' C12' C13' C14' F1 F1' F2' F3' F4' F5' F6' F7' F8' F9' F10' C16 C17 C18 C19 C20 C15' C16' C4 C5 C6 C7 C8 C9 C17' C18' C19' C20' C21' B C22 C23 C24 C25 C26 C27 F12 F13 F14 F15 F16 F17 F18 F19 F20 C33 C22' C23' C24' C25' C26' F11 F11' F12' F13' F14' F15' F16' F17' F18' F19' F20' C28 C29 C30 C31 C32 C27' C28' C29' C30' C31' C32' C33' (1) (2)

11 Table S6. Selected bond lengths (Å), angles and torsion angles ( ) of A1. Si1 C (2) C2 C1 H (13) Si1 C (2) Si1 C1 H (14) Si1 C (2) C3 C2 C (19) Si1 C (2) C2 C3 C (18) C1 C (3) C5 C4 C (2) C1 C (3) C6 C5 C (19) C1 H (2) C5 C6 C (18) C2 C (3) C8 Si1 C1 C (15) C3 C (3) C9 Si1 C1 C (15) C4 C (3) C7 Si1 C1 C (16) C5 C (3) C8 Si1 C1 C (14) C8 Si1 C (12) C9 Si1 C1 C (17) C8 Si1 C (10) C7 Si1 C1 C (16) C9 Si1 C (13) C6 C1 C2 C3 5.1 (3) C8 Si1 C (10) Si1 C1 C2 C (19) C9 Si1 C (10) C1 C2 C3 C4 2.5 (3) C7 Si1 C (9) C2 C3 C4 C5 0.3 (3) C6 C1 C (19) C3 C4 C5 C6 0.6 (3) C6 C1 Si (14) C4 C5 C6 C1 2.0 (3) C2 C1 Si (13) C2 C1 C6 C5 4.8 (3) C6 C1 H (13) Si1 C1 C6 C (19) 11

12 12 Scheme S2. Numbering scheme of A2. Si C1 C2 C3 (1) B C10 C11 C12 C13 C14 C15 F2 F3 F4 F5 F6 F7 F8 F9 F10 C21 C10' C11' C12' C13' C14' F1 F1' F2' F3' F4' F5' F6' F7' F8' F9' F10' C16 C17 C18 C19 C20 C15' C16' C4 C5 C6 C7 C8 C9 C17' C18' C19' C20' C21' B C22 C23 C24 C25 C26 C27 F12 F13 F14 F15 F16 F17 F18 F19 F20 C33 C22' C23' C24' C25' C26' F11 F11' F12' F13' F14' F15' F16' F17' F18' F19' F20' C28 C29 C30 C31 C32 C27' C28' C29' C30' C31' C32' C33' (1) (2)

13 Table S7. Selected bond lengths (Å), angles and torsion angles ( ) of A2. Si1 C (2) C6 C1 H (16) Si1 C (3) Si1 C1 H (18) Si1 C (3) C3 C2 C (2) Si1 C (3) C2 C3 C (2) C1 C (3) C5 C4 C (2) C1 C (3) C6 C5 C (2) C1 H (3) C5 C6 C (2) C2 C (3) C8 Si1 C1 C (16) C3 C (3) C7 Si1 C1 C (18) C4 C (3) C9 Si1 C1 C (2) C5 C (3) C8 Si1 C1 C (18) C8 Si1 C (12) C7 Si1 C1 C (19) C8 Si1 C (13) C9 Si1 C1 C (18) C7 Si1 C (14) C6 C1 C2 C3 5.2 (4) C8 Si1 C (11) Si1 C1 C2 C (2) C7 Si1 C (11) C1 C2 C3 C4 2.2 (4) C9 Si1 C (12) C2 C3 C4 C5 1.0 (4) C2 C1 C (2) C3 C4 C5 C6 1.2 (4) C2 C1 Si (16) C4 C5 C6 C1 1.8 (4) C6 C1 Si (16) C2 C1 C6 C5 4.9 (4) C2 C1 H (17) Si1 C1 C6 C (2) 13

14 14 Scheme S3. Numbering scheme of A3. Si C1 C2 C3 (1) B C10 C11 C12 C13 C14 C15 F2 F3 F4 F5 F6 F7 F8 F9 F10 C21 C22 C23 C24 C25 C26 F1 F11 F12 F13 F14 F15 F16 F17 F18 F19 F20 C16 C17 C18 C19 C20 C27 C28 C4 C5 C6 C7 C8 C9 C29 C30 C31 C32 C33 B C43 C44 C45 C46 C47 C48 F22 F23 F24 F25 F26 F27 F28 F29 F30 C54 C55 C56 C57 C58 C59 F21 F31 F32 F33 F34 F35 F40 F39 F38 F37 F36 C49 C50 C51 C52 C53 C60 C61 C66 C65 C64 C63 C62 (1) (2) Si C34 C35 C36 (2) C37 C38 C39 C40 C41 C42 F Si Si (41) (4) (3) C67 C68 C69 C70 C71 C72

15 Table S8. Selected bond lengths (Å), angles and torsion angles ( ) of A3. Si1 C (3) C35 C34 H (3) Si1 C (3) C39 C34 H (4) Si1 C (3) Si2 C34 H34 93 (3) Si1 C (4) C34 C35 C (9) C1 C (6) C35 C36 C (8) C1 C (6) C38 C37 C (8) C1 H (5) C39 C38 C (9) C2 C (5) C38 C39 C (7) C3 C (5) Si4 F41 Si (6) C4 C (6) F41 Si3 C (5) C5 C (6) F41 Si3 C (9) Si2 C (8) C69 Si3 C (11) Si2 C (11) F41 Si3 C (5) Si2 C (8) C69 Si3 C (6) Si2 C (7) C67 Si3 C (11) C34 C (13) F41 Si4 C (5) C34 C (10) F41 Si4 C (7) C34 H (7) C71 Si4 C (9) C35 C (12) F41 Si4 C (7) C36 C (11) C71 Si4 C (6) C37 C (13) C72 Si4 C (9) C38 C (12) C9 Si1 C1 C (3) F41 Si (7) C7 Si1 C1 C (3) F41 Si (7) C8 Si1 C1 C (3) Si3 C (11) C9 Si1 C1 C (3) Si3 C (2) C7 Si1 C1 C (3) Si3 C (14) C8 Si1 C1 C (3) Si4 C (11) C6 C1 C2 C3 4.0 (6) Si4 C (16) Si1 C1 C2 C (4) 15

16 Si4 C (19) C1 C2 C3 C4 1.8 (6) C9 Si1 C (18) C2 C3 C4 C5 0.1 (6) C9 Si1 C (16) C3 C4 C5 C6 0.5 (7) C7 Si1 C (17) C4 C5 C6 C1 2.8 (7) C9 Si1 C (17) C2 C1 C6 C5 4.5 (6) C7 Si1 C (17) Si1 C1 C6 C (4) C8 Si1 C (17) C42 Si2 C34 C (7) C2 C1 C (4) C41 Si2 C34 C (8) C2 C1 Si (3) C40 Si2 C34 C (6) C6 C1 Si (3) C42 Si2 C34 C (6) C2 C1 H1 120 (3) C41 Si2 C34 C (7) C6 C1 H1 120 (3) C40 Si2 C34 C (5) Si1 C1 H1 88 (3) C39 C34 C35 C (13) C3 C2 C (4) Si2 C34 C35 C (9) C4 C3 C (4) C34 C35 C36 C (13) C5 C4 C (4) C35 C36 C37 C (12) C6 C5 C (4) C36 C37 C38 C (14) C5 C6 C (4) C37 C38 C39 C (14) C42 Si2 C (6) C35 C34 C39 C (12) C42 Si2 C (4) Si2 C34 C39 C (8) C41 Si2 C (5) Si4 F41 Si3 C (14) C42 Si2 C (4) Si4 F41 Si3 C (18) C41 Si2 C (5) Si4 F41 Si3 C (16) C40 Si2 C (4) Si3 F41 Si4 C (15) C35 C34 C (8) Si3 F41 Si4 C (16) C35 C34 Si (6) Si3 F41 Si4 C (16) C39 C34 Si (5) (i) x+2, y, z+2. 16

17 Scheme S4. Numbering scheme of B1. F3 F4 C14 C13 F2 C15 C12 F17 F5 F16 C16 C11 F1 F10 F9 C3 C7 C4 C5 F18 C30 C31 C29 C32 C34 C33 B (1) C21 C22 C20 C17 C19 C18 F8 C2 C9 C1 (1) Si C8 C6 C10 F19 F20 F11 F12 C23 C28 C24 C27 C25 C26 F15 F14 F6 F7 F13 Table S9. Selected bond lengths (Å), angles and torsion angles ( ) of B1. Si1 C (6) C3 C2 C (6) Si1 C (5) C2 C3 C (5) Si1 C (6) C3 C4 C (5) Si1 C (5) C3 C4 C (5) C1 C (7) C5 C4 C (6) C1 C (7) C6 C5 C (5) C1 H (6) C5 C6 C (5) C2 C (7) C8 Si1 C1 C (5) C3 C (7) C10 Si1 C1 C (5) C4 C (7) C9 Si1 C1 C (4) C4 C (7) C8 Si1 C1 C (4) 17

18 C5 C (7) C10 Si1 C1 C (4) C8 Si1 C (3) C9 Si1 C1 C (4) C8 Si1 C (3) C6 C1 C2 C3 5.5 (8) C10 Si1 C (3) Si1 C1 C2 C (5) C8 Si1 C (3) C1 C2 C3 C4 3.1 (8) C10 Si1 C (2) C2 C3 C4 C5 1.0 (8) C9 Si1 C (3) C2 C3 C4 C (5) C2 C1 C (6) C3 C4 C5 C6 1.4 (8) C2 C1 Si (3) C7 C4 C5 C (5) C6 C1 Si (4) C4 C5 C6 C1 4.1 (8) C2 C1 H1 118 (3) C2 C1 C6 C5 6.0 (8) C6 C1 H1 120 (3) Si1 C1 C6 C (5) Si1 C1 H1 92 (3) 18

19 Scheme S5. Numbering scheme of B2. C7a F3 C3a C4a C5a F4 C15 C14 C13 F2 C2a C9a C1a (1) Si C8a C6a C10a F18 F17 C31 C32 C30 F5 F16 C29 C16 C11 B (1) C12 F1 F10 C22 C17 C21 F9 C20 F8 C1b C3b Si (2) (21) F C2b F19 C33 C34 F20 F11 C24 C23 C28 F6 F15 C18 C19 F7 C6b (3) Si C4b C5b F12 C25 C26 F13 C27 F14 Table S10. Selected bond lengths (Å), angles and torsion angles ( ) of B2. C1A C6A (3) C9A Si1 C1A (10) C1A C2A (3) C10A Si1 C1A (13) C1A Si (2) Si3 F21 Si2 158 (2) C1A H1A 0.95 (2) F21 Si2 C1B (17) C2A C3A (3) F21 Si2 C2B (13) C3A C4A (3) C1B Si2 C2B (12) C4A C5A (3) F21 Si2 C3B 97.5 (15) C4A C7A (3) C1B Si2 C3B (14) C5A C6A (3) C2B Si2 C3B (13) Si1 C8A (3) F21 Si3 C4B 95.6 (16) Si1 C9A (3) F21 Si3 C5B (15) 19

20 Si1 C10A (3) C4B Si3 C5B (19) F21 Si (2) F21 Si3 C6B (16) F21 Si (2) C4B Si3 C6B 115 (2) Si2 C1B (17) C5B Si3 C6B (19) Si2 C2B (15) C6A C1A C2A C3A 5.5 (3) Si2 C3B (17) Si1 C1A C2A C3A (2) Si3 C4B 1.88 (2) C1A C2A C3A C4A 3.0 (3) Si3 C5B 1.90 (2) C2A C3A C4A C5A 0.3 (3) Si3 C6B 1.90 (2) C2A C3A C4A C7A (2) C6A C1A C2A (19) C3A C4A C5A C6A 0.2 (3) C6A C1A Si (14) C7A C4A C5A C6A (2) C2A C1A Si (15) C4A C5A C6A C1A 2.8 (3) C6A C1A H1A (14) C2A C1A C6A C5A 5.4 (3) C2A C1A H1A (15) Si1 C1A C6A C5A (19) Si1 C1A H1A 88.3 (14) C6A C1A Si1 C8A (18) C3A C2A C1A (2) C2A C1A Si1 C8A (19) C2A C3A C4A (2) C6A C1A Si1 C9A (18) C5A C4A C3A (2) C2A C1A Si1 C9A (18) C5A C4A C7A (2) C6A C1A Si1 C10A (15) C3A C4A C7A (2) C2A C1A Si1 C10A (17) C6A C5A C4A (2) Si3 F21 Si2 C1B 176 (5) C5A C6A C1A (19) Si3 F21 Si2 C2B 56 (5) C8A Si1 C9A (17) Si3 F21 Si2 C3B 63 (5) C8A Si1 C10A (16) Si2 F21 Si3 C4B 148 (5) C9A Si1 C10A (14) Si2 F21 Si3 C5B 87 (5) C8A Si1 C1A (11) Si2 F21 Si3 C6B 31 (6) 20

21 Scheme S6. Numbering scheme of C. F3 F4 C16 C15 C14 F2 C3 C7 C4 C8 C5 F17 C32 C31 F5 F16 C17 C12 C13 F1 F10 C23 C22 F9 C2 C9 C1 (1) Si C10 F18 C6 C33 F19 C11 C43 C42 C36 C34 C30 C35 F20 F11 F12 B C24 C29 C25 C28 C26 C27 C18 F6 F15 F14 C19 C21 C20 F7 F8 C41 C37 F13 C40 C39 C38 Table S11. Selected bond lengths (Å), angles and torsion angles ( ) of C. Si1 C (3) C5 C6 C (3) Si1 C (3) C8 C7 C (3) Si1 C (3) C37 C36 C (3) Si1 C (3) C37 C36 C (4) C1 C (4) C41 C36 C (4) C1 C (4) C36 C37 C (3) C1 H (3) C39 C38 C (4) C2 C (4) C40 C39 C (4) C3 C (4) C39 C40 C (4) 21

22 C4 C (4) C40 C41 C (3) C4 C (4) C43 C42 C (3) C5 C (4) C9 Si1 C1 C (2) C7 C (5) C11 Si1 C1 C (2) C36 C (5) C10 Si1 C1 C (2) C36 C (4) C9 Si1 C1 C (2) C36 C (5) C11 Si1 C1 C (2) C37 C (5) C10 Si1 C1 C (2) C38 C (5) C6 C1 C2 C3 6.6 (4) C39 C (6) Si1 C1 C2 C (3) C40 C (5) C1 C2 C3 C4 2.9 (4) C42 C (6) C2 C3 C4 C5 0.7 (4) C9 Si1 C (14) C2 C3 C4 C (3) C9 Si1 C (16) C3 C4 C5 C6 0.4 (4) C11 Si1 C (15) C7 C4 C5 C (3) C9 Si1 C (13) C4 C5 C6 C1 3.5 (4) C11 Si1 C (16) C2 C1 C6 C5 6.9 (4) C10 Si1 C (14) Si1 C1 C6 C (3) C6 C1 C (3) C3 C4 C7 C (4) C6 C1 Si (19) C5 C4 C7 C (4) C2 C1 Si (2) C41 C36 C37 C (5) C6 C1 H (16) C42 C36 C37 C (3) C2 C1 H (16) C36 C37 C38 C (5) Si1 C1 H (16) C37 C38 C39 C (6) C3 C2 C (3) C38 C39 C40 C (6) C2 C3 C (3) C39 C40 C41 C (5) C3 C4 C (3) C37 C36 C41 C (5) C3 C4 C (3) C42 C36 C41 C (3) C5 C4 C (3) C37 C36 C42 C (6) C6 C5 C (3) C41 C36 C42 C (5) 22

23 23 Scheme S7. Numbering scheme of D. Si C1 C2 C3 (1) B C11 C12 C13 C14 C15 C16 C17 C18 F2 F3 F4 F5 F6 F7 F8 F9 F10 C24 C25 C26 C27 C28 C29 F1 F11 F12 F13 F14 F15 F16 F17 F18 F19 F20 C19 C20 C21 C22 C23 C30 C31 C4 C5 C6 C7 C8 C9 C10 C32 C33 C34 C35 C36 B C49 C50 C51 C52 C53 C54 F22 F23 F24 F25 F26 F27 F28 F29 F30 C60 C61 C62 C63 C64 C65 F21 F31 F32 F33 F34 F35 F36 F37 F38 F39 F40 C55 C56 C57 C58 C59 C66 C67 C68 C69 C70 C71 C72 Si C37 C38 C39 (2) C47 C48 C40 C41 C42 C43 C44 C45 C46 (1) (2)

24 Table S12. Selected bond lengths (Å), angles and torsion angles ( ) of D. Si1 C (2) C48 Si2 C (10) Si1 C (2) C42 C37 C (19) Si1 C (2) C42 C37 Si (13) Si1 C (19) C38 C37 Si (13) C1 C (3) C42 C37 H (13) C1 C (3) C38 C37 H (12) C1 H (2) Si2 C37 H (12) C2 C (3) C39 C38 C (18) C3 C (3) C38 C39 C (18) C4 C (3) C41 C40 C (19) C4 C (3) C41 C40 C (2) C5 C (3) C39 C40 C (2) C7 C (3) C42 C41 C (19) C8 C (3) C41 C42 C (18) Si2 C (2) C40 C43 C (2) Si2 C (2) C43 C44 C (2) Si2 C (2) C11 Si1 C1 C (16) Si2 C (2) C12 Si1 C1 C (15) C37 C (3) C10 Si1 C1 C (16) C37 C (3) C11 Si1 C1 C (15) C37 H (2) C12 Si1 C1 C (16) C38 C (3) C10 Si1 C1 C (17) C39 C (3) C6 C1 C2 C3 6.6 (3) C40 C (3) Si1 C1 C2 C (18) C40 C (3) C1 C2 C3 C4 2.3 (3) C41 C (3) C2 C3 C4 C5 2.0 (3) C43 C (3) C2 C3 C4 C (17) C44 C (3) C3 C4 C5 C6 1.9 (3) C11 Si1 C (13) C7 C4 C5 C (17) 24

25 C11 Si1 C (12) C4 C5 C6 C1 2.5 (3) C12 Si1 C (13) C2 C1 C6 C5 6.7 (3) C11 Si1 C (10) Si1 C1 C6 C (17) C12 Si1 C (9) C3 C4 C7 C (2) C10 Si1 C (9) C5 C4 C7 C (2) C6 C1 C (19) C4 C7 C8 C (19) C6 C1 Si (12) C47 Si2 C37 C (17) C2 C1 Si (12) C46 Si2 C37 C (17) C6 C1 H (12) C48 Si2 C37 C (15) C2 C1 H (12) C47 Si2 C37 C (15) Si1 C1 H (12) C46 Si2 C37 C (16) C3 C2 C (18) C48 Si2 C37 C (16) C2 C3 C (17) C42 C37 C38 C (3) C3 C4 C (18) Si2 C37 C38 C (19) C3 C4 C (17) C37 C38 C39 C (3) C5 C4 C (17) C38 C39 C40 C (3) C6 C5 C (18) C38 C39 C40 C (2) C5 C6 C (17) C39 C40 C41 C (3) C4 C7 C (16) C43 C40 C41 C (2) C9 C8 C (2) C40 C41 C42 C (3) C47 Si2 C (12) C38 C37 C42 C (3) C47 Si2 C (12) Si2 C37 C42 C (19) C46 Si2 C (12) C41 C40 C43 C (3) C47 Si2 C (10) C39 C40 C43 C (3) C46 Si2 C (9) C40 C43 C44 C (2) 25

26 Scheme S8. Numbering scheme of E. F3 F4 C17 C16 C15 F2 C9 C3 C7 C4 C8 C5 F17 C33 C32 F5 F16 C18 C13 C14 F1 F10 C24 C23 F9 C2 C10 C1 (1) Si C11 C6 C12 F18 C34 F19 C35 C31 C36 F20 F11 C26 B C25 C30 C19 F6 F15 C20 C22 C21 F7 F8 C29 F12 C27 C28 F14 F13 Table S13. Selected bond lengths (Å), angles and torsion angles ( ) of E. Si1 C (2) C2 C3 C (16) Si1 C (2) C5 C4 C (16) Si1 C (2) C5 C4 C (16) Si1 C (19) C3 C4 C (16) C1 C (2) C6 C5 C (17) C1 C (3) C5 C6 C (17) C1 H (3) C4 C7 C (18) C2 C (2) C4 C7 C (16) C2 H C9 C7 C (2) C3 C (2) C10 Si1 C1 C (15) C3 H C12 Si1 C1 C (14) 26

27 C4 C (3) C11 Si1 C1 C (13) C4 C (3) C10 Si1 C1 C (15) C5 C (3) C12 Si1 C1 C (14) C7 C (3) C11 Si1 C1 C (14) C7 C (3) C6 C1 C2 C3 6.4 (3) C10 Si1 C (12) Si1 C1 C2 C (15) C10 Si1 C (12) C1 C2 C3 C4 2.4 (2) C12 Si1 C (11) C2 C3 C4 C5 1.8 (3) C10 Si1 C (8) C2 C3 C4 C (16) C12 Si1 C (9) C3 C4 C5 C6 1.9 (3) C11 Si1 C (11) C7 C4 C5 C (19) C2 C1 C (16) C4 C5 C6 C1 2.2 (3) C2 C1 Si (11) C2 C1 C6 C5 6.3 (3) C6 C1 Si (13) Si1 C1 C6 C (2) C2 C1 H (16) C5 C4 C7 C (2) C6 C1 H (16) C3 C4 C7 C (3) Si1 C1 H (16) C5 C4 C7 C (2) C3 C2 C (15) C3 C4 C7 C (2) 27

28 28 Scheme S9. Numbering scheme of F. Si C1 C2 C3 (1) B C11 C12 C13 C14 C15 C16 C17 F2 F3 F4 F5 F6 F7 F8 F9 F10 C23 C24 C25 C26 C27 C28 F1 F11 F12 F13 F14 F15 F16 F17 F18 F19 F20 C18 C19 C20 C21 C22 C29 C30 C4 C5 C6 C7 C8 C9 C10 C31 C32 C33 C34 C35 B C47 C48 C49 C50 C51 C52 F22 F23 F24 F25 F26 F27 F28 F29 F30 C58 C59 C60 C61 C62 C63 F21 F31 F32 F33 F34 F35 F36 F37 F38 F39 F40 C53 C54 C55 C56 C57 C64 C65 C66 C67 C68 C69 C70 Si C36 C37 C38 (2) C46 C39 C40 C41 C42 C43 C44 C45 (1) (2)

29 Table S14. Selected bond lengths (Å), angles and torsion angles ( ) of F. Si1 C (2) C45 Si2 C (10) Si1 C (3) C37 C36 C (2) Si1 C (3) C37 C36 Si (14) Si1 C (3) C41 C36 Si (13) C1 C (3) C37 C36 H (12) C1 C (3) C41 C36 H (13) C1 H (2) Si2 C36 H (12) C2 C (3) C38 C37 C (2) C2 H C37 C38 C (2) C3 C (3) C37 C38 C (19) C3 C (3) C39 C38 C (2) C4 C (3) C40 C39 C (2) C4 C (3) C40 C39 C (2) C5 C (3) C38 C39 C (2) Si2 C (2) C41 C40 C (2) Si2 C (2) C40 C41 C (2) Si2 C (2) C9 Si1 C1 C (2) Si2 C (2) C11 Si1 C1 C (18) C36 C (3) C10 Si1 C1 C (2) C36 C (3) C9 Si1 C1 C (19) C36 H (2) C11 Si1 C1 C (2) C37 C (3) C10 Si1 C1 C (18) C37 H C6 C1 C2 C3 4.2 (3) C38 C (3) Si1 C1 C2 C (2) C38 C (3) C1 C2 C3 C4 1.1 (3) C39 C (3) C1 C2 C3 C (2) C39 C (3) C2 C3 C4 C5 0.0 (3) C40 C (3) C7 C3 C4 C (2) C9 Si1 C (11) C2 C3 C4 C (2) 29

30 C9 Si1 C (13) C7 C3 C4 C8 0.9 (3) C11 Si1 C (15) C3 C4 C5 C6 2.2 (3) C9 Si1 C (11) C8 C4 C5 C (2) C11 Si1 C (13) C4 C5 C6 C1 5.4 (3) C10 Si1 C (12) C2 C1 C6 C5 6.2 (3) C6 C1 C (3) Si1 C1 C6 C (2) C6 C1 Si (15) C44 Si2 C36 C (16) C2 C1 Si (16) C46 Si2 C36 C (17) C6 C1 H (14) C45 Si2 C36 C (16) C2 C1 H (14) C44 Si2 C36 C (17) Si1 C1 H (14) C46 Si2 C36 C (15) C3 C2 C (2) C45 Si2 C36 C (17) C2 C3 C (2) C41 C36 C37 C (3) C2 C3 C (2) Si2 C36 C37 C (19) C4 C3 C (2) C36 C37 C38 C (3) C5 C4 C (2) C36 C37 C38 C (2) C5 C4 C (2) C37 C38 C39 C (3) C3 C4 C (2) C42 C38 C39 C (19) C6 C5 C (2) C37 C38 C39 C (19) C5 C6 C (2) C42 C38 C39 C (3) C44 Si2 C (10) C38 C39 C40 C (3) C44 Si2 C (12) C43 C39 C40 C (2) C46 Si2 C (11) C39 C40 C41 C (3) C44 Si2 C (9) C37 C36 C41 C (3) C46 Si2 C (9) Si2 C36 C41 C (19) 30

31 Scheme S10. Numbering scheme of G. C8 F3 C7 C3 C2 C4 C1 (1) Si C5 C6 F17 F4 F5 F16 C15 C14 C16 C13 C17 C12 F2 F1 F10 F9 C9 C10 C11 F18 C32 C33 C31 C30 B C23 C18 C22 C21 F8 C34 C35 C19 C20 C43 F19 F20 F11 C25 C24 C29 F15 F6 F7 C37 C38 C39 F12 C26 C27 C28 F14 C42 C36 C41 C40 F13 Table S15. Selected bond lengths (Å), angles and torsion angles ( ) of G. Si1 C (2) C5 C6 C (2) Si1 C (2) C37 C36 C (2) Si1 C (2) C37 C36 C (2) Si1 C (2) C41 C36 C (2) C1 C (3) C36 C37 C (2) C1 C (3) C39 C38 C (2) C1 H (3) C39 C38 C (2) C2 C (3) C37 C38 C (2) C2 C (3) C40 C39 C (2) C3 C (3) C39 C40 C (2) C4 C (4) C40 C41 C (2) 31

32 C4 C (4) C11 Si1 C1 C (17) C5 C (3) C10 Si1 C1 C (17) C36 C (3) C9 Si1 C1 C (18) C36 C (3) C11 Si1 C1 C (18) C37 C (3) C10 Si1 C1 C (16) C38 C (3) C9 Si1 C1 C (18) C38 C (4) C6 C1 C2 C (3) C39 C (4) Si1 C1 C2 C (2) C40 C (4) C6 C1 C2 C (2) C11 Si1 C (12) Si1 C1 C2 C (2) C11 Si1 C (13) C1 C2 C3 C4 5.5 (3) C10 Si1 C (11) C7 C2 C3 C (2) C11 Si1 C (10) C2 C3 C4 C5 1.9 (4) C10 Si1 C (11) C2 C3 C4 C (2) C9 Si1 C (10) C3 C4 C5 C6 3.4 (4) C2 C1 C (2) C8 C4 C5 C (2) C2 C1 Si (14) C4 C5 C6 C1 2.4 (4) C6 C1 Si (15) C2 C1 C6 C5 9.7 (3) C2 C1 H (15) Si1 C1 C6 C (2) C6 C1 H (15) C41 C36 C37 C (4) Si1 C1 H (14) C42 C36 C37 C (2) C3 C2 C (2) C36 C37 C38 C (4) C3 C2 C (2) C36 C37 C38 C (3) C1 C2 C (2) C37 C38 C39 C (4) C2 C3 C (2) C43 C38 C39 C (3) C3 C4 C (2) C38 C39 C40 C (4) C3 C4 C (3) C39 C40 C41 C (4) C5 C4 C (3) C37 C36 C41 C (4) C6 C5 C (2) C42 C36 C41 C (2) 32

33 Scheme S11. Numbering scheme of H. F3 C7 C3 C2 C4 C1 (1) Si C5 C6 C8 F17 F4 F5 F16 C15 C14 C16 C13 C17 C12 F2 F1 F10 F9 C9 C10 C11 F18 C32 C33 C31 C30 B C23 C18 C22 C21 F8 C43 C34 C35 C19 C20 C38 C39 C40 F19 F20 F11 C25 C24 C29 F6 F15 F7 C37 C36 C41 F12 C26 C27 C28 F14 C42 F13 Table S16. Selected bond lengths (Å), angles and torsion angles ( ) of H. Si1 C (5) C3 C2 C (5) Si1 C (5) C1 C2 C (5) Si1 C (5) C4 C3 C (5) Si1 C (5) C3 C4 C (5) C1 C (7) C6 C5 C (5) C1 C (7) C6 C5 C (5) C1 H (5) C4 C5 C (5) C2 C (7) C5 C6 C (5) C2 C (7) C37 C36 C (6) C3 C (7) C37 C36 C (5) C4 C (7) C41 C36 C (5) 33

34 C5 C (7) C36 C37 C (5) C5 C (7) C37 C38 C (5) C36 C (7) C40 C39 C (6) C36 C (7) C40 C39 C (6) C36 C (8) C38 C39 C (6) C37 C (7) C41 C40 C (6) C38 C (7) C40 C41 C (6) C39 C (8) C9 Si1 C1 C (4) C39 C (9) C10 Si1 C1 C (4) C40 C (9) C11 Si1 C1 C (4) C36 C (7) C9 Si1 C1 C (4) C36 C (7) C10 Si1 C1 C (3) C36 C (8) C11 Si1 C1 C (4) C37 C (7) C6 C1 C2 C3 9.0 (7) C38 C (7) Si1 C1 C2 C (5) C39 C (8) C6 C1 C2 C (5) C39 C (9) Si1 C1 C2 C (5) C40 C (9) C1 C2 C3 C4 3.9 (7) C36 C (7) C7 C2 C3 C (5) C36 C (7) C2 C3 C4 C5 1.1 (8) C36 C (8) C3 C4 C5 C6 0.8 (7) C37 C (7) C3 C4 C5 C (5) C38 C (7) C4 C5 C6 C1 4.5 (7) C9 Si1 C (2) C8 C5 C6 C (5) C9 Si1 C (3) C2 C1 C6 C5 9.7 (8) C10 Si1 C (3) Si1 C1 C6 C (5) C9 Si1 C (2) C41 C36 C37 C (8) C10 Si1 C (2) C42 C36 C37 C (5) C11 Si1 C (2) C36 C37 C38 C (7) C2 C1 C (5) C37 C38 C39 C (8) C2 C1 Si (3) C37 C38 C39 C (5) 34

35 C6 C1 Si (3) C38 C39 C40 C (10) C2 C1 H1 118 (3) C43 C39 C40 C (7) C6 C1 H1 117 (3) C39 C40 C41 C (11) Si1 C1 H1 93 (3) C37 C36 C41 C (10) C3 C2 C (5) C42 C36 C41 C (7) 35

36 Scheme S12. Numbering scheme of I. C9b C7a C8b C4b C3a C3b C2b C2a C4a C5bC5a C6bC6a C8a F4 C17 F3 C16 C15 F2 C7b C1b C1a (1b) (1a) Si Si C10 C11 C12 C9a F17 C33 C32 F5 F16 C18 C13 C14 F1 F10 C24 C23 F9 F18 C34 C31 B (1) C19 C22 F8 C35 C36 C20 C21 F19 C44b C44a C43a C37a C45b C43b C37b C38b C45a C42a C42b C38a C41a C39b C41b C39a C40b C40a F20 F11 F12 C25 C30 C26 C29 C27 C28 F13 F15 F14 F6 F7 Table S17. Selected bond lengths (Å), angles and torsion angles ( ) of I. Si1A C (7) C3A C2A C1A (8) Si1A C (6) C2A C3A C4A (11) Si1A C (7) C5A C4A C3A (18) Si1A C1A (5) C5A C4A C7A (14) C1A C6A (11) C3A C4A C7A (17) C1A C2A (16) C4A C5A C6A (10) C2A C3A (7) C4A C5A C8A (11) C3A C4A 1.39 (2) C6A C5A C8A (6) C4A C5A 1.35 (2) C1A C6A C5A (8) C4A C7A 1.58 (2) C1A C6A C9A (8) 36

37 C5A C6A (8) C5A C6A C9A (6) C5A C8A (8) C2B C1B C6B 118 (3) C6A C9A (6) C2B C1B Si1B (16) Si1B C1B (9) C6B C1B Si1B (12) C1B C2B 1.41 (4) C1B C2B C7B (15) C1B C6B 1.52 (2) C1B C2B C3B 123 (2) C2B C7B (12) C7B C2B C3B (18) C2B C3B 1.54 (5) C8B C3B C4B 129 (4) C3B C8B 1.39 (5) C8B C3B C2B 121 (3) C3B C4B 1.43 (5) C4B C3B C2B 109 (3) C4B C5B (17) C5B C4B C3B 126 (2) C4B C9B (16) C5B C4B C9B (13) C5B C6B (15) C3B C4B C9B 111 (2) C37A C38A C4B C5B C6B (12) C37A C40A C5B C6B C1B 113 (2) C37A C44A (10) C38A C37A C40A C38A C39A C38A C37A C44A (10) C38A C45A (9) C40A C37A C44A (10) C39A C41A C39A C38A C37A C41A C42A C39A C38A C45A (7) C42A C40A C37A C38A C45A (7) C40A C43A (9) C38A C39A C41A C37B C38B C42A C41A C39A C37B C42B C40A C42A C41A C37B C44B (11) C42A C40A C37A C38B C39B C42A C40A C43A (7) C38B C45B (10) C37A C40A C43A (7) C39B C40B C38B C37B C42B C40B C41B C38B C37B C44B (12) C41B C42B C42B C37B C44B (12) C42B C43B (10) C37B C38B C39B

38 C10 Si1A C (4) C37B C38B C45B (8) C10 Si1A C (3) C39B C38B C45B (8) C11 Si1A C (3) C40B C39B C38B C10 Si1A C1A (5) C39B C40B C41B C11 Si1A C1A (3) C40B C41B C42B C12 Si1A C1A (5) C41B C42B C37B C6A C1A C2A (13) C41B C42B C43B (8) C6A C1A Si1A 98.7 (5) C37B C42B C43B (8) C2A C1A Si1A 98.3 (6) 38

39 Scheme S13. Numbering scheme of J. C8a C8b C9b C4a C4b C9a C3a C5a C5b C3b C2a C6b C6a C2b C7a C1a C1b C7b C12b (1b) Si Si (1a) C12a F17 C11b C11a C10a C10b C33 C32 F4 F5 F16 F3 C16 C15 C17 C14 C18 C13 F2 F1 F10 C24 C23 F9 F18 C34 C31 B (1) C19 C22 F8 C35 C36 C20 C21 C43a C37a C43b C42a C42b C38a C41b C37b C38b C41a C39a C39b C40b C40a C44a C44b C45b C45a F19 F20 F11 F12 C25 C30 C26 C29 C27 C28 F13 F15 F14 F6 F7 Table S18. Selected bond lengths (Å), angles and torsion angles ( ) of J. Si1A C11A (4) C38A C37A C43A (7) Si1A C10A (3) C42A C37A C43A (7) Si1A C12A (4) C39A C38A C37A Si1A C1A (3) C38A C39A C40A C1A C2A (5) C38A C39A C44A (9) C1A C6A (5) C40A C39A C44A (9) C1A H1A 1.01 (2) C41A C40A C39A C2A C3A (4) C41A C40A C45A (9) C2A C7A (4) C39A C40A C45A (9) C3A C4A (4) C42A C41A C40A

40 C4A C5A (5) C41A C42A C37A C4A C8A (4) C37B C42B C41B C5A C6A (5) C38B C37B C42B C5A C9A (5) C38B C37B C43B (8) Si1B C10B (16) C42B C37B C43B (8) Si1B C12B (17) C37B C38B C39B Si1B C11B (16) C40B C39B C38B Si1B C1B (17) C40B C39B C44B (10) C1B C2B (19) C38B C39B C44B (10) C1B C6B (19) C39B C40B C41B C1B H1B C39B C40B C45B (10) C1B H1A 1.05 (4) C41B C40B C45B (10) C2B C3B (17) C40B C41B C42B C2B C7B (15) C11A Si1A C1A C2A (3) C3B C4B (16) C10A Si1A C1A C2A 67.6 (4) C4B C5B (17) C12A Si1A C1A C2A 54.3 (3) C4B C8B (16) C11A Si1A C1A C6A 66.0 (3) C5B C6B (17) C10A Si1A C1A C6A 54.6 (4) C5B C9B (18) C12A Si1A C1A C6A (3) C37A C38A C6A C1A C2A C3A 11.9 (5) C37A C42A Si1A C1A C2A C3A 95.2 (4) C37A C43A (7) C6A C1A C2A C7A (3) C38A C39A Si1A C1A C2A C7A 88.0 (4) C39A C40A C1A C2A C3A C4A 5.5 (5) C39A C44A 1.54 (2) C7A C2A C3A C4A (3) C40A C41A C2A C3A C4A C5A 4.2 (5) C40A C45A (15) C2A C3A C4A C8A (3) C41A C42A C3A C4A C5A C6A 7.1 (5) C42B C37B C8A C4A C5A C6A (3) C42B C41B C3A C4A C5A C9A (3) C37B C38B C8A C4A C5A C9A 4.6 (5) 40

41 C37B C43B (10) C4A C5A C6A C1A 0.4 (5) C38B C39B C9A C5A C6A C1A (3) C39B C40B C2A C1A C6A C5A 9.3 (5) C39B C44B (18) Si1A C1A C6A C5A 99.4 (3) C40B C41B C10B Si1B C1B C2B 60 (2) C40B C45B 1.47 (3) C12B Si1B C1B C2B (16) C11A Si1A C10A (3) C11B Si1B C1B C2B 61 (2) C11A Si1A C12A (3) C10B Si1B C1B C6B 63 (2) C10A Si1A C12A (3) C12B Si1B C1B C6B 58.6 (17) C11A Si1A C1A (2) C11B Si1B C1B C6B 176 (2) C10A Si1A C1A (3) C6B C1B C2B C3B 8(3) C12A Si1A C1A (2) Si1B C1B C2B C3B 95.3 (17) C2A C1A C6A (3) C6B C1B C2B C7B 164 (2) C2A C1A Si1A (3) Si1B C1B C2B C7B 93 (2) C6A C1A Si1A 98.8 (2) C1B C2B C3B C4B 4(3) C2A C1A H1A (14) C7B C2B C3B C4B 176 (2) C6A C1A H1A (14) C2B C3B C4B C5B 13 (4) Si1A C1A H1A 90.8 (14) C2B C3B C4B C8B 176 (2) C3A C2A C1A (3) C3B C4B C5B C6B 11 (4) C3A C2A C7A (3) C8B C4B C5B C6B 179 (3) C1A C2A C7A (3) C3B C4B C5B C9B 172 (2) C2A C3A C4A (3) C8B C4B C5B C9B 17 (4) C5A C4A C3A (3) C4B C5B C6B C1B 0(4) C5A C4A C8A (3) C9B C5B C6B C1B 160 (2) C3A C4A C8A (3) C2B C1B C6B C5B 9(4) C6A C5A C4A (3) Si1B C1B C6B C5B 94 (3) C6A C5A C9A (4) C42A C37A C38A C39A 0.0 C4A C5A C9A (4) C43A C37A C38A C39A (7) C5A C6A C1A (3) C37A C38A C39A C40A 0.0 C10B Si1B C12B (18) C37A C38A C39A C44A (13) C10B Si1B C11B (18) C38A C39A C40A C41A

42 C12B Si1B C11B (17) C44A C39A C40A C41A (12) C10B Si1B C1B (17) C38A C39A C40A C45A (14) C12B Si1B C1B (12) C44A C39A C40A C45A 6.3 (12) C11B Si1B C1B (13) C39A C40A C41A C42A 0.0 C2B C1B C6B (18) C45A C40A C41A C42A (12) C2B C1B Si1B 97.2 (14) C40A C41A C42A C37A 0.0 C6B C1B Si1B 97.4 (16) C38A C37A C42A C41A 0.0 C2B C1B H1B C43A C37A C42A C41A (8) C6B C1B H1B C41B C42B C37B C38B 0.0 Si1B C1B H1B C41B C42B C37B C43B (8) C3B C2B C1B (15) C42B C37B C38B C39B 0.0 C3B C2B C7B (15) C43B C37B C38B C39B (8) C1B C2B C7B (16) C37B C38B C39B C40B 0.0 C2B C3B C4B (16) C37B C38B C39B C44B (15) C5B C4B C3B (15) C38B C39B C40B C41B 0.0 C5B C4B C8B (16) C44B C39B C40B C41B (15) C3B C4B C8B (17) C38B C39B C40B C45B (16) C4B C5B C6B (16) C44B C39B C40B C45B 5.2 (16) C4B C5B C9B (16) C39B C40B C41B C42B 0.0 C6B C5B C9B (17) C45B C40B C41B C42B (14) C5B C6B C1B (18) C37B C42B C41B C40B 0.0 C38A C37A C42A

43 43 Scheme S14. Numbering scheme of K. B C13 C14 C15 C16 C17 C18 F2 F3 F4 F5 F6 F7 F8 F9 F10 C24 C25 C26 C27 C28 C29 F1 F11 F12 F13 F14 F15 F16 F17 F18 F19 F20 C19 C20 C21 C22 C23 C30 C31 C32 C33 C34 C35 C36 (1) C43 C44 C45 C37 C38 C39 C40 C41 C42 Si C1 C2 C3 C11 C12 C4 C5 C6 C7 C8 C9 C10 B C58 C59 C60 C61 C62 C63 F22 F23 F24 F25 F26 F27 F28 F29 F30 C69 C70 C71 C72 C73 C74 F21 F31 F32 F33 F34 F35 F36 F37 F38 F39 F40 C64 C65 C66 C67 C68 C75 C76 C77 C78 C79 C80 C81 (1) Si Si C46a C46b C47a C47b C48a C48b C49a C49b C50a C50b C51a C51b C52a C52b C53a C53b C54a C54b C55a C55b C56a C56b C57a C57b (2a) (2b) C82 C83 C84 C85 C86 C87 C89 C90 C88 C82' C83' C84' C85' C86' C87' C89' C90' C88' (1)

44 Table S19. Selected bond lengths (Å), angles and torsion angles ( ) of K. Si1 C (3) C57B Si2B C46B (10) Si1 C (2) C55B Si2B C46B (9) Si1 C (3) C56B Si2B C46B (10) Si1 C (2) C47B C46B C51B 119 (2) C1 C (3) C47B C46B Si2B (14) C1 C (3) C51B C46B Si2B 104 (2) C1 H (3) C47B C46B H (3) C2 C (4) C51B C46B H46 96 (3) C2 C (4) Si2B C46B H (3) C3 C (4) C46B C47B C48B (19) C4 C (3) C46B C47B C52B (18) C4 C (4) C48B C47B C52B (17) C5 C (3) C49B C48B C47B (19) C6 C (3) C53B C49B C48B 129 (3) C37 C (3) C53B C49B C50B 129 (3) C37 C (3) C48B C49B C50B 103 (2) C37 C (4) C51B C50B C49B 125 (3) C38 C (3) C50B C51B C46B 117 (3) C39 C (3) C50B C51B C54B 101 (3) C39 C (3) C46B C51B C54B 138 (4) C40 C (3) C83 C82 C C41 C (3) C83 C82 C (10) C41 C (3) C87 C82 C (10) Si2A C55A (9) C82 C83 C Si2A C56A (12) C83 C84 C Si2A C57A (8) C83 C84 C (13) Si2A C46A (6) C85 C84 C (13) C46A C47A (13) C86 C85 C C46A C51A (11) C87 C86 C

45 C46A H (5) C87 C86 C (10) C47A C48A (10) C85 C86 C (10) C47A C52A (11) C86 C87 C C48A C49A (14) C12 Si1 C1 C (18) C49A C50A (15) C10 Si1 C1 C (18) C49A C53A (17) C11 Si1 C1 C (2) C50A C51A (11) C12 Si1 C1 C (2) C51A C54A 1.50 (3) C10 Si1 C1 C (19) Si2B C57B (16) C11 Si1 C1 C (19) Si2B C55B 1.95 (2) C6 C1 C2 C (3) Si2B C56B 1.98 (2) Si1 C1 C2 C (2) Si2B C46B (19) C6 C1 C2 C (2) C46B C47B 1.39 (3) Si1 C1 C2 C (2) C46B C51B (19) C1 C2 C3 C4 5.3 (3) C46B H (5) C7 C2 C3 C (2) C47B C48B 1.41 (3) C2 C3 C4 C5 1.4 (3) C47B C52B 1.52 (3) C2 C3 C4 C (2) C48B C49B 1.31 (4) C3 C4 C5 C6 1.0 (3) C49B C53B 1.25 (4) C8 C4 C5 C (2) C49B C50B 1.65 (4) C4 C5 C6 C1 5.9 (3) C50B C51B 1.33 (3) C4 C5 C6 C (2) C51B C54B 1.51 (6) C2 C1 C6 C (3) C82 C Si1 C1 C6 C (2) C82 C C2 C1 C6 C (2) C82 C (17) Si1 C1 C6 C (2) C83 C C42 C37 C38 C (3) C84 C C43 C37 C38 C (2) C84 C (13) C37 C38 C39 C (3) C85 C C37 C38 C39 C (2) C86 C C38 C39 C40 C (3) C86 C (14) C44 C39 C40 C (2) 45

46 C12 Si1 C (14) C39 C40 C41 C (3) C12 Si1 C (17) C39 C40 C41 C (2) C10 Si1 C (15) C38 C37 C42 C (3) C12 Si1 C (13) C43 C37 C42 C (2) C10 Si1 C (11) C40 C41 C42 C (3) C11 Si1 C (12) C45 C41 C42 C (2) C6 C1 C (2) C55A Si2A C46A C47A 49.5 (8) C6 C1 Si (15) C56A Si2A C46A C47A (9) C2 C1 Si (14) C57A Si2A C46A C47A 69.7 (7) C6 C1 H (15) C55A Si2A C46A C51A 72.0 (8) C2 C1 H (14) C56A Si2A C46A C51A 46.3 (10) Si1 C1 H (14) C57A Si2A C46A C51A (7) C3 C2 C (2) C51A C46A C47A C48A 11.6 (10) C3 C2 C (2) Si2A C46A C47A C48A 90.5 (6) C1 C2 C (2) C51A C46A C47A C52A (8) C2 C3 C (2) Si2A C46A C47A C52A 87.7 (7) C6 C1 H (15) C46A C47A C48A C49A 12.8 (8) C2 C1 H (14) C52A C47A C48A C49A (5) C3 C4 C (2) C47A C48A C49A C50A 7.9 (9) C3 C4 C (2) C47A C48A C49A C53A (6) C5 C4 C (2) C48A C49A C50A C51A 0.9 (13) C6 C5 C (2) C53A C49A C50A C51A (9) C5 C6 C (2) C49A C50A C51A C46A 0.2 (16) C5 C6 C (2) C49A C50A C51A C54A (17) C1 C6 C (2) C47A C46A C51A C50A 5.0 (14) C42 C37 C (2) Si2A C46A C51A C50A 98.2 (11) C42 C37 C (2) C47A C46A C51A C54A (14) C38 C37 C (2) Si2A C46A C51A C54A 94.6 (15) C37 C38 C (2) C57B Si2B C46B C47B 97.5 (18) C40 C39 C (2) C55B Si2B C46B C47B 20 (2) C40 C39 C (2) C56B Si2B C46B C47B (16) 46

47 C38 C39 C (2) C57B Si2B C46B C51B 137 (2) C41 C40 C (2) C55B Si2B C46B C51B 105 (2) C42 C41 C (2) C56B Si2B C46B C51B 13 (2) C42 C41 C (2) C51B C46B C47B C48B 33 (3) C40 C41 C (2) Si2B C46B C47B C48B 82.4 (14) C37 C42 C (2) C51B C46B C47B C52B (19) C55A Si2A C56A (7) Si2B C46B C47B C52B 79.8 (19) C55A Si2A C57A (4) C46B C47B C48B C49B 21.4 (19) C56A Si2A C57A (7) C52B C47B C48B C49B (16) C55A Si2A C46A (3) C47B C48B C49B C53B 174 (2) C56A Si2A C46A (4) C47B C48B C49B C50B 3.6 (16) C57A Si2A C46A (4) C53B C49B C50B C51B 180 (3) C47A C46A C51A (9) C48B C49B C50B C51B 3(3) C47A C46A Si2A 98.2 (5) C49B C50B C51B C46B 10 (5) C51A C46A Si2A 96.3 (8) C49B C50B C51B C54B 173 (3) C47A C46A H (2) C47B C46B C51B C50B 29 (4) C51A C46A H (2) Si2B C46B C51B C50B 86 (4) Si2A C46A H46 85 (2) C47B C46B C51B C54B 177 (4) C48A C47A C46A (8) Si2B C46B C51B C54B 67 (5) C48A C47A C52A (7) C87 C82 C83 C C46A C47A C52A (7) C88 C82 C83 C (9) C47A C48A C49A (7) C82 C83 C84 C C50A C49A C48A (11) C82 C83 C84 C (13) C50A C49A C53A (11) C83 C84 C85 C C48A C49A C53A (10) C89 C84 C85 C (13) C49A C50A C51A (12) C84 C85 C86 C C50A C51A C46A (12) C84 C85 C86 C (7) C50A C51A C54A (11) C85 C86 C87 C C46A C51A C54A (9) C90 C86 C87 C (8) C57B Si2B C55B (10) C83 C82 C87 C C57B Si2B C56B (12) C88 C82 C87 C (8) 47

48 C55B Si2B C56B (11) 48

49 Scheme S15. Numbering scheme of L. C5' C3' C2 C7 C6' C4' C1' C1 C4 C6 C7' C2' C3 C5 Table S20. Selected bond lengths (Å), angles and torsion angles ( ) of L. C1 C (12) C7 C4 C (9) C1 C (12) C1 C4 C (8) C1 C (12) C7 C4 C (9) C2 C3 i (13) C6 C4 C (10) C3 C2 i (13) C3 C1 C2 C3 i 0.30 (15) C4 C (14) C4 C1 C2 C3 i (9) C4 C (16) C2 C1 C3 C2 i 0.30 (15) C4 C (16) C4 C1 C3 C2 i (9) C3 C1 C (8) C3 C1 C4 C (14) C3 C1 C (8) C2 C1 C4 C (9) C2 C1 C (8) C3 C1 C4 C (11) C3 i C2 C (8) C2 C1 C4 C (12) C2 i C3 C (8) C3 C1 C4 C (11) C1 C4 C (8) C2 C1 C4 C (12) C1 C4 C (8) Symmetry code: (i) x, y+1, z. 49

50 50 Scheme S16. Numbering scheme of M. C1 C2 C3 (1) B C7 C8 C9 C10 C11 C12 F6 F7 F8 F9 F10 F11 F12 F13 F14 C18 C19 C21 C22 C23 C24 F5 F15 F16 F17 F18 F19 C13 C14 C15 C16 C17 C25 C4 C5 C6 (1) C20 S S F1 F2 F3 F4 (2) C26 C27 C28 (3) B C32 C33 C34 C35 C36 C37 F25 F26 F27 F28 F29 F30 F31 F32 F33 C43 C44 C46 C47 C48 C49 F24 F34 F35 F36 F37 F38 C38 C39 C40 C41 C42 C50 C29 C30 C31 (2) C45 S S F20 F21 F22 F23 (4)

51 Table S21. Selected bond lengths (Å), angles and torsion angles ( ) of M. S1 C (17) F21 C30 C (2) S1 C (18) F21 C30 C (18) S2 C (18) C29 C30 C (18) S2 C (17) F22 C31 C (19) C1 B (2) F22 C31 C (18) C2 C (3) C32 C31 C (18) C2 C (2) F23 C32 C (17) C3 C (2) F23 C32 C (17) C4 F (2) C31 C32 C (19) C4 C (3) C39 B2 C (13) C5 F (2) C39 B2 C (14) C5 C (3) C45 B2 C (14) C6 F (2) C39 B2 C (14) C6 C (3) C45 B2 C (13) C7 F (2) C33 B2 C (13) C8 B (3) C3 S1 C1 B (14) C14 B (3) C3 S1 C1 S (12) C20 B (3) C2 S2 C1 B (13) S3 C (17) C2 S2 C1 S (12) S3 C (19) C1 S2 C2 C (16) S4 C (18) C1 S2 C2 C (15) S4 C (18) C7 C2 C3 C4 1.3 (3) C26 B (3) S2 C2 C3 C (13) C27 C (3) C7 C2 C3 S (14) C27 C (2) S2 C2 C3 S (18) C28 C (3) C1 S1 C3 C (15) C29 F (2) C1 S1 C3 C (16) C29 C (3) C2 C3 C4 F (15) C30 F (2) S1 C3 C4 F1 0.0 (2) 51

52 C30 C (3) C2 C3 C4 C5 0.3 (3) C31 F (2) S1 C3 C4 C (14) C31 C (3) F1 C4 C5 F2 1.6 (3) C32 F (2) C3 C4 C5 F (16) C33 B (3) F1 C4 C5 C (16) C39 B (3) C3 C4 C5 C6 2.3 (3) C45 B (3) F2 C5 C6 F3 2.8 (3) C1 S1 C (9) C4 C5 C6 F (16) C1 S2 C (8) F2 C5 C6 C (16) B1 C1 S (13) C4 C5 C6 C7 2.8 (3) B1 C1 S (12) F3 C6 C7 F4 0.7 (3) S1 C1 S (10) C5 C6 C7 F (16) C7 C2 C (16) F3 C6 C7 C (16) C7 C2 S (14) C5 C6 C7 C2 1.3 (3) C3 C2 S (13) C3 C2 C7 F (16) C2 C3 C (17) S2 C2 C7 F4 1.2 (3) C2 C3 S (13) C3 C2 C7 C6 0.7 (3) C4 C3 S (14) S2 C2 C7 C (14) F1 C4 C (16) C27 S4 C26 B (13) F1 C4 C (17) C27 S4 C26 S (11) C5 C4 C (17) C28 S3 C26 B (13) F2 C5 C (17) C28 S3 C26 S (11) F2 C5 C (17) C26 S4 C27 C (15) C4 C5 C (16) C26 S4 C27 C (14) F3 C6 C (18) C32 C27 C28 C (3) F3 C6 C (16) S4 C27 C28 C (13) C7 C6 C (17) C32 C27 C28 S (14) F4 C7 C (17) S4 C27 C28 S (17) F4 C7 C (16) C26 S3 C28 C (16) C6 C7 C (17) C26 S3 C28 C (14) C26 S3 C (9) C27 C28 C29 F (15) 52