Supporting Information for. Grafting trimethylaluminum and its halogen derivatives on silica: General trends for

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Electronic Supplementary Material (ESI) for Physical Chemistry Chemical Physics. This journal is the Owner Societies 2015 Supporting Information for Grafting trimethylaluminum and its halogen derivatives on silica: General trends for 27 Al SS-NMR response from first principles calculations Rachel Nathaniel Kerber, # Philippe Sautet* Torsten Kerber,^ Xavier Rozanska, Δ Françoise Delbecq, and Université de Lyon, CNRS, Institut de Chimie de Lyon, Ecole Normale Supérieure de Lyon, 46 allée d Italie, F-69364 Lyon Cedex 07, France. # Present address: University of Cambridge, Department of Chemistry, Lensfield Road, Cambridge, CB2 1EW, United Kingdom. ^ Present address: think-cell Software, Chausseestr. 8E, 10115 Berlin, Germany. Δ Present address: Materials Design, 18 rue de Saisset, F-92120 Montrouge, France. *Corresponding author: Philippe.Sautet@ens-lyon.fr Contents 27 AL SS- NMR FOR MONOMERIC SPECIES IN GAS- PHASE AND GRAFTED ON SILICA... 2 27 AL SS- NMR FOR DIMERIC SPECIES... 4 DIMERIC SPECIES IN GAS PHASE... 4 DIMERIC SPECIES GRAFTED ON SILICA... 8 Monografted dimers... 8 Bigrafted dimers... 12 1

27 Al SS- NMR for monomeric species in gas- phase and grafted on silica 27 Al SS- NMR for monomeric species in gas- phase and grafted on silica Monomers in gas- phase and grafted Species δ ISO (ppm) CQ (MHz) Gas- phase AlF 3 57 36 AlCl 3 149 29 Al(OH) 3 96 33 Al(OH) 2 Cl 110 32 Al(OH)Cl 2 129 30 Al(OH) 2 Me 143 36 Al(OH)Me 2 221 41 Al(OH)MeCl 165 35 Al(OMe) 3 70 32 Al(Me) 3 321 47 AlMe 2 Cl 261 40 AlMeCl 2 197 34 Cluster models Al(OSi(OH) 3 ) 3 52 36 AlMe(OSi(OH) 3 ) 2 123 38 AlMe 2 (OSi(OH) 3 ) 214 42 AlMeCl(OSi(OH) 3 ) 151 36 Surface models O SURF AlMe 2 228 43 (O SURF ) 2 AlMe 2 174 34 O SURF AlMeCl 165 37 (O SURF ) 2 AlMeCl 127 25 O SURF AlCl 2 122 32 (O SURF ) 2 AlCl 2 95 18 (O SURF ) 2 AlMe 134 37 (O SURF ) 2 AlCl 103 33 Table S1. DFT-calculated 27 Al NMR parameters δ ISO (ppm) and C Q (MHz) for all monomeric species presented in Figure 1. 2

Scheme S1. Schematic representation of all models of Al monomers used in the 2D map: AlMe 3, AlMe 2 Cl, AlMeCl 2, AlMe 2 OH, AlCl 2 OH, AlMe(OH) 2, AlCl(OH) 2, AlMeClOH, Al(OH) 3, Al(OMe) 3, AlF 3, Al(OSi(OH) 3 ) 3, AlMe(OSi(OH) 3 ) 2, AlMe 2 (OSi(OH) 3 ), AlMeCl(OSi(OH) 3 ), O SURF AlMe 2, O SURF AlMeCl, O SURF AlCl 2, O SURF AlMe 2 O SURF, O SURF AlMeCl O SURF, O SURF AlCl 2 O SURF, (O SURF ) 2 AlMe, (O SURF ) 2 AlCl. 3

27 Al SS- NMR for dimeric species Dimeric species in gas phase Figure S1 Relative energy as a function of the number of Cl for the dimers in gas phase with general formula Me n Cl 2-n Al1(µ 2 -Me n Cl 1-n )Al2Me n Cl 2-n. The small c and t, stand for cis and trans isomers, respectively. The crossed diamond represents Me in bridge position, the circle corresponds to mixed MeCl bridge, and the star shows that in bridge we have Cl. The position of the Cl atoms is indicated as in the main text of the paper. 4

Relative energies of gas- phase dimers Species Number of Cl atoms Cl position 0 1 2 3 4 5 6 Me2Al1(µ 2 -Me)Al2Me 2 000 - - - - - - Me 2 Al1(µ-MeCl)Al2Me 2 010-0 - - - - Me 2 Al1(µ 2 -Me)Al2MeCl 001-18 - - - - Me2Al1(µ 2 -Cl)Al2Me 2 020 - - 0 - - - Me2Al1(µ-MeCl)Al2MeCl 011 - - 36 - - - MeClAl1(µ 2 -Me)Al2MeCl 101t - - 52 - - - MeClAl1(µ 2 -Me)Al2MeCl 101c - - 55 - - - Me2Al1(µ 2 -Me)Al2Cl 2 002 - - 61 - - - Me2Al1(µ 2 -Cl)Al2MeCl 021 - - - 0 - - MeClAl1(µ-MeCl)Al2MeCl 111t - - - 33 - - MeClAl1(µ-MeCl)Al2MeCl 111c - - - 35 - - Me 2 Al1(µ-MeCl)Al2Cl 2 012 - - - 43 - - MeClAl1(µ 2 -Me)Al2Cl 2 102 - - - 57 - - MeClAl1(µ 2 -Cl)Al2MeCl 121t - - - - 0 - MeClAl1(µ 2 -Cl)Al2MeCl 121c - - - - 2 - Me 2 Al1(µ 2 -Cl)Al2Cl 2 022 - - - - 11 - MeClAl1(µ-MeCl)Al2Cl 2 112 - - - - 43 - Cl 2 Al1(µ 2 -Me)Al2Cl 2 202 - - - - 63 - MeClAl1(µ 2 -Cl)Al2Cl 2 122 - - - - - 0 Cl 2 Al1(µ-MeCl)Al2Cl 2 212 38 Cl 2 Al1(µ 2 -Cl)Al2Cl 2 222 - - - - - - - Table S2. Relative energy differences for the bigrafted dimers in gas phase as a function of the number of Cl with general formula Me n Cl 2-n Al1-(µ 2 -Me n Cl 1-n )Al2Me n Cl 2-n. 5

Gas- phase dimers Species δ ISO CQ Cl positions Al (ppm) (MHz) Me 2 Al1(µ 2 -Me)Al2Me 2 000 Al1 152 25 Al2 152 25 Me2Al1(µ2-Me)Al2MeCl 0 01 Al1 153 28 00 1 Al2 134 18 Me2Al1(µ2-Me)Al2Cl2 0 02 Al1 155 31 00 2 Al2 117 5 MeClAl1(µ2-Me)Al2MeCl c 101c Al1 131 19 Al2 131 19 MeClAl1(µ2-Me)Al2MeCl t 101 * t Al1 130 20 Al2 130 20 MeClAl1(µ2-Me)Al2Cl2 1 02 Al1 128 20 10 2 Al2 112 7 Cl2Al1(µ2-Me)Al2Cl2 202 Al1 107 9 Al2 107 9 Me2Al1(µ-MeCl)Al2Me2 010 Al1 161 30 Al2 161 30 Me2Al1(µ-MeCl)Al2MeCl 0 11 Al1 165 34 01 1 Al2 133 21 Me2Al1(µ-MeCl)Al2Cl2 0 12 Al1 169 36 01 2 Al2 110 11 MeClAl1(µ-MeCl)Al2MeCl c 111c Al1 130 22 Al2 130 22 MeClAl1(µ-MeCl)Al2MeCl t 111t Al1 132 23 Al2 132 23 MeClAl1(µ-MeCl)Al2Cl2 1 12 Al1 128 24 11 2 Al2 107 12 Cl2Al1(µ-MeCl)Al2Cl2 212 Al1 103 12 Al2 103 12 Me 2 Al1(µ 2 -Cl)Al2Me 2 020 * Al1 180 36 Al2 180 36 Me 2 Al1(µ 2 -Cl)Al2MeCl 0 21 Al1 183 38 02 1 Al2 137 24 Me 2 Al1(µ 2 -Cl)Al2Cl 2 0 22 Al1 183 39 02 2 Al2 104 13 MeClAl1(µ 2 -Cl)Al2MeCl c Al1 136 25 121c Al2 136 25 MeClAl1(µ 2 -Cl)Al2MeCl t Al1 137 25 121t Al2 137 25 MeClAl1(µ 2 -Cl)Al2Cl 2 1 22 Al1 136 26 12 2 Al2 103 14 Cl 2 Al1(µ 2 -Cl)Al2Cl 2 222 Al1 101 16 Al2 101 16 Table S3. DFT-calculated 27 Al NMR parameters δ ISO (ppm) and C Q (MHz) for all dimeric species in gas-phase presented in Figure 2. Small c and t are indicating the cis and trans position of the substituent. Labels x yz and xy z indicate the position of the considered Al 6

(Al1(left) and Al2(right). In bold are the two dimer references used for the EFG calculations in terms of NBOs and NLMOs. Me Me Al O O Al Me Me O Me Al Me Me Al Me O 020 101t Scheme S2. Representation of the two dimers with methyl and oxygen substituents used for the decomposition on localized molecular orbitals. NLMO contributions # 020 # 101 BD σ(al-c) 2-0.355 1-0.473 BD σ(al-o) 2 0.151 1-0.103 Σσ(Al-X) -0.408-0.576 BD σ(c-h) 2-0.040-0.109 3C (Al 1 -Al 2 -C) - 2 0.116 Al core -0.396-0.313 C core 2-0.056 1-0.072 O core 2 0.040 - ΣAnalysis # -0.916-0.838 Total calculated V 33 0.773 0.552 NBO charges Al 1.829 1.709 Cl -1.318-1.314 C t -1.268-1.267 C br - -1.240 Table S4 NLMO analysis of aluminum V 33 (in au) principal component for Me 2 Al1(µ 2 -OSiH 3 )Al2Me 2 and Me(OSiH 3 )Al1(µ 2 -Me)Al2Me(OSiH 3 ) dimers in gas phase. Here are presented the following labels: 2-center bond (BD), 3-center bond (3C), and 1-center core pair (CR). Total calculated is the actual V 33. ΣAnalysis corresponds to the sums of all terms shown here from NLMO analysis with >5% contribution. 7

Dimeric species grafted on silica Monografted dimers Relative energies of Species monografted dimers Type / Cl Number of Cl atoms position 0 1 2 3 4 5 Me 2 Al1(µ-MeO SURF )Al2Me 2 2.1 / 000 0 - - - - - O SURF MeAl1(µ 2 -Me)Al2Me 2 2.2 / 000 27 - - - - - Me 2 Al1(µ-ClO SURF )Al2Me 2 2.1 / 010-0 - - - - Me 2 Al1(µ-MeO SURF )Al2MeCl 2.1 / 001-35 - - - - O SURF MeAl1(µ-MeCl)Al2Cl 2 2.2 / 010-49 - - - - O SURF ClAl1(µ 2 -Me)Al2Cl 2 2.2 / 100-60 - - - - O SURF MeAl1(µ 2 -Me)Al2MeCl 2.2 / 001-75 - - - - Me 2 Al1(µ-ClO SURF )Al2MeCl 2.1 / 011 - - 0 - - - MeClAl1(µ-MeO SURF )Al2MeCl trans 2.1 / 101t - - 8 - - - O SURF MeAl1(µ 2 -Cl)Al2Me 2 2.2 / 020 - - 14 - - - Me 2 Al1(µ-MeO SURF )Al2Cl 2 2.1 / 002 - - 19 - - - MeClAl1(µ-MeO SURF )Al2MeCl cis 2.1 / 101c - - 29 - - - O SURF ClAl1(µ-MeCl)Al2Me 2 2.2 / 110 - - 48 - - - O SURF MeAl1(µ-MeCl)Al2MeCl 2.2 / 011 - - 58 - - - O SURF ClAl1(µ 2 -Me)Al2MeCl cis 2.2 / 101c - - 69 - - - O SURF MeAl1(µ 2 -Me)Al2Cl 2 2.2 / 002 - - 78 - - - O SURF ClAl1(µ 2 -Me)Al2MeCl trans 2.2 / 101t - - 80 - - - MeClAl1(µ-ClO SURF )Al2MeCl trans 2.1 / 111t - - - 0 - - Me 2 Al1(µ-ClO SURF )Al2Cl 2 2.1 / 012 - - - 14 - - MeClAl1(µ-ClO SURF )Al2MeCl cis 2.1 / 111c - - - 20 - - O SURF ClAl1(µ 2 -Cl)Al2Me 2 2.2 / 120 - - - 38 - - O SURF MeAl1(µ 2 -Cl)Al2MeCl 2.2 / 021 - - - 48 - - MeClAl1(µ-MeO SURF )Al2Cl 2 2.1 / 102 - - - 57 - - O SURF ClAl1(µ-MeCl)Al2MeCl cis 2.2 / 111c - - - 82 - - O SURF MeAl1(µ-MeCl)Al2Cl 2 2.2 / 012 - - - 89 - - O SURF ClAl1(µ-MeCl)Al2MeCl trans 2.2 / 111t - - - 90 - - O SURF ClAl1(µ 2 -Me)Al2Cl 2 2.2 / 102 - - - 109 - - MeClAl1(µ-ClO SURF )Al2Cl 2 2.1 / 112 - - - - 0 - O SURF ClAl1(µ 2 -Cl)Al2MeCl cis 2.2 / 121c - - - - 25 - O SURF MeAl1(µ2-Cl)Al2Cl 2 2.2 / 022 - - - - 31 - O SURF ClAl1(µ2-Cl)Al2MeCl trans 2.2 / 121t - - - - 32 - Cl 2 Al1(µ-MeO SURF )Al2Cl 2 2.1 / 202 - - - - 34 - O SURF ClAl1(µ-MeCl)Al2Cl 2 2.2 / 112 - - - - 73 - Cl 2 Al1(µ-ClO SURF )Al2Cl 2 2.1 / 212 - - - - - 0 O SURF ClAl1(µ 2 -Cl)Al2Cl 2 2.2 / 122 - - - - - 37 Table S4. Relative energy differences for the monografted dimers- grafted via terminal (GvT) and grafted via bridge (GvB) as a function of the number of Cl with general formula O SURF Me n Cl 1-n Al1-(µ 2 -Me n Cl 1-n )Al2Me n Cl 2-n and Me n Cl 2-n Al1(µ-Me n Cl 1-n O SURF )Al2Me n Cl 2-n, respectively. 8

GvB Species Cl δ ISO CQ Al position (ppm) (MHz) Me 2 Al1(µ-MeO SURF )Al2Me 2 000 Al1 157 25 Al2 157 25 Me 2 Al1(µ-MeO SURF )Al2MeCl 001 Al1 159 27 Al2 128 19 Me 2 Al1(µ-MeO SURF )Al2Cl 2 002 Al1 169 33 Al2 106 7 MeClAl1(µ-MeO SURF )Al2MeCl c 101c Al1 126 20 Al2 126 20 MeClAl1(µ-MeO SURF )Al2MeCl t 101t Al1 127 21 Al2 127 21 MeClAl1(µ-MeO SURF )Al2Cl 2 102 Al1 126 20 Al2 100 9 Cl 2 Al1(µ-MeO SURF )Al2Cl 2 202 Al1 99 11 Al2 99 11 Me 2 Al1(µ-ClO SURF )Al2Me 2 010 Al1 171 30 Al2 171 30 Me 2 Al1(µ-ClO SURF )Al2MeCl 011 Al1 172 31 Al2 130 22 Me 2 Al1(µ-ClO SURF )Al2Cl 2 012 Al1 177 35 Al2 97 11 MeClAl1(µ-ClO SURF )Al2MeCl c 111c Al1 130 22 Al2 130 22 MeClAl1(µ-ClO SURF )Al2MeCl t 111t Al1 130 23 Al2 130 23 MeClAl1(µ-ClO SURF )Al2Cl 2 112 Al1 129 22 Al2 97 13 Cl 2 Al1(µ-ClO SURF )Al2Cl 2 212 Al1 97 14 Al2 97 14 Table S5. DFT-calculated 27 Al NMR parameters δ ISO (ppm) and C Q (MHz) for all GvB species (Me n Cl 2-n Al1(µ-Me n Cl 1-n O SURF )Al2Me n Cl 2-n ) in Figure 5 of the manuscript. Small c and t are indicating the cis and trans position of the substituent, respectively. 9

Figure S2. All methylaluminum monografted dimers via terminal (GvT) position are presented in two 2D plots, one for each Al (a for Al1 and b for Al2 environments), respectively together with their chloro derivatives grafted on the {001} silica surface. 10

Species Cl position O SURF MeAl1(µ 2 -Me)Al2Me 2 000 O SURF MeAl1(µ 2 -Me)Al2MeCl 001 O SURF ClAl1(µ 2 -Me)Al2Me 2 100 O SURF MeAl1(µ 2 -Me)Al2Cl 2 002 O SURF ClAl1(µ 2 -Me)Al2MeCl O SURF ClAl1(µ 2 -Me)Al2MeCl 11 101c 101t O SURF ClAl1(µ 2 -Me)Al2Cl 2 102 GvT Al δ ISO CQ (ppm) (MHz) Al1 113 16 Al2 153 27 Al1 108 18 Al2 130 18 Al1 95 8 Al2 156 30 Al1 105 21 Al2 110 7 Al1 90 9 Al2 127 22 Al1 89 10 Al2 127 20 Al1 84 11 Al2 105 10 O SURF MeAl1(µ-MeCl)Al2Me 2 010 Al1 110 20 Al2 164 33 O SURF MeAl1(µ-MeCl)Al2MeCl 011 Al1 109 23 Al2 130 21 O SURF ClAl1(µ-MeCl)Al2Me 2 110 Al1 88 13 Al2 169 36 O SURF MeAl1(µ-MeCl)Al2Cl 2 012 Al1 106 25 Al2 104 12 O SURF ClAl1(µ-MeCl)Al2MeCl 111c Al1 85 13 Al2 129 25 O SURF ClAl1(µ-MeCl)Al2MeCl 111t Al1 85 14 Al2 129 23 O SURF ClAl1(µ-MeCl)Al2Cl 2 112 Al1 82 15 Al2 100 12 O SURF MeAl1(µ 2 -Cl)Al2Me 2 020 O SURF MeAl1(µ 2 -Cl)Al2MeCl 021 O SURF ClAl1(µ 2 -Cl)Al2Me 2 120 O SURF MeAl1(µ 2 -Cl)Al2Cl 2 022 O SURF ClAl1(µ 2 -Cl)Al2MeCl O SURF ClAl1(µ 2 -Cl)Al2MeCl 121c 121t O SURF ClAl1(µ 2 -Cl)Al2Cl 2 122 Al1 110 25 Al2 182 38 Al1 109 28 Al2 136 26 Al1 81 16 Al2 185 40 Al1 108 29 Al2 103 15 Al1 80 17 Al2 136 28 Al1 81 17 Al2 136 27 Al1 79 19 Al2 102 16 Table S6. DFT-calculated 27 Al NMR parameters δ ISO (ppm) and C Q (MHz) for all GvT species (O SURF Me n Cl 1-n Al1-(µ 2 -Me n Cl 1-n )Al2Me n Cl 2-n ) shown in Figure S2. Small c and t are indicating the cis and trans position of the substituent, respectively.

Bigrafted dimers 27 Al SS- NMR for bigrafted dimeric species on silica Relative energies of Species Type / Cl Number of Cl atoms position 0 1 2 3 4 O SURF MeAl1(µ-MeO SURF )Al2Me 2 2.3/ 000 0 - - - - Me 2 Al1(µ 2 -O SURF )Al2Me 2 2.4 / 000 26 - - - - O SURF MeAl1(µ 2 -Me)Al2MeO SURF 2.5 / 000 31 - - - - (O SURF ) 2 Al1(µ 2 -Me)Al2Me 2 2.6 / 000 57 - - - - O SURF Me 2 Al1(µ-ClO SURF )Al2Me 2 2.3 / 010-0 - - - O SURF Me 2 Al1(µ-MeO SURF )Al2MeCl 2.3 / 001-33 - - - O SURF ClAl1(µ-MeO SURF )Al2Me 2 2.3 / 100-38 - - - O SURF MeAl1(µ-MeCl)Al2MeO SURF 2.5 / 010-52 - - - MeClAl1(µ 2 -O SURF )Al2Me 2 2.4 / 100-64 - - - O SURF ClAl1(µ 2 -Me)Al2MeO SURF 2.5 / 100-73 - - - (O SURF ) 2 Al1(µ-MeCl)Al2Me 2 2.6 / 010-82 - - - (O SURF ) 2 Al1(µ 2 -Me)Al2MeCl 2.6 / 001-94 - - - O SURF MeAl1(µ-ClO SURF )Al2MeCl 2.3 / 011 - - 0 - - O SURF ClAl1(µ-ClO SURF )Al2Me 2 2.3 / 110 - - 11 - - O SURF MeAl1(µ 2 -Cl)Al2MeO SURF 2.5 / 020 - - 24 - - O SURF ClAl1(µ-MeO SURF )Al2MeCl 2.3 / 101t - - 38 - - O SURF ClAl1(µ-MeO SURF )Al2MeCl 2.3 / 101c - - 40 - - O SURF MeAl1(µ-MeO SURF )Al2Cl 2 2.3 / 002 - - 42 - - (O SURF ) 2 Al1(µ 2 -Cl)Al2Me 2 2.6 / 020 - - 54 - - O SURF MeAl1(µ-MeCl)Al2ClO SURF 2.5 / 011 - - 63 - - MeClAl1(µ 2 -O SURF )Al2MeCl 2.4 / 101c - - 65 - - Me 2 Al1(µ 2 -O SURF )Al2Cl 2 2.4 / 002 - - 77 - - (O SURF ) 2 Al1(µ-MeCl)Al2MeCl 2.6 / 011 - - 85 - - O SURF ClAl1(µ 2 -Me)Al2ClO SURF 2.5 / 101 - - 88 - - (O SURF ) 2 Al1(µ 2 -Me)Al2Cl 2.6 / 002 - - 102 - - O SURF ClAl1(µ-ClO SURF )Al2MeCl 2.3 / 111t - - - 0 - O SURF ClAl1(µ-ClO SURF )Al2MeCl 2.3 / 111c - - - 0 - O SURF MeAl1(µ-ClO SURF )Al2Cl 2 2.3 / 012 - - - 4 - O SURF ClAl1(µ 2 -Cl)Al2MeO SURF 2.5 / 120 - - - 23 - O SURF ClAl1(µ-MeO SURF )Al2Cl 2 2.3 / 102 - - - 33 - (O SURF ) 2 Al1(µ 2 -Cl)Al2MeCl 2.6 / 021 - - - 45 - O SURF ClAl1(µ-MeCl)Al2ClO SURF 2.5 / 111 - - - 64 - MeClAl1(µ 2 -O SURF )Al2Cl 2 2.4 / 102 - - - 66 - (O SURF ) 2 Al1(µ-MeCl)Al2Cl 2 2.6 / 012 - - - 80 - O SURF ClAl1(µ-ClO SURF )Al2Cl 2 2.3 / 112 - - - - 0 O SURF ClAl1(µ 2 -Cl)Al2ClO SURF 2.5 / 121 - - - - 30 (O SURF ) 2 Al1(µ 2 -Cl)Al2Cl 2 2.6 / 022 - - - - 51 Cl 2 Al1(µ 2 -O SURF )Al2Cl 2 2.4 / 202 - - - - 69 Table S7. Relative energy differences for the bigrafted dimers- 2.3 (O SURF Me n Cl 1-n Al1(µ-Me n Cl 1- no SURF )Al2Me n Cl 2-n ), 2.4 (Me n Cl 2-n Al1(µ 2 -O SURF )Al2Me n Cl 2-n ), 2.5 (O SURF Me n Cl 1-n Al1(µ- Me n Cl 2-n )Al2Me n Cl 1-n O SURF ), and 2.6 (O SURF ) 2 Al1(µ-Me n Cl 2-n )Al2Me n Cl 2-n. 12

Figure S3. All methylaluminum bigrafted dimers and their chloro derivatives in which the Al-Al axis is parallel to the {001} silica surface. For the 2.4 dimers (Me n Cl 2-n Al1(µ 2 -O SURF ) Me n Cl 2-n ) we see clearly the effect of the number of the Cl atoms. Starting from Me 2 Al1(µ 2 -O SURF ) Me 2 (where Al1 and Al2 are equivalent) we start from 167 ppm and 28 MHz, to 130 ppm and 21 MHz for the MeClAl1(µ 2 -O SURF ) MeCl, and ending with 99 ppm and 15 MHz for the Cl 2 Al1(µ 2 -O SURF ) Cl 2. Along that linear correlation the δ ISO and the C Q both shift towards the small values with 68 ppm and 13 MHz respectively. This is exactly what we would expect based on the already observed trend for the monografted dimers. 13

Figure S4. All methylaluminum bigrafted dimers and their chloro derivatives in which the Al-Al axis is parallel to the {001} silica surface. Figure S5. All methylaluminum bigrafted dimers and their chloro derivatives in which the Al-Al axis is perpendicular to the {001} silica surface. 14

Species Cl position 15 Al BG dimers δ ISO (ppm) CQ (MHz) 2.3 O SURF MeAl1(µ-O SURF Me)Al2Me 2 000 Al1 116 19 Al2 162 29 O SURF MeAl1(µ-O SURF Me)Al2MeCl 001 Al1 114 20 Al2 128 20 O SURF ClAl1(µ-O SURF Me)Al2Me 2 100 Al1 92 13 Al2 170 33 O SURF MeAl1(µ-O SURF Me)Al2Cl 2 002 Al1 112 22 Al2 100 9 O SURF ClAl1(µ-O SURF Me)Al2MeCl c 101c Al1 88 13 Al2 127 23 O SURF ClAl1(µ-O SURF Me)Al2MeCl t O SURF ClAl1(µ-O SURF Me)Al2Cl 2 101t Al1 89 13 Al2 129 22 102 Al1 86 14 Al2 98 12 O SURF MeAl1(µ-O SURF Cl)Al2Me 2 010 Al1 111 22 Al2 175 33 O SURF MeAl1(µ-O SURF Cl)Al2MeCl 011 Al1 111 24 Al2 132 23 O SURF ClAl1(µ-O SURF Cl)Al2Me 2 110 Al1 82 14 Al2 180 35 O SURF MeAl1(µ-O SURF Cl)Al2Cl 2 012 Al1 111 26 Al2 99 14 O SURF ClAl1(µ-O SURF Cl)Al2MeCl c 111c Al1 82 15 Al2 132 25 111t Al1 82 15 O SURF ClAl1(µ-O SURF Cl)Al2MeCl t Al2 133 24 112 Al1 81 16 O SURF ClAl1(µ-O SURF Cl)Al2Cl 2 Al2 98 16 2.4 Me 2 Al1(µ 2 -O SURF )Al2Me 2 000 Al1 167 28 Al2 167 28 Me 2 Al1(µ 2 -O SURF )Al2MeCl 001 Al1 169 30 Al2 128 21 Me 2 Al1(µ 2 -O SURF )Al2Cl 2 002 Al1 173 32 Al2 98 13 MeClAl1(µ 2 -O SURF )Al2MeCl 101 Al1 130 21 Al2 130 21 MeClAl1(µ 2 -O SURF )Al2Cl 2 102 Al1 131 22 Al2 98 14 Cl 2 Al1(µ 2 -O SURF )Al2Cl 2 202 Al1 99 15 Al2 99 15 2.5 O SURF MeAl1(µ 2 -Me)Al2MeO SURF 000 Al1 106 22 Al2 106 22

O SURF MeAl1(µ 2 -Me)Al2ClO SURF 001 Al1 102 24 16 Al2 86 10 O SURF ClAl1(µ 2 -Me)Al2ClO SURF 101 Al1 79 12 Al2 79 12 O SURF MeAl1(µ-MeCl)Al2MeO SURF 010 Al1 102 26 Al2 102 26 O SURF MeAl1(µ-MeCl)Al2ClO SURF 011 Al1 99 27 Al2 78 15 O SURF ClAl1(µ-MeCl)Al2ClO SURF 111 Al1 73 17 Al2 73 17 O SURF MeAl1(µ 2 -Cl)Al2MeO SURF 020 Al1 103 30 Al2 103 30 O SURF MeAl1(µ 2 -Cl)Al2ClO SURF 021 Al1 74 19 Al2 100 31 O SURF ClAl1(µ 2 -Cl)Al2ClO SURF 121 Al1 72 21 Al2 72 21 (O SURF ) 2 Al1(µ 2 -Me)Al2Me 2 000 Al1 78 11 2.6 Al2 156 28 (O SURF ) 2 Al1(µ 2 -Me)Al2MeCl 001 Al1 75 13 Al2 133 20 (O SURF ) 2 Al1(µ 2 -Me)Al2Cl 2 002 Al1 71 15 Al2 111 8 (O SURF ) 2 Al1(µ-MeCl)Al2Me 2 010 Al1 71 15 Al2 171 34 (O SURF ) 2 Al1(µ-MeCl)Al2MeCl 011 Al1 69 16 Al2 136 23 (O SURF ) 2 Al1(µ-MeCl)Al2Cl 2 012 Al1 67 16 Al2 107 12 (O SURF ) 2 Al1(µ 2 -Cl)Al2Me 2 020 Al1 70 16 Al2 183 39 (O SURF ) 2 Al1(µ 2 -Cl)Al2MeCl 021 Al1 69 17 Al2 137 27 (O SURF ) 2 Al1(µ 2 -Cl)Al2Cl 2 121 Al1 68 18 Al2 103 16 Table S6. DFT-calculated 27 Al NMR parameters δ ISO (ppm) and C Q (MHz) for all bigrafted dimeric species on silica surface some of which presented in Figure 5, S2-S5.

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