Electronic supplementary information. Strategy to Enhance Solid-State Fluorescence and. Aggregation-Induced Emission Enhancement Effect in Pyrimidine

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1 Electronic Supplementary Material (ESI) for Dalton Transactions. This journal is The Royal Society of Chemistry 2015 Electronic supplementary information Strategy to Enhance Solid-State Fluorescence and Aggregation-Induced Emission Enhancement Effect in Pyrimidine Boron Complexes Yasuhiro Kubota,* Kouhei Kasatani, Hiroki Takai, Kazumasa Funabiki and Masaki Matsui* Department of Chemistry and Biomolecular Science, Faculty of Engineering, Gifu University, 1-1 Yanagido, Gifu , Japan (Y. Kubota), (M. Matsui) Contents 1. UV-vis absorption and fluorescence spectra (Figure S1 S6) 2. AIEE check (Figure S7 S12) 3. UV-vis absorption and fluorescence properties (Table S1 S6) 4. X ray crystal data (Table S7 S36) 5. Cartesian coordinates of the optimized structures 6. 1 H and 13 C NMR spectra (Figure S13 Figure S30)

2 (a) 0.4 (b) Absorbance Hexane Toluene Chloroform THF Dichloromethane Acetonitrile Wavelength / nm Figure S1. (a) UV-vis absorption and (b) fluorescence spectra of 8 in various solvents ( M). The solubility of 8 in n-hexane was poor. (a) (b) Figure S2. (a) UV-vis absorption and (b) fluorescence spectra of 9 in various solvents ( M). (a) (b) Figure S3. (a) UV-vis absorption and (b) fluorescence spectra of 11 in various solvents ( M).

3 (a) (b) Figure S4. (a) UV-vis absorption and (b) fluorescence spectra of 12 in various solvents ( M). (a) (b) Figure S5. (a) UV-vis absorption and (b) fluorescence spectra of 13 in various solvents ( M).

4 (a) (b) Figure S6. (a) UV-vis absorption and (b) fluorescence spectra of 14 in various solvents ( M). 0.3 Fluorescence quantum yield Water fraction (vol%) Figure S7. Fluorescence quantum yields of 6 and 12 in THF water mixtures with different volume fractions of water (10-4 M). 0% 40% 80% 85% 90% 95% Laser pointer Figure S8. Check of Tyndall phenomenon of 6.

5 3 2 1 Water fraction (vol%) Figure S9. UV-vis absorption spectra of 6 in THF water mixtures with different volume fractions of water (10-4 M). 0% 40% 70% 80% 90% 95% Laser pointer Figure S10. Check of Tyndall phenomenon of Water fraction (vol%) Figure S11. UV-vis absorption spectra of 12 in THF water mixtures with different volume fractions of water (10-4 M).

6 (a) 0.2 Absorbance Ethylene glycol content 0% 20% 40% 60% 80% Wavelength / nm (b) Absorbance Ethylene glycol content 0% 20% 40% 60% 80% Wavelength / nm Figure S12. UV-vis absorption spectra of (a) 6 and (b) 12 in methanol ethylene glycol mixtures with different volume fractions of ethylene glycol. Table S1. Absorption and fluorescence properties of 8 in various solvents a Cl CN N N B O F F 8 solvent max ( ) b F max Stokes shift f c s d e f k f k nr (nm) (nm) (cm -1 ) (ns) (10 9 s -1 ) (10 9 s -1 ) Hexane 376, 392 g 411, 430 3,340 <0.01 h Toluene 381 (32,200) 398 (21,100) 446 3, h CHCl (31,900) 395 (20,100) 413, 433 3, h THF 378 (36,000) 395 (22,400) 435 3, h CH 2 Cl (36,800) 393 (23,300) 414, 433 3, h MeCN 374 (35,000) 391 (21,300) 434 3, h a Measured at a concentration of 1.0 x 10-5 mol dm -3. b The excitation wavelengths ( ex ) were as follows: hexane (371 nm), toluene (381 nm), chloroform (378 nm), THF (378 nm), dichloromethane (378 nm) and acetonitrile (354 nm). c Measured using an integrating sphere method. d Measured using a single-photon-counting method. e Radiative rate constant (k f = f / s ). f Non-radiative rate constant (k nr =(1- f)/ s ). g Poor solubility. h Tooshorttobemeasured( s <0.1ns).

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8 Table S3. Absorption and fluorescence properties of 11 in various solvents a Cl N N B O Ph Ph 11 solvent max ( ) b F max Stokes shift f c s d e f k f k nr (nm) (nm) (cm -1 ) (ns) (10 9 s -1 ) (10 9 s -1 ) Hexane 397 (22,200) 445, 466 2, Toluene 401 (21,400) 456, 470 3, CHCl (23,000) 451, 470 2, THF 399 (22,600) 452, 467 2, CH 2 Cl (23,300) 452, 469 3, MeCN 395 (22,500) 456 3, a Measured at a concentration of 1.0 x 10-5 mol dm -3. b The excitation wavelengths ( ex ) were as follows: hexane (397 nm), toluene (401 nm), toluene (399 nm), chloroform (400 nm), THF (399 nm), dichloromethane (400 nm) and acetonitrile (396 nm). c Measured using an integrating sphere method. d Measured using a single-photon-counting method. e Radiative rate constant (k f = f / s ). f Non-radiative rate constant (k nr =(1- f)/ s ).

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11 Table S6. Absorption and fluorescence properties of 14 in various solvents a Cl OMe N N B O Ph Ph 14 solvent Hexane Toluene max ( ) b F max Stokes shift f c s d e f k f k nr (nm) (nm) (cm -1 ) (ns) (10 9 s -1 ) (10 9 s -1 ) 404 (29,800) 421 (27,300) 409 (27,800) 425 (25,800) 445, , 469 2,280 2, CHCl (30,300) 422 (28,400) 453, 469 2, THF 409(29,400) 455 2, CH 2 Cl (30,900) 455, 474 2, MeCN 404 (28,900) 457 2, a Measured at a concentration of 1.0 x 10-5 mol dm -3. b The excitation wavelengths ( ex ) were as follows: hexane (409 nm), toluene (409 nm), 1,4-dioxane (409 nm), chloroform (409 nm), THF (409 nm), dichloromethane (409 nm) and acetonitrile (409 nm). c Measured using an integrating sphere method. d Measured using a single-photon-counting method. e Radiative rate constant (k f = f/ s ). f Non-radiative rate constant (k nr =(1- f)/ s ). Table S7. Crystal data and structure refinement for 11. Identification code 11 Empirical formula C24 H18 B Cl N2 O Formula weight Temperature 293(2) K Wavelength Å Crystal system Monoclinic Space group P 21/c Unit cell dimensions a = 9.467(3) Å = 90. b = (7) Å = (10). c = (3) Å = 90. Volume (11) Å 3 Z 4 Density (calculated) Mg/m 3

12 Absorption coefficient mm -1 F(000) 824 Crystal size 0.20 x 0.20 x 0.20 mm 3 Theta range for data collection 2.17 to Index ranges -12<=h<=12, -26<=k<=26, -13<=l<=13 Reflections collected Independent reflections 4594 [R(int) = ] Completeness to theta = % Absorption correction Integration Max. and min. transmission and Refinement method Full-matrix least-squares on F 2 Data / restraints / parameters 4594 / 0 / 262 Goodness-of-fit on F Final R indices [I>2sigma(I)] R1 = , wr2 = R indices (all data) R1 = , wr2 = Largest diff. peak and hole and e.å -3 Table S8. Atomic coordinates ( x 10 4 ) and equivalent isotropic displacement parameters (Å 2 x 10 3 ) for 11. U(eq) is defined as one third of the trace of the orthogonalized U ij tensor. x y z U(eq) C(1) 4892(2) -640(1) 7645(2) 43(1) C(2) 4466(2) -165(1) 6767(2) 48(1) C(3) 3309(2) -263(1) 5803(2) 42(1) C(4) 2655(2) 240(1) 5040(2) 50(1) C(5) 1637(2) -965(1) 4737(2) 49(1) C(6) 5972(2) -556(1) 8768(2) 48(1) C(7) 6380(2) -1090(1) 9533(2) 70(1) C(8) 7412(3) -1033(1) 10569(3) 92(1) C(9) 8057(3) -443(1) 10871(2) 86(1) C(10) 7660(3) 80(1) 10133(3) 90(1) C(11) 6623(3) 37(1) 9086(2) 73(1) C(12) 1552(2) 79(1) 4144(2) 49(1) C(13) 4856(2) -1677(1) 5380(2) 44(1) C(14) 6230(2) -1850(1) 5909(2) 50(1) C(15) 7262(2) -2044(1) 5145(2) 60(1)

13 C(16) 6950(2) -2067(1) 3829(2) 65(1) C(17) 5613(2) -1901(1) 3272(2) 65(1) C(18) 4586(2) -1708(1) 4039(2) 55(1) C(19) 2558(2) -2051(1) 6591(2) 44(1) C(20) 2460(2) -2645(1) 5955(2) 59(1) C(21) 1478(3) -3116(1) 6261(2) 74(1) C(22) 599(2) -3001(1) 7183(2) 69(1) C(23) 677(2) -2423(1) 7833(2) 65(1) C(24) 1646(2) -1956(1) 7530(2) 53(1) B(1) 3651(2) -1482(1) 6293(2) 41(1) N(1) 2768(1) -878(1) 5606(1) 41(1) N(2) 995(2) -518(1) 3979(1) 53(1) O(1) 4306(1) -1225(1) 7560(1) 46(1) Cl(1) 754(1) 671(1) 3133(1) 69(1) Table S9. Bond lengths [Å] and angles [ ] for 11. C(1)-O(1) (18) C(1)-C(2) 1.366(2) C(1)-C(6) 1.472(2) C(2)-C(3) 1.412(2) C(3)-N(1) (19) C(3)-C(4) 1.404(2) C(4)-C(12) 1.358(2) C(5)-N(2) 1.315(2) C(5)-N(1) 1.331(2) C(6)-C(7) 1.385(3) C(6)-C(11) 1.388(2) C(7)-C(8) 1.374(3) C(8)-C(9) 1.378(4) C(9)-C(10) 1.350(4) C(10)-C(11) 1.383(3) C(12)-N(2) 1.339(2) C(12)-Cl(1) (17) C(13)-C(18) 1.395(2) C(13)-C(14) 1.397(2) C(13)-B(1) 1.622(2) C(14)-C(15) 1.391(3)

14 C(15)-C(16) 1.372(3) C(16)-C(17) 1.372(3) C(17)-C(18) 1.389(3) C(19)-C(20) 1.388(2) C(19)-C(24) 1.395(2) C(19)-B(1) 1.616(2) C(20)-C(21) 1.405(3) C(21)-C(22) 1.367(3) C(22)-C(23) 1.368(3) C(23)-C(24) 1.390(2) B(1)-O(1) 1.490(2) B(1)-N(1) 1.616(2) O(1)-C(1)-C(2) (14) O(1)-C(1)-C(6) (13) C(2)-C(1)-C(6) (14) C(1)-C(2)-C(3) (14) N(1)-C(3)-C(4) (14) N(1)-C(3)-C(2) (13) C(4)-C(3)-C(2) (14) C(12)-C(4)-C(3) (15) N(2)-C(5)-N(1) (15) C(7)-C(6)-C(11) (18) C(7)-C(6)-C(1) (15) C(11)-C(6)-C(1) (16) C(8)-C(7)-C(6) 120.7(2) C(7)-C(8)-C(9) 120.6(2) C(10)-C(9)-C(8) 119.0(2) C(9)-C(10)-C(11) 121.6(2) C(10)-C(11)-C(6) 119.9(2) N(2)-C(12)-C(4) (15) N(2)-C(12)-Cl(1) (13) C(4)-C(12)-Cl(1) (13) C(18)-C(13)-C(14) (15) C(18)-C(13)-B(1) (14) C(14)-C(13)-B(1) (15) C(15)-C(14)-C(13) (17) C(16)-C(15)-C(14) (17) C(17)-C(16)-C(15) (17) C(16)-C(17)-C(18) (19)

15 C(17)-C(18)-C(13) (17) C(20)-C(19)-C(24) (15) C(20)-C(19)-B(1) (16) C(24)-C(19)-B(1) (14) C(19)-C(20)-C(21) 120.4(2) C(22)-C(21)-C(20) (19) C(21)-C(22)-C(23) (18) C(22)-C(23)-C(24) 119.1(2) C(23)-C(24)-C(19) (18) O(1)-B(1)-C(19) (13) O(1)-B(1)-N(1) (11) C(19)-B(1)-N(1) (12) O(1)-B(1)-C(13) (13) C(19)-B(1)-C(13) (13) N(1)-B(1)-C(13) (12) C(5)-N(1)-C(3) (13) C(5)-N(1)-B(1) (12) C(3)-N(1)-B(1) (12) C(5)-N(2)-C(12) (15) C(1)-O(1)-B(1) (12) Symmetry transformations used to generate equivalent atoms: Table S10. Anisotropic displacement parameters (Å 2 x 10 3 ) for 11. The anisotropic displacement factor exponent takes the form: -2 2 [ h 2 a* 2 U h k a* b* U 12 ] U 11 U 22 U 33 U 23 U 13 U 12 C(1) 40(1) 41(1) 48(1) -5(1) 6(1) -3(1) C(2) 45(1) 40(1) 59(1) -2(1) 4(1) -6(1) C(3) 39(1) 38(1) 51(1) 1(1) 11(1) 2(1) C(4) 47(1) 40(1) 63(1) 7(1) 7(1) 4(1) C(5) 46(1) 44(1) 56(1) 1(1) 1(1) 2(1) C(6) 44(1) 51(1) 49(1) -6(1) 4(1) -4(1) C(7) 68(1) 62(1) 75(1) 8(1) -19(1) -11(1) C(8) 90(2) 86(2) 87(2) 15(1) -36(1) -12(1) C(9) 82(2) 96(2) 72(1) -5(1) -26(1) -21(1) C(10) 97(2) 77(2) 86(2) -12(1) -24(1) -31(1) C(11) 87(2) 57(1) 70(1) -5(1) -12(1) -17(1)

16 C(12) 44(1) 49(1) 55(1) 7(1) 11(1) 9(1) C(13) 41(1) 37(1) 53(1) 0(1) 3(1) 0(1) C(14) 46(1) 44(1) 59(1) 6(1) -2(1) 4(1) C(15) 40(1) 54(1) 85(1) 2(1) 3(1) 9(1) C(16) 50(1) 68(1) 80(1) -15(1) 17(1) 7(1) C(17) 57(1) 81(1) 58(1) -16(1) 8(1) 5(1) C(18) 42(1) 66(1) 56(1) -9(1) 1(1) 6(1) C(19) 41(1) 40(1) 49(1) 5(1) -7(1) -2(1) C(20) 64(1) 45(1) 66(1) -4(1) 0(1) -9(1) C(21) 85(2) 45(1) 88(2) -4(1) -12(1) -18(1) C(22) 57(1) 68(1) 75(1) 20(1) -14(1) -22(1) C(23) 48(1) 77(1) 69(1) 14(1) 2(1) -13(1) C(24) 45(1) 53(1) 60(1) 5(1) 3(1) -5(1) B(1) 40(1) 38(1) 45(1) 1(1) -2(1) 1(1) N(1) 37(1) 39(1) 47(1) 0(1) 5(1) 2(1) N(2) 47(1) 52(1) 57(1) 4(1) -3(1) 5(1) O(1) 49(1) 42(1) 47(1) 1(1) -1(1) -7(1) Cl(1) 67(1) 61(1) 76(1) 20(1) -4(1) 13(1) Table S11. Hydrogen coordinates ( x 10 4 ) and isotropic displacement parameters (Å 2 x 10 3 ) for 11. x y z U(eq) H(2) H(4) H(7) H(8) H(9) H(10) H(11) H(14) H(15) H(16) H(17) H(18) H(20)

17 H(21) H(22) H(23) H(23A) H(24) Table S12. Torsion angles [ ] for 11. O(1)-C(1)-C(2)-C(3) 5.4(2) C(6)-C(1)-C(2)-C(3) (15) C(1)-C(2)-C(3)-N(1) -11.5(2) C(1)-C(2)-C(3)-C(4) (15) N(1)-C(3)-C(4)-C(12) -1.3(2) C(2)-C(3)-C(4)-C(12) (16) O(1)-C(1)-C(6)-C(7) 6.5(2) C(2)-C(1)-C(6)-C(7) (18) O(1)-C(1)-C(6)-C(11) (18) C(2)-C(1)-C(6)-C(11) 3.5(3) C(11)-C(6)-C(7)-C(8) -0.7(3) C(1)-C(6)-C(7)-C(8) 178.3(2) C(6)-C(7)-C(8)-C(9) 0.3(4) C(7)-C(8)-C(9)-C(10) 0.0(5) C(8)-C(9)-C(10)-C(11) 0.1(5) C(9)-C(10)-C(11)-C(6) -0.5(4) C(7)-C(6)-C(11)-C(10) 0.7(3) C(1)-C(6)-C(11)-C(10) (2) C(3)-C(4)-C(12)-N(2) 3.6(3) C(3)-C(4)-C(12)-Cl(1) (12) C(18)-C(13)-C(14)-C(15) -0.5(2) B(1)-C(13)-C(14)-C(15) (15) C(13)-C(14)-C(15)-C(16) 0.4(3) C(14)-C(15)-C(16)-C(17) -0.4(3) C(15)-C(16)-C(17)-C(18) 0.3(3) C(16)-C(17)-C(18)-C(13) -0.4(3) C(14)-C(13)-C(18)-C(17) 0.4(3) B(1)-C(13)-C(18)-C(17) (17) C(24)-C(19)-C(20)-C(21) 0.2(3) B(1)-C(19)-C(20)-C(21) (16)

18 C(19)-C(20)-C(21)-C(22) 0.2(3) C(20)-C(21)-C(22)-C(23) -0.6(3) C(21)-C(22)-C(23)-C(24) 0.7(3) C(22)-C(23)-C(24)-C(19) -0.3(3) C(20)-C(19)-C(24)-C(23) -0.1(2) B(1)-C(19)-C(24)-C(23) (16) C(20)-C(19)-B(1)-O(1) (15) C(24)-C(19)-B(1)-O(1) 44.31(18) C(20)-C(19)-B(1)-N(1) (17) C(24)-C(19)-B(1)-N(1) (18) C(20)-C(19)-B(1)-C(13) -10.7(2) C(24)-C(19)-B(1)-C(13) (14) C(18)-C(13)-B(1)-O(1) (14) C(14)-C(13)-B(1)-O(1) 25.68(19) C(18)-C(13)-B(1)-C(19) 80.37(19) C(14)-C(13)-B(1)-C(19) (17) C(18)-C(13)-B(1)-N(1) (19) C(14)-C(13)-B(1)-N(1) (14) N(2)-C(5)-N(1)-C(3) 3.4(3) N(2)-C(5)-N(1)-B(1) (16) C(4)-C(3)-N(1)-C(5) -1.9(2) C(2)-C(3)-N(1)-C(5) (14) C(4)-C(3)-N(1)-B(1) (13) C(2)-C(3)-N(1)-B(1) -11.2(2) O(1)-B(1)-N(1)-C(5) (14) C(19)-B(1)-N(1)-C(5) (19) C(13)-B(1)-N(1)-C(5) 88.28(17) O(1)-B(1)-N(1)-C(3) 35.11(17) C(19)-B(1)-N(1)-C(3) (13) C(13)-B(1)-N(1)-C(3) (16) N(1)-C(5)-N(2)-C(12) -1.3(3) C(4)-C(12)-N(2)-C(5) -2.3(3) Cl(1)-C(12)-N(2)-C(5) (13) C(2)-C(1)-O(1)-B(1) 25.7(2) C(6)-C(1)-O(1)-B(1) (13) C(19)-B(1)-O(1)-C(1) (13) N(1)-B(1)-O(1)-C(1) (17) C(13)-B(1)-O(1)-C(1) 72.81(16) Symmetry transformations used to generate equivalent atoms:

19 Table S13. Crystal data and structure refinement for 12. Identification code 12 Empirical formula C25 H17 B Cl F3 N2 O Formula weight Temperature 293(2) K Wavelength Å Crystal system Monoclinic Space group P21/c Unit cell dimensions a = (3) Å = 90. b = (8) Å = (11). c = (2) Å = 90. Volume (12) Å 3 Z 4 Density (calculated) Mg/m 3 Absorption coefficient mm -1 F(000) 952 Crystal size 0.20 x 0.20 x 0.20 mm 3 Theta range for data collection 1.97 to Index ranges -13<=h<=13, -26<=k<=26, -13<=l<=13 Reflections collected Independent reflections 5121 [R(int) = ] Completeness to theta = % Absorption correction Integration Max. and min. transmission and Refinement method Full-matrix least-squares on F 2 Data / restraints / parameters 5121 / 0 / 298 Goodness-of-fit on F Final R indices [I>2sigma(I)] R1 = , wr2 = R indices (all data) R1 = , wr2 = Largest diff. peak and hole and e.å -3 Table S14. Atomic coordinates ( x 10 4 ) and equivalent isotropic displacement parameters (Å 2 x 10 3 ) for 12. U(eq) is defined as one third of the trace of the orthogonalized U ij tensor. x y z U(eq)

20 C(1) 5481(2) 10635(1) 12313(2) 42(1) C(2) 5793(2) 10154(1) 11479(2) 45(1) C(3) 6822(2) 10238(1) 10635(2) 42(1) C(4) 7349(2) 9722(1) 9947(2) 48(1) C(5) 8355(2) 10919(1) 9740(2) 53(1) C(6) 4517(2) 10558(1) 13307(2) 41(1) C(7) 4167(2) 11104(1) 14021(2) 53(1) C(8) 3244(2) 11052(1) 14928(2) 56(1) C(9) 2661(2) 10453(1) 15153(2) 47(1) C(10) 3005(2) 9906(1) 14461(2) 54(1) C(11) 3929(2) 9957(1) 13546(2) 50(1) C(12) 8340(2) 9861(1) 9166(2) 51(1) C(13) 5482(2) 11690(1) 10092(2) 48(1) C(14) 4241(2) 11848(1) 10477(2) 54(1) C(15) 3261(2) 12051(1) 9613(3) 66(1) C(16) 3501(3) 12102(1) 8338(3) 73(1) C(17) 4712(3) 11956(1) 7925(3) 72(1) C(18) 5680(2) 11753(1) 8786(2) 62(1) C(19) 7670(2) 12026(1) 11527(2) 48(1) C(20) 7758(2) 12631(1) 10923(3) 69(1) C(21) 8689(3) 13089(1) 11313(3) 85(1) C(22) 9542(3) 12960(1) 12312(3) 78(1) C(23) 9485(3) 12366(1) 12928(3) 78(1) C(24) 8558(2) 11909(1) 12535(2) 64(1) C(25) 1640(2) 10408(1) 16113(2) 57(1) O(1) 6053(1) 11217(1) 12310(1) 46(1) N(1) 7349(2) 10848(1) 10499(2) 43(1) N(2) 8877(2) 10452(1) 9051(2) 57(1) F(1) 1464(2) 9802(1) 16542(2) 82(1) F(2) 493(1) 10620(1) 15656(2) 85(1) F(3) 1919(2) 10780(1) 17152(1) 79(1) Cl(1) 8975(1) 9242(1) 8259(1) 69(1) B(1) 6615(2) 11474(1) 11117(2) 45(1) Table S15. Bond lengths [Å] and angles [ ] for 12. C(1)-O(1) 1.325(2)

21 C(1)-C(2) 1.363(3) C(1)-C(6) 1.485(3) C(2)-C(3) 1.428(3) C(3)-N(1) 1.367(2) C(3)-C(4) 1.400(3) C(4)-C(12) 1.372(3) C(5)-N(2) 1.327(3) C(5)-N(1) 1.348(3) C(6)-C(11) 1.395(3) C(6)-C(7) 1.399(3) C(7)-C(8) 1.384(3) C(8)-C(9) 1.387(3) C(9)-C(10) 1.386(3) C(9)-C(25) 1.497(3) C(10)-C(11) 1.391(3) C(12)-N(2) 1.334(3) C(12)-Cl(1) 1.729(2) C(13)-C(14) 1.401(3) C(13)-C(18) 1.404(3) C(13)-B(1) 1.616(3) C(14)-C(15) 1.392(3) C(15)-C(16) 1.379(4) C(16)-C(17) 1.376(4) C(17)-C(18) 1.382(3) C(19)-C(24) 1.391(3) C(19)-C(20) 1.391(3) C(19)-B(1) 1.612(3) C(20)-C(21) 1.390(3) C(21)-C(22) 1.365(4) C(22)-C(23) 1.375(4) C(23)-C(24) 1.386(3) C(25)-F(1) 1.329(3) C(25)-F(2) 1.331(3) C(25)-F(3) 1.350(3) O(1)-B(1) 1.500(3) N(1)-B(1) 1.633(3) O(1)-C(1)-C(2) (17) O(1)-C(1)-C(6) (16) C(2)-C(1)-C(6) (16)

22 C(1)-C(2)-C(3) (17) N(1)-C(3)-C(4) (18) N(1)-C(3)-C(2) (16) C(4)-C(3)-C(2) (17) C(12)-C(4)-C(3) (18) N(2)-C(5)-N(1) (19) C(11)-C(6)-C(7) (18) C(11)-C(6)-C(1) (16) C(7)-C(6)-C(1) (16) C(8)-C(7)-C(6) (18) C(7)-C(8)-C(9) (18) C(10)-C(9)-C(8) (19) C(10)-C(9)-C(25) (18) C(8)-C(9)-C(25) (18) C(9)-C(10)-C(11) (18) C(10)-C(11)-C(6) (18) N(2)-C(12)-C(4) (18) N(2)-C(12)-Cl(1) (16) C(4)-C(12)-Cl(1) (16) C(14)-C(13)-C(18) 116.0(2) C(14)-C(13)-B(1) (19) C(18)-C(13)-B(1) (19) C(15)-C(14)-C(13) 121.9(2) C(16)-C(15)-C(14) 120.0(2) C(17)-C(16)-C(15) 119.8(2) C(16)-C(17)-C(18) 120.0(3) C(17)-C(18)-C(13) 122.3(2) C(24)-C(19)-C(20) 116.4(2) C(24)-C(19)-B(1) (18) C(20)-C(19)-B(1) 123.6(2) C(21)-C(20)-C(19) 121.3(2) C(22)-C(21)-C(20) 120.8(2) C(21)-C(22)-C(23) 119.5(2) C(22)-C(23)-C(24) 119.6(3) C(23)-C(24)-C(19) 122.4(2) F(1)-C(25)-F(2) 106.9(2) F(1)-C(25)-F(3) (19) F(2)-C(25)-F(3) (18) F(1)-C(25)-C(9) (17) F(2)-C(25)-C(9) (19)

23 F(3)-C(25)-C(9) (19) C(1)-O(1)-B(1) (15) C(5)-N(1)-C(3) (16) C(5)-N(1)-B(1) (15) C(3)-N(1)-B(1) (15) C(5)-N(2)-C(12) (19) O(1)-B(1)-C(19) (16) O(1)-B(1)-C(13) (16) C(19)-B(1)-C(13) (16) O(1)-B(1)-N(1) (14) C(19)-B(1)-N(1) (16) C(13)-B(1)-N(1) (15) Symmetry transformations used to generate equivalent atoms: Table S16. Anisotropic displacement parameters (Å 2 x 10 3 ) for 12. The anisotropic displacement factor exponent takes the form: -2 2 [ h 2 a* 2 U h k a* b* U 12 ] U 11 U 22 U 33 U 23 U 13 U 12 C(1) 44(1) 35(1) 46(1) 2(1) -1(1) -3(1) C(2) 48(1) 38(1) 50(1) -3(1) 7(1) -7(1) C(3) 44(1) 39(1) 43(1) -2(1) -1(1) -2(1) C(4) 53(1) 41(1) 51(1) -6(1) 3(1) -1(1) C(5) 52(1) 49(1) 59(1) 0(1) 10(1) -5(1) C(6) 43(1) 38(1) 43(1) 1(1) 2(1) 0(1) C(7) 64(1) 38(1) 57(1) -1(1) 13(1) -5(1) C(8) 67(1) 42(1) 58(1) -4(1) 14(1) 4(1) C(9) 45(1) 49(1) 49(1) 4(1) 5(1) 4(1) C(10) 56(1) 43(1) 64(1) -1(1) 12(1) -8(1) C(11) 56(1) 38(1) 58(1) -3(1) 9(1) -4(1) C(12) 48(1) 54(1) 51(1) -7(1) 1(1) 6(1) C(13) 55(1) 33(1) 56(1) 0(1) 2(1) -5(1) C(14) 55(1) 40(1) 66(1) -1(1) 3(1) -3(1) C(15) 56(1) 44(1) 99(2) 4(1) -6(1) 0(1) C(16) 76(2) 56(1) 83(2) 9(1) -23(1) -1(1) C(17) 88(2) 69(2) 59(1) 10(1) -7(1) 4(1) C(18) 68(1) 61(1) 57(1) 5(1) 4(1) 6(1) C(19) 50(1) 38(1) 56(1) -5(1) 10(1) -5(1)

24 C(20) 67(1) 47(1) 92(2) 10(1) -1(1) -13(1) C(21) 79(2) 45(1) 130(3) 9(1) 4(2) -22(1) C(22) 70(2) 61(1) 104(2) -18(1) 13(2) -28(1) C(23) 72(2) 81(2) 81(2) -9(1) -9(1) -23(1) C(24) 70(1) 53(1) 69(1) -2(1) -4(1) -16(1) C(25) 52(1) 60(1) 61(1) 1(1) 10(1) 7(1) O(1) 53(1) 38(1) 49(1) -4(1) 9(1) -9(1) N(1) 44(1) 38(1) 47(1) 1(1) 3(1) -2(1) N(2) 53(1) 60(1) 60(1) -5(1) 11(1) -3(1) F(1) 85(1) 68(1) 96(1) 16(1) 40(1) -4(1) F(2) 52(1) 106(1) 96(1) -1(1) 9(1) 19(1) F(3) 83(1) 93(1) 61(1) -11(1) 22(1) -4(1) Cl(1) 67(1) 72(1) 71(1) -21(1) 15(1) 9(1) B(1) 48(1) 36(1) 50(1) -1(1) 6(1) -4(1) Table S17. Hydrogen coordinates ( x 10 4 ) and isotropic displacement parameters (Å 2 x 10 3 ) for 12. x y z U(eq) H(2) H(4) H(5) H(7) H(8) H(10) H(11) H(14) H(15) H(16) H(17) H(18) H(20) H(21) H(22) H(23) H(24)

25 Table S18. Torsion angles [ ] for 12. O(1)-C(1)-C(2)-C(3) 5.1(3) C(6)-C(1)-C(2)-C(3) (17) C(1)-C(2)-C(3)-N(1) -11.8(3) C(1)-C(2)-C(3)-C(4) (19) N(1)-C(3)-C(4)-C(12) -1.1(3) C(2)-C(3)-C(4)-C(12) (18) O(1)-C(1)-C(6)-C(11) (17) C(2)-C(1)-C(6)-C(11) 6.0(3) O(1)-C(1)-C(6)-C(7) 8.3(3) C(2)-C(1)-C(6)-C(7) (19) C(11)-C(6)-C(7)-C(8) -1.1(3) C(1)-C(6)-C(7)-C(8) (19) C(6)-C(7)-C(8)-C(9) 0.9(3) C(7)-C(8)-C(9)-C(10) -0.3(3) C(7)-C(8)-C(9)-C(25) (2) C(8)-C(9)-C(10)-C(11) 0.1(3) C(25)-C(9)-C(10)-C(11) 178.2(2) C(9)-C(10)-C(11)-C(6) -0.4(3) C(7)-C(6)-C(11)-C(10) 0.8(3) C(1)-C(6)-C(11)-C(10) (18) C(3)-C(4)-C(12)-N(2) 2.8(3) C(3)-C(4)-C(12)-Cl(1) (14) C(18)-C(13)-C(14)-C(15) 0.5(3) B(1)-C(13)-C(14)-C(15) (18) C(13)-C(14)-C(15)-C(16) -0.1(3) C(14)-C(15)-C(16)-C(17) -0.4(3) C(15)-C(16)-C(17)-C(18) 0.5(4) C(16)-C(17)-C(18)-C(13) -0.1(4) C(14)-C(13)-C(18)-C(17) -0.4(3) B(1)-C(13)-C(18)-C(17) (2) C(24)-C(19)-C(20)-C(21) 0.2(4) B(1)-C(19)-C(20)-C(21) (2) C(19)-C(20)-C(21)-C(22) -0.5(5) C(20)-C(21)-C(22)-C(23) 0.7(5) C(21)-C(22)-C(23)-C(24) -0.6(4)

26 C(22)-C(23)-C(24)-C(19) 0.2(4) C(20)-C(19)-C(24)-C(23) 0.0(4) B(1)-C(19)-C(24)-C(23) (2) C(10)-C(9)-C(25)-F(1) 22.5(3) C(8)-C(9)-C(25)-F(1) (2) C(10)-C(9)-C(25)-F(2) -98.8(2) C(8)-C(9)-C(25)-F(2) 79.3(3) C(10)-C(9)-C(25)-F(3) 142.6(2) C(8)-C(9)-C(25)-F(3) -39.3(3) C(2)-C(1)-O(1)-B(1) 25.9(3) C(6)-C(1)-O(1)-B(1) (16) N(2)-C(5)-N(1)-C(3) 2.7(3) N(2)-C(5)-N(1)-B(1) (2) C(4)-C(3)-N(1)-C(5) -1.4(3) C(2)-C(3)-N(1)-C(5) (17) C(4)-C(3)-N(1)-B(1) (17) C(2)-C(3)-N(1)-B(1) -10.4(2) N(1)-C(5)-N(2)-C(12) -1.2(3) C(4)-C(12)-N(2)-C(5) -1.6(3) Cl(1)-C(12)-N(2)-C(5) (16) C(1)-O(1)-B(1)-C(19) (16) C(1)-O(1)-B(1)-C(13) 72.4(2) C(1)-O(1)-B(1)-N(1) -42.4(2) C(24)-C(19)-B(1)-O(1) 45.3(3) C(20)-C(19)-B(1)-O(1) (2) C(24)-C(19)-B(1)-C(13) 170.5(2) C(20)-C(19)-B(1)-C(13) -9.4(3) C(24)-C(19)-B(1)-N(1) -68.7(2) C(20)-C(19)-B(1)-N(1) 111.4(2) C(14)-C(13)-B(1)-O(1) 22.5(2) C(18)-C(13)-B(1)-O(1) (18) C(14)-C(13)-B(1)-C(19) (2) C(18)-C(13)-B(1)-C(19) 76.5(2) C(14)-C(13)-B(1)-N(1) (17) C(18)-C(13)-B(1)-N(1) -45.7(2) C(5)-N(1)-B(1)-O(1) (17) C(3)-N(1)-B(1)-O(1) 34.4(2) C(5)-N(1)-B(1)-C(19) -38.3(2) C(3)-N(1)-B(1)-C(19) (16) C(5)-N(1)-B(1)-C(13) 88.5(2)

27 C(3)-N(1)-B(1)-C(13) (19) Symmetry transformations used to generate equivalent atoms: Table S19. Crystal data and structure refinement for 13. Identification code 13 Empirical formula C25 H17 B Cl N3 O Formula weight Temperature 293(2) K Wavelength Å Crystal system Monoclinic Space group P21/a Unit cell dimensions a = (4) Å = 90. b = (6) Å = (8). c = (3) Å = 90. Volume (12) Å 3 Z 4 Density (calculated) Mg/m 3 Absorption coefficient mm -1 F(000) 872 Crystal size 0.20 x 0.20 x 0.20 mm 3 Theta range for data collection 1.91 to Index ranges -13<=h<=13, -27<=k<=27, -13<=l<=13 Reflections collected Independent reflections 4786 [R(int) = ] Completeness to theta = % Absorption correction Integration Max. and min. transmission and Refinement method Full-matrix least-squares on F 2 Data / restraints / parameters 4786 / 0 / 280 Goodness-of-fit on F Final R indices [I>2sigma(I)] R1 = , wr2 = R indices (all data) R1 = , wr2 = Largest diff. peak and hole and e.å -3

28 Table S20. Atomic coordinates ( x 10 4 ) and equivalent isotropic displacement parameters (Å 2 x 10 3 ) for 13. U(eq) is defined as one third of the trace of the orthogonalized U ij tensor. x y z U(eq) C(1) 7371(2) 9131(1) 5258(2) 46(1) C(2) 7826(2) 9624(1) 4764(2) 51(1) C(3) 8223(2) 9551(1) 3653(2) 45(1) C(4) 8459(2) 10048(1) 2932(2) 54(1) C(5) 8658(2) 8880(1) 2171(2) 53(1) C(6) 6816(2) 9180(1) 6313(2) 48(1) C(7) 6671(2) 8638(1) 6958(2) 54(1) C(8) 6216(2) 8663(1) 7983(2) 59(1) C(9) 5862(2) 9235(1) 8360(2) 52(1) C(10) 5966(3) 9777(1) 7709(2) 61(1) C(11) 6449(3) 9751(1) 6696(2) 60(1) C(12) 8817(2) 9904(1) 1879(2) 54(1) N(1) 8354(2) 8956(1) 3253(2) 44(1) N(2) 8906(2) 9325(1) 1459(2) 55(1) N(3) 5044(3) 9240(1) 10312(2) 78(1) O(1) 7364(2) 8553(1) 4811(1) 49(1) B(1) 8358(2) 8364(1) 4217(2) 44(1) C(13) 9983(2) 8281(1) 5453(2) 46(1) C(14) 10280(2) 8162(1) 6855(2) 52(1) C(15) 11664(3) 8060(1) 7914(2) 60(1) C(16) 12800(3) 8064(1) 7607(2) 66(1) C(17) 12558(3) 8175(1) 6236(3) 69(1) C(18) 11175(2) 8280(1) 5190(2) 59(1) C(19) 7669(2) 7770(1) 3202(2) 50(1) C(20) 8436(3) 7223(1) 3305(3) 71(1) C(21) 7764(5) 6720(1) 2404(5) 107(1) C(22) 6340(5) 6752(2) 1409(4) 114(2) C(23) 5577(4) 7287(2) 1280(3) 94(1) C(24) 6228(3) 7788(1) 2166(2) 66(1) C(25) 5389(3) 9246(1) 9447(2) 60(1) Cl(1) 9197(1) 10487(1) 991(1) 91(1) Table S21. Bond lengths [Å] and angles [ ] for 13.

29 C(1)-O(1) 1.320(2) C(1)-C(2) 1.354(3) C(1)-C(6) 1.477(3) C(2)-C(3) 1.422(3) C(3)-N(1) 1.366(2) C(3)-C(4) 1.392(3) C(4)-C(12) 1.362(3) C(5)-N(2) 1.309(3) C(5)-N(1) 1.329(2) C(6)-C(7) 1.386(3) C(6)-C(11) 1.394(3) C(7)-C(8) 1.369(3) C(8)-C(9) 1.386(3) C(9)-C(10) 1.377(3) C(9)-C(25) 1.442(3) C(10)-C(11) 1.377(3) C(12)-N(2) 1.331(3) C(12)-Cl(1) 1.711(2) N(1)-B(1) 1.621(3) N(3)-C(25) 1.127(3) O(1)-B(1) 1.492(2) B(1)-C(19) 1.604(3) B(1)-C(13) 1.608(3) C(13)-C(18) 1.392(3) C(13)-C(14) 1.393(3) C(14)-C(15) 1.381(3) C(15)-C(16) 1.364(3) C(16)-C(17) 1.373(3) C(17)-C(18) 1.376(3) C(19)-C(20) 1.390(3) C(19)-C(24) 1.398(3) C(20)-C(21) 1.394(4) C(21)-C(22) 1.373(6) C(22)-C(23) 1.364(5) C(23)-C(24) 1.378(3) O(1)-C(1)-C(2) (17) O(1)-C(1)-C(6) (17) C(2)-C(1)-C(6) (17)

30 C(1)-C(2)-C(3) (17) N(1)-C(3)-C(4) (17) N(1)-C(3)-C(2) (16) C(4)-C(3)-C(2) (17) C(12)-C(4)-C(3) (18) N(2)-C(5)-N(1) (18) C(7)-C(6)-C(11) (18) C(7)-C(6)-C(1) (16) C(11)-C(6)-C(1) (19) C(8)-C(7)-C(6) (18) C(7)-C(8)-C(9) 119.8(2) C(10)-C(9)-C(8) (19) C(10)-C(9)-C(25) (18) C(8)-C(9)-C(25) 118.4(2) C(9)-C(10)-C(11) (19) C(10)-C(11)-C(6) 120.5(2) N(2)-C(12)-C(4) (19) N(2)-C(12)-Cl(1) (16) C(4)-C(12)-Cl(1) (16) C(5)-N(1)-C(3) (16) C(5)-N(1)-B(1) (15) C(3)-N(1)-B(1) (15) C(5)-N(2)-C(12) (18) C(1)-O(1)-B(1) (15) O(1)-B(1)-C(19) (16) O(1)-B(1)-C(13) (15) C(19)-B(1)-C(13) (16) O(1)-B(1)-N(1) (14) C(19)-B(1)-N(1) (15) C(13)-B(1)-N(1) (15) C(18)-C(13)-C(14) (19) C(18)-C(13)-B(1) (17) C(14)-C(13)-B(1) (17) C(15)-C(14)-C(13) 122.2(2) C(16)-C(15)-C(14) 120.4(2) C(15)-C(16)-C(17) 119.5(2) C(16)-C(17)-C(18) 119.7(2) C(17)-C(18)-C(13) 122.9(2) C(20)-C(19)-C(24) 117.3(2) C(20)-C(19)-B(1) 123.1(2)

31 C(24)-C(19)-B(1) (19) C(19)-C(20)-C(21) 120.2(3) C(22)-C(21)-C(20) 121.0(3) C(23)-C(22)-C(21) 119.6(3) C(22)-C(23)-C(24) 120.0(3) C(23)-C(24)-C(19) 121.9(3) N(3)-C(25)-C(9) 178.0(3) Symmetry transformations used to generate equivalent atoms: Table S22. Anisotropic displacement parameters (Å 2 x 10 3 ) for 13. The anisotropic displacement factor exponent takes the form: -2 2 [ h 2 a* 2 U h k a* b* U 12 ] U 11 U 22 U 33 U 23 U 13 U 12 C(1) 48(1) 45(1) 48(1) -8(1) 24(1) 3(1) C(2) 64(1) 42(1) 54(1) -10(1) 32(1) 0(1) C(3) 49(1) 39(1) 48(1) -6(1) 23(1) -1(1) C(4) 71(1) 38(1) 59(1) -5(1) 35(1) -2(1) C(5) 72(1) 42(1) 56(1) -4(1) 40(1) -1(1) C(6) 47(1) 51(1) 49(1) -8(1) 26(1) 4(1) C(7) 64(1) 45(1) 70(1) -11(1) 45(1) -1(1) C(8) 71(1) 53(1) 71(1) -5(1) 49(1) -1(1) C(9) 55(1) 59(1) 51(1) -9(1) 31(1) 3(1) C(10) 83(2) 53(1) 62(1) -4(1) 45(1) 13(1) C(11) 83(2) 51(1) 62(1) 1(1) 47(1) 14(1) C(12) 68(1) 44(1) 54(1) 1(1) 32(1) -4(1) N(1) 53(1) 38(1) 48(1) -4(1) 29(1) -2(1) N(2) 74(1) 45(1) 57(1) -1(1) 40(1) -1(1) N(3) 111(2) 69(1) 83(1) -2(1) 70(1) 10(1) O(1) 60(1) 43(1) 58(1) -9(1) 39(1) -3(1) B(1) 57(1) 37(1) 49(1) -5(1) 34(1) 0(1) C(13) 57(1) 39(1) 50(1) -7(1) 32(1) -2(1) C(14) 62(1) 50(1) 53(1) -2(1) 35(1) 0(1) C(15) 73(1) 61(1) 50(1) 1(1) 31(1) 4(1) C(16) 61(1) 73(2) 59(1) -2(1) 24(1) 2(1) C(17) 57(1) 89(2) 68(1) -3(1) 36(1) 1(1) C(18) 60(1) 72(1) 55(1) -2(1) 36(1) 1(1) C(19) 71(1) 42(1) 52(1) -7(1) 42(1) -11(1)

32 C(20) 100(2) 45(1) 96(2) -15(1) 70(2) -7(1) C(21) 167(3) 55(2) 166(3) -44(2) 135(3) -33(2) C(22) 179(4) 103(3) 114(3) -69(2) 113(3) -89(3) C(23) 129(3) 102(2) 57(1) -24(1) 50(2) -65(2) C(24) 81(2) 65(1) 55(1) -4(1) 34(1) -23(1) C(25) 76(1) 55(1) 60(1) -7(1) 42(1) 4(1) Cl(1) 160(1) 51(1) 94(1) 5(1) 86(1) -13(1) Table S23. Hydrogen coordinates ( x 10 4 ) and isotropic displacement parameters (Å 2 x 10 3 ) for 13. x y z U(eq) H(2) H(4) H(5) H(7) H(8) H(10) H(11) H(14) H(15) H(16) H(17) H(18) H(20) H(21) H(22) H(23) H(24) Table S24. Torsion angles [ ] for 13. O(1)-C(1)-C(2)-C(3) 4.7(3) C(6)-C(1)-C(2)-C(3) (19)

33 C(1)-C(2)-C(3)-N(1) -10.3(3) C(1)-C(2)-C(3)-C(4) 168.5(2) N(1)-C(3)-C(4)-C(12) -0.4(3) C(2)-C(3)-C(4)-C(12) (2) O(1)-C(1)-C(6)-C(7) 14.6(3) C(2)-C(1)-C(6)-C(7) (2) O(1)-C(1)-C(6)-C(11) (19) C(2)-C(1)-C(6)-C(11) 12.7(3) C(11)-C(6)-C(7)-C(8) -1.8(3) C(1)-C(6)-C(7)-C(8) 177.4(2) C(6)-C(7)-C(8)-C(9) 1.5(3) C(7)-C(8)-C(9)-C(10) 0.0(4) C(7)-C(8)-C(9)-C(25) (2) C(8)-C(9)-C(10)-C(11) -1.2(4) C(25)-C(9)-C(10)-C(11) 178.7(2) C(9)-C(10)-C(11)-C(6) 0.8(4) C(7)-C(6)-C(11)-C(10) 0.7(3) C(1)-C(6)-C(11)-C(10) (2) C(3)-C(4)-C(12)-N(2) 2.5(3) C(3)-C(4)-C(12)-Cl(1) (16) N(2)-C(5)-N(1)-C(3) 2.9(3) N(2)-C(5)-N(1)-B(1) (2) C(4)-C(3)-N(1)-C(5) -2.0(3) C(2)-C(3)-N(1)-C(5) (18) C(4)-C(3)-N(1)-B(1) (18) C(2)-C(3)-N(1)-B(1) -11.4(3) N(1)-C(5)-N(2)-C(12) -1.0(3) C(4)-C(12)-N(2)-C(5) -1.8(3) Cl(1)-C(12)-N(2)-C(5) (17) C(2)-C(1)-O(1)-B(1) 24.8(3) C(6)-C(1)-O(1)-B(1) (17) C(1)-O(1)-B(1)-C(19) (16) C(1)-O(1)-B(1)-C(13) 75.1(2) C(1)-O(1)-B(1)-N(1) -40.4(2) C(5)-N(1)-B(1)-O(1) (17) C(3)-N(1)-B(1)-O(1) 33.9(2) C(5)-N(1)-B(1)-C(19) -39.3(2) C(3)-N(1)-B(1)-C(19) (17) C(5)-N(1)-B(1)-C(13) 87.0(2) C(3)-N(1)-B(1)-C(13) (19)

34 O(1)-B(1)-C(13)-C(18) (18) C(19)-B(1)-C(13)-C(18) 74.2(2) N(1)-B(1)-C(13)-C(18) -47.8(2) O(1)-B(1)-C(13)-C(14) 22.8(2) C(19)-B(1)-C(13)-C(14) (2) N(1)-B(1)-C(13)-C(14) (17) C(18)-C(13)-C(14)-C(15) 0.9(3) B(1)-C(13)-C(14)-C(15) (19) C(13)-C(14)-C(15)-C(16) -0.8(3) C(14)-C(15)-C(16)-C(17) 0.3(4) C(15)-C(16)-C(17)-C(18) 0.1(4) C(16)-C(17)-C(18)-C(13) 0.0(4) C(14)-C(13)-C(18)-C(17) -0.5(3) B(1)-C(13)-C(18)-C(17) (2) O(1)-B(1)-C(19)-C(20) (2) C(13)-B(1)-C(19)-C(20) -3.9(3) N(1)-B(1)-C(19)-C(20) 117.2(2) O(1)-B(1)-C(19)-C(24) 49.6(2) C(13)-B(1)-C(19)-C(24) (17) N(1)-B(1)-C(19)-C(24) -63.4(2) C(24)-C(19)-C(20)-C(21) -0.4(3) B(1)-C(19)-C(20)-C(21) 179.0(2) C(19)-C(20)-C(21)-C(22) -0.4(4) C(20)-C(21)-C(22)-C(23) 1.3(5) C(21)-C(22)-C(23)-C(24) -1.3(4) C(22)-C(23)-C(24)-C(19) 0.5(4) C(20)-C(19)-C(24)-C(23) 0.3(3) B(1)-C(19)-C(24)-C(23) (19) C(10)-C(9)-C(25)-N(3) -150(8) C(8)-C(9)-C(25)-N(3) 30(9) Symmetry transformations used to generate equivalent atoms: Table S25. Crystal data and structure refinement for 14. Identification code 14 Empirical formula C25 H20 B Cl N2 O2 Formula weight Temperature 293(2) K

35 Wavelength Å Crystal system Monoclinic Space group P 21/c Unit cell dimensions a = (2) Å = 90. b = (4) Å = (10). c = (2) Å = 90. Volume (7) Å 3 Z 4 Density (calculated) Mg/m 3 Absorption coefficient mm -1 F(000) 888 Crystal size 0.20 x 0.20 x 0.20 mm 3 Theta range for data collection 2.79 to Index ranges -13<=h<=13, -26<=k<=26, -13<=l<=13 Reflections collected Independent reflections 4931 [R(int) = ] Completeness to theta = % Absorption correction Integration Max. and min. transmission and Refinement method Full-matrix least-squares on F 2 Data / restraints / parameters 4931 / 0 / 281 Goodness-of-fit on F Final R indices [I>2sigma(I)] R1 = , wr2 = R indices (all data) R1 = , wr2 = Largest diff. peak and hole and e.å -3 Table S26. Atomic coordinates ( x 10 4 ) and equivalent isotropic displacement parameters (Å 2 x 10 3 ) for 14. U(eq) is defined as one third of the trace of the orthogonalized U ij tensor. x y z U(eq) C(1) 487(2) 10703(1) 7218(2) 41(1) C(2) 811(2) 10193(1) 6443(2) 47(1) C(3) 1844(2) 10256(1) 5595(2) 42(1) C(4) 2366(2) 9709(1) 4959(2) 49(1) C(5) 3392(2) 10916(1) 4615(2) 48(1) C(6) -477(2) 10648(1) 8210(2) 46(1) C(7) -885(2) 11219(1) 8835(2) 57(1)

36 C(8) -1828(3) 11187(1) 9732(2) 67(1) C(9) -2368(2) 10583(1) 10051(2) 63(1) C(10) -1958(2) 10009(1) 9473(2) 65(1) C(11) -1021(2) 10042(1) 8546(2) 57(1) C(12) 3356(2) 9826(1) 4170(2) 49(1) C(13) 466(2) 11706(1) 4899(2) 43(1) C(14) -807(2) 11869(1) 5259(2) 49(1) C(15) -1817(2) 12023(1) 4382(3) 63(1) C(16) -1573(3) 12020(1) 3123(3) 70(1) C(17) -326(3) 11874(1) 2733(2) 69(1) C(18) 670(2) 11718(1) 3613(2) 57(1) C(19) 2700(2) 12098(1) 6266(2) 44(1) C(20) 2805(3) 12682(1) 5587(3) 66(1) C(21) 3770(3) 13158(1) 5911(3) 83(1) C(22) 4625(3) 13064(1) 6919(3) 77(1) C(23) 4533(3) 12492(1) 7621(3) 72(1) C(24) 3581(2) 12017(1) 7289(2) 57(1) C(25) -3809(3) 10015(2) 11416(3) 82(1) N(1) 2381(1) 10870(1) 5388(1) 40(1) N(2) 3911(2) 10424(1) 3976(2) 53(1) O(1) 1053(1) 11296(1) 7128(1) 44(1) O(2) -3293(2) 10612(1) 10955(2) 88(1) Cl(1) 3987(1) 9164(1) 3344(1) 67(1) B(1) 1630(2) 11519(1) 5934(2) 40(1) Table S27. Bond lengths [Å] and angles [ ] for 14. C(1)-O(1) 1.325(2) C(1)-C(2) 1.364(3) C(1)-C(6) 1.476(3) C(2)-C(3) 1.419(3) C(3)-N(1) 1.366(2) C(3)-C(4) 1.405(3) C(4)-C(12) 1.358(3) C(5)-N(2) 1.320(2) C(5)-N(1) 1.346(2) C(6)-C(11) 1.386(3) C(6)-C(7) 1.396(3)

37 C(7)-C(8) 1.383(3) C(8)-C(9) 1.376(4) C(9)-O(2) 1.375(3) C(9)-C(10) 1.378(4) C(10)-C(11) 1.402(3) C(12)-N(2) 1.344(3) C(12)-Cl(1) (19) C(13)-C(18) 1.397(3) C(13)-C(14) 1.398(3) C(13)-B(1) 1.618(3) C(14)-C(15) 1.386(3) C(15)-C(16) 1.376(4) C(16)-C(17) 1.377(4) C(17)-C(18) 1.378(3) C(19)-C(20) 1.384(3) C(19)-C(24) 1.385(3) C(19)-B(1) 1.613(3) C(20)-C(21) 1.395(3) C(21)-C(22) 1.360(4) C(22)-C(23) 1.374(4) C(23)-C(24) 1.386(3) C(25)-O(2) 1.402(3) N(1)-B(1) 1.627(2) O(1)-B(1) 1.494(2) O(1)-C(1)-C(2) (16) O(1)-C(1)-C(6) (16) C(2)-C(1)-C(6) (16) C(1)-C(2)-C(3) (16) N(1)-C(3)-C(4) (17) N(1)-C(3)-C(2) (16) C(4)-C(3)-C(2) (17) C(12)-C(4)-C(3) (17) N(2)-C(5)-N(1) (18) C(11)-C(6)-C(7) (18) C(11)-C(6)-C(1) (18) C(7)-C(6)-C(1) (17) C(8)-C(7)-C(6) 121.4(2) C(9)-C(8)-C(7) 120.4(2) O(2)-C(9)-C(8) 115.3(2)

38 O(2)-C(9)-C(10) 125.3(2) C(8)-C(9)-C(10) 119.4(2) C(9)-C(10)-C(11) 120.3(2) C(6)-C(11)-C(10) 120.8(2) N(2)-C(12)-C(4) (17) N(2)-C(12)-Cl(1) (15) C(4)-C(12)-Cl(1) (15) C(18)-C(13)-C(14) (18) C(18)-C(13)-B(1) (17) C(14)-C(13)-B(1) (17) C(15)-C(14)-C(13) 121.6(2) C(16)-C(15)-C(14) 119.8(2) C(15)-C(16)-C(17) 120.3(2) C(16)-C(17)-C(18) 119.4(2) C(17)-C(18)-C(13) 122.4(2) C(20)-C(19)-C(24) (19) C(20)-C(19)-B(1) (18) C(24)-C(19)-B(1) (17) C(19)-C(20)-C(21) 121.2(2) C(22)-C(21)-C(20) 120.8(3) C(21)-C(22)-C(23) 119.3(2) C(22)-C(23)-C(24) 119.8(3) C(19)-C(24)-C(23) 122.2(2) C(5)-N(1)-C(3) (15) C(5)-N(1)-B(1) (14) C(3)-N(1)-B(1) (14) C(5)-N(2)-C(12) (17) C(1)-O(1)-B(1) (14) C(9)-O(2)-C(25) 119.1(2) O(1)-B(1)-C(19) (15) O(1)-B(1)-C(13) (15) C(19)-B(1)-C(13) (15) O(1)-B(1)-N(1) (13) C(19)-B(1)-N(1) (14) C(13)-B(1)-N(1) (14) Symmetry transformations used to generate equivalent atoms: Table S28. Anisotropic displacement parameters (Å 2 x 10 3 ) for 14. The anisotropic

39 displacement factor exponent takes the form: -2 2 [ h 2 a* 2 U h k a* b* U 12 ] U 11 U 22 U 33 U 23 U 13 U 12 C(1) 38(1) 43(1) 43(1) 5(1) -1(1) -4(1) C(2) 44(1) 41(1) 57(1) 1(1) 5(1) -7(1) C(3) 37(1) 38(1) 49(1) -2(1) -1(1) -1(1) C(4) 46(1) 41(1) 61(1) -7(1) 3(1) -2(1) C(5) 45(1) 45(1) 56(1) 0(1) 7(1) -1(1) C(6) 42(1) 54(1) 42(1) 6(1) 2(1) -5(1) C(7) 63(1) 58(1) 51(1) -1(1) 14(1) -7(1) C(8) 77(2) 67(1) 59(1) -7(1) 24(1) -5(1) C(9) 66(1) 73(1) 51(1) 4(1) 17(1) -5(1) C(10) 61(1) 63(1) 72(1) 19(1) 12(1) -13(1) C(11) 58(1) 55(1) 58(1) 7(1) 10(1) -5(1) C(12) 42(1) 49(1) 54(1) -9(1) -3(1) 7(1) C(13) 43(1) 34(1) 52(1) 0(1) 1(1) -2(1) C(14) 46(1) 41(1) 62(1) -1(1) 2(1) -2(1) C(15) 44(1) 51(1) 94(2) 10(1) -6(1) 3(1) C(16) 64(1) 65(1) 79(2) 14(1) -22(1) 1(1) C(17) 76(2) 73(2) 56(1) 9(1) -9(1) 5(1) C(18) 56(1) 61(1) 54(1) 4(1) 1(1) 7(1) C(19) 41(1) 39(1) 53(1) -7(1) 8(1) -2(1) C(20) 69(1) 50(1) 79(2) 8(1) -2(1) -13(1) C(21) 85(2) 48(1) 116(2) 8(1) 6(2) -23(1) C(22) 62(1) 62(1) 106(2) -21(1) 5(1) -22(1) C(23) 59(1) 75(2) 82(2) -15(1) -9(1) -14(1) C(24) 54(1) 53(1) 64(1) -4(1) -4(1) -9(1) C(25) 75(2) 103(2) 69(2) 13(1) 26(1) -12(2) N(1) 37(1) 37(1) 45(1) 0(1) 1(1) -1(1) N(2) 46(1) 53(1) 59(1) -6(1) 10(1) 2(1) O(1) 46(1) 42(1) 46(1) -2(1) 7(1) -6(1) O(2) 97(1) 81(1) 90(1) 1(1) 49(1) -4(1) Cl(1) 64(1) 60(1) 77(1) -21(1) 12(1) 9(1) B(1) 38(1) 37(1) 45(1) 1(1) 4(1) -2(1) Table S29. Hydrogen coordinates ( x 10 4 ) and isotropic displacement parameters (Å 2 x 10 3 ) for 14.

40 x y z U(eq) H(2) H(4) H(5) H(7) H(8) H(10) H(11) H(14) H(15) H(16) H(17) H(18) H(20) H(21) H(22) H(23) H(24) H(25) H(25A) H(25B) Table S30. Torsion angles [ ] for 14. O(1)-C(1)-C(2)-C(3) 5.8(3) C(6)-C(1)-C(2)-C(3) (17) C(1)-C(2)-C(3)-N(1) -11.2(3) C(1)-C(2)-C(3)-C(4) (18) N(1)-C(3)-C(4)-C(12) -0.9(3) C(2)-C(3)-C(4)-C(12) (18) O(1)-C(1)-C(6)-C(11) (17) C(2)-C(1)-C(6)-C(11) 8.2(3) O(1)-C(1)-C(6)-C(7) 9.9(3) C(2)-C(1)-C(6)-C(7) (19) C(11)-C(6)-C(7)-C(8) -1.9(3)

41 C(1)-C(6)-C(7)-C(8) 177.2(2) C(6)-C(7)-C(8)-C(9) 1.5(4) C(7)-C(8)-C(9)-O(2) 179.8(2) C(7)-C(8)-C(9)-C(10) 0.2(4) O(2)-C(9)-C(10)-C(11) 179.0(2) C(8)-C(9)-C(10)-C(11) -1.5(4) C(7)-C(6)-C(11)-C(10) 0.7(3) C(1)-C(6)-C(11)-C(10) (19) C(9)-C(10)-C(11)-C(6) 1.0(4) C(3)-C(4)-C(12)-N(2) 2.3(3) C(3)-C(4)-C(12)-Cl(1) (14) C(18)-C(13)-C(14)-C(15) 1.0(3) B(1)-C(13)-C(14)-C(15) (17) C(13)-C(14)-C(15)-C(16) -0.2(3) C(14)-C(15)-C(16)-C(17) -0.9(4) C(15)-C(16)-C(17)-C(18) 1.2(4) C(16)-C(17)-C(18)-C(13) -0.3(4) C(14)-C(13)-C(18)-C(17) -0.7(3) B(1)-C(13)-C(18)-C(17) 179.5(2) C(24)-C(19)-C(20)-C(21) 1.2(4) B(1)-C(19)-C(20)-C(21) (2) C(19)-C(20)-C(21)-C(22) -1.0(5) C(20)-C(21)-C(22)-C(23) 0.2(5) C(21)-C(22)-C(23)-C(24) 0.5(4) C(20)-C(19)-C(24)-C(23) -0.5(3) B(1)-C(19)-C(24)-C(23) 179.4(2) C(22)-C(23)-C(24)-C(19) -0.3(4) N(2)-C(5)-N(1)-C(3) 2.7(3) N(2)-C(5)-N(1)-B(1) (18) C(4)-C(3)-N(1)-C(5) -1.4(3) C(2)-C(3)-N(1)-C(5) (17) C(4)-C(3)-N(1)-B(1) (16) C(2)-C(3)-N(1)-B(1) -10.8(2) N(1)-C(5)-N(2)-C(12) -1.4(3) C(4)-C(12)-N(2)-C(5) -1.2(3) Cl(1)-C(12)-N(2)-C(5) (14) C(2)-C(1)-O(1)-B(1) 24.0(2) C(6)-C(1)-O(1)-B(1) (15) C(8)-C(9)-O(2)-C(25) (2) C(10)-C(9)-O(2)-C(25) 5.1(4)

42 C(1)-O(1)-B(1)-C(19) (15) C(1)-O(1)-B(1)-C(13) 73.64(19) C(1)-O(1)-B(1)-N(1) -40.9(2) C(20)-C(19)-B(1)-O(1) (2) C(24)-C(19)-B(1)-O(1) 44.0(2) C(20)-C(19)-B(1)-C(13) -11.2(3) C(24)-C(19)-B(1)-C(13) (18) C(20)-C(19)-B(1)-N(1) 109.0(2) C(24)-C(19)-B(1)-N(1) -71.0(2) C(18)-C(13)-B(1)-O(1) (17) C(14)-C(13)-B(1)-O(1) 21.6(2) C(18)-C(13)-B(1)-C(19) 77.7(2) C(14)-C(13)-B(1)-C(19) (19) C(18)-C(13)-B(1)-N(1) -44.3(2) C(14)-C(13)-B(1)-N(1) (16) C(5)-N(1)-B(1)-O(1) (16) C(3)-N(1)-B(1)-O(1) 33.7(2) C(5)-N(1)-B(1)-C(19) -38.8(2) C(3)-N(1)-B(1)-C(19) (15) C(5)-N(1)-B(1)-C(13) 87.34(19) C(3)-N(1)-B(1)-C(13) (18) Symmetry transformations used to generate equivalent atoms: Table S31. Crystal data and structure refinement for 15. Identification code 15 Empirical formula C26 H23 B Cl N3 O Formula weight Temperature 293(2) K Wavelength Å Crystal system Monoclinic Space group P21/n Unit cell dimensions a = 8.885(8) Å = 90. b = (11) Å = (12). c = (19) Å = 90. Volume 2267(4) Å 3 Z 4 Density (calculated) Mg/m 3

43 Absorption coefficient mm -1 F(000) 920 Crystal size 0.20 x 0.20 x 0.20 mm 3 Theta range for data collection 2.62 to Index ranges -11<=h<=11, -15<=k<=15, -27<=l<=26 Reflections collected Independent reflections 5132 [R(int) = ] Completeness to theta = % Absorption correction Integration Max. and min. transmission and Refinement method Full-matrix least-squares on F 2 Data / restraints / parameters 5132 / 0 / 291 Goodness-of-fit on F Final R indices [I>2sigma(I)] R1 = , wr2 = R indices (all data) R1 = , wr2 = Largest diff. peak and hole and e.å -3 Table S32. Atomic coordinates ( x 10 4 ) and equivalent isotropic displacement parameters (Å 2 x 10 3 ) for 15. U(eq) is defined as one third of the trace of the orthogonalized U ij tensor. x y z U(eq) C(1) 9588(2) 11730(1) 10831(1) 47(1) C(2) 9054(2) 11114(2) 10307(1) 49(1) C(3) 8035(2) 10251(1) 10349(1) 45(1) C(4) 7238(2) 9742(2) 9809(1) 49(1) C(5) 6759(2) 9088(2) 10982(1) 57(1) C(6) 10534(2) 12694(1) 10790(1) 48(1) C(7) 11356(2) 13141(2) 11338(1) 55(1) C(8) 12299(2) 14018(2) 11307(1) 59(1) C(9) 12445(2) 14533(2) 10721(1) 54(1) C(10) 11618(3) 14086(2) 10168(1) 65(1) C(11) 10703(2) 13196(2) 10205(1) 60(1) C(12) 6267(2) 8924(2) 9914(1) 51(1) C(19) 8021(2) 10279(2) 12194(1) 52(1) C(24) 7219(3) 11162(2) 12372(1) 70(1) C(23) 6405(3) 11125(2) 12904(1) 88(1) C(22) 6354(3) 10192(2) 13253(1) 80(1)

44 C(21) 7130(3) 9304(2) 13091(1) 79(1) C(20) 7963(3) 9352(2) 12568(1) 69(1) C(13) 10444(2) 9608(2) 11619(1) 48(1) C(14) 11811(2) 10063(2) 11894(1) 60(1) C(15) 13155(2) 9472(2) 11974(1) 70(1) C(16) 13168(2) 8411(2) 11789(1) 71(1) C(17) 11844(2) 7935(2) 11514(1) 67(1) C(18) 10510(2) 8526(2) 11430(1) 54(1) C(25) 13416(3) 16003(2) 10084(1) 84(1) C(26) 14415(3) 15747(2) 11229(1) 85(1) N(1) 7795(2) 9875(1) 10947(1) 46(1) N(2) 5979(2) 8582(1) 10497(1) 58(1) N(3) 13343(2) 15433(2) 10685(1) 72(1) O(1) 9254(2) 11476(1) 11414(1) 53(1) Cl(1) 5276(1) 8267(1) 9266(1) 69(1) B(1) 8901(2) 10317(2) 11561(1) 49(1) Table S33. Bond lengths [Å] and angles [ ] for 15. C(1)-O(1) 1.328(2) C(1)-C(2) 1.368(3) C(1)-C(6) 1.461(3) C(2)-C(3) 1.404(3) C(2)-H(2) C(3)-N(1) 1.373(2) C(3)-C(4) 1.404(3) C(4)-C(12) 1.359(3) C(4)-H(4) C(5)-N(2) 1.312(3) C(5)-N(1) 1.344(2) C(5)-H(5) C(6)-C(7) 1.394(3) C(6)-C(11) 1.396(3) C(7)-C(8) 1.372(3) C(7)-H(7) C(8)-C(9) 1.399(3) C(8)-H(8) C(9)-N(3) 1.372(3)

45 C(9)-C(10) 1.404(3) C(10)-C(11) 1.370(3) C(10)-H(10) C(11)-H(11) C(12)-N(2) 1.344(3) C(12)-Cl(1) 1.724(2) C(19)-C(24) 1.375(3) C(19)-C(20) 1.387(3) C(19)-B(1) 1.619(3) C(24)-C(23) 1.400(3) C(24)-H(24) C(23)-C(22) 1.363(4) C(23)-H(23) C(22)-C(21) 1.356(4) C(22)-H(22) C(21)-C(20) 1.394(3) C(21)-H(21) C(20)-H(20) C(13)-C(18) 1.390(3) C(13)-C(14) 1.395(3) C(13)-B(1) 1.616(3) C(14)-C(15) 1.389(3) C(14)-H(14) C(15)-C(16) 1.360(4) C(15)-H(15) C(16)-C(17) 1.375(3) C(16)-H(16) C(17)-C(18) 1.383(3) C(17)-H(17) C(18)-H(18) C(25)-N(3) 1.447(3) C(25)-H(25) C(25)-H(25A) C(25)-H(25B) C(26)-N(3) 1.445(3) C(26)-H(26) C(26)-H(26A) C(26)-H(26B) N(1)-B(1) 1.613(3) O(1)-B(1) 1.498(3)

46 O(1)-C(1)-C(2) (17) O(1)-C(1)-C(6) (16) C(2)-C(1)-C(6) (16) C(1)-C(2)-C(3) (16) C(1)-C(2)-H(2) C(3)-C(2)-H(2) N(1)-C(3)-C(2) (16) N(1)-C(3)-C(4) (17) C(2)-C(3)-C(4) (16) C(12)-C(4)-C(3) (17) C(12)-C(4)-H(4) C(3)-C(4)-H(4) N(2)-C(5)-N(1) (18) N(2)-C(5)-H(5) N(1)-C(5)-H(5) C(7)-C(6)-C(11) (18) C(7)-C(6)-C(1) (17) C(11)-C(6)-C(1) (18) C(8)-C(7)-C(6) (18) C(8)-C(7)-H(7) C(6)-C(7)-H(7) C(7)-C(8)-C(9) (19) C(7)-C(8)-H(8) C(9)-C(8)-H(8) N(3)-C(9)-C(8) (19) N(3)-C(9)-C(10) (19) C(8)-C(9)-C(10) (19) C(11)-C(10)-C(9) (19) C(11)-C(10)-H(10) C(9)-C(10)-H(10) C(10)-C(11)-C(6) 122.1(2) C(10)-C(11)-H(11) C(6)-C(11)-H(11) N(2)-C(12)-C(4) (17) N(2)-C(12)-Cl(1) (15) C(4)-C(12)-Cl(1) (15) C(24)-C(19)-C(20) (19) C(24)-C(19)-B(1) (18) C(20)-C(19)-B(1) (18)

47 C(19)-C(24)-C(23) 121.8(2) C(19)-C(24)-H(24) C(23)-C(24)-H(24) C(22)-C(23)-C(24) 120.4(2) C(22)-C(23)-H(23) C(24)-C(23)-H(23) C(21)-C(22)-C(23) 119.5(2) C(21)-C(22)-H(22) C(23)-C(22)-H(22) C(22)-C(21)-C(20) 119.8(2) C(22)-C(21)-H(21) C(20)-C(21)-H(21) C(19)-C(20)-C(21) 122.5(2) C(19)-C(20)-H(20) C(21)-C(20)-H(20) C(18)-C(13)-C(14) (18) C(18)-C(13)-B(1) (17) C(14)-C(13)-B(1) (18) C(15)-C(14)-C(13) 122.2(2) C(15)-C(14)-H(14) C(13)-C(14)-H(14) C(16)-C(15)-C(14) 120.2(2) C(16)-C(15)-H(15) C(14)-C(15)-H(15) C(15)-C(16)-C(17) 119.3(2) C(15)-C(16)-H(16) C(17)-C(16)-H(16) C(16)-C(17)-C(18) 120.4(2) C(16)-C(17)-H(17) C(18)-C(17)-H(17) C(17)-C(18)-C(13) 122.1(2) C(17)-C(18)-H(18) C(13)-C(18)-H(18) N(3)-C(25)-H(25) N(3)-C(25)-H(25A) H(25)-C(25)-H(25A) N(3)-C(25)-H(25B) H(25)-C(25)-H(25B) H(25A)-C(25)-H(25B) N(3)-C(26)-H(26) 109.5

48 N(3)-C(26)-H(26A) H(26)-C(26)-H(26A) N(3)-C(26)-H(26B) H(26)-C(26)-H(26B) H(26A)-C(26)-H(26B) C(5)-N(1)-C(3) (16) C(5)-N(1)-B(1) (15) C(3)-N(1)-B(1) (15) C(5)-N(2)-C(12) (17) C(9)-N(3)-C(26) 120.3(2) C(9)-N(3)-C(25) 121.7(2) C(26)-N(3)-C(25) 117.4(2) C(1)-O(1)-B(1) (14) O(1)-B(1)-N(1) (15) O(1)-B(1)-C(13) (16) N(1)-B(1)-C(13) (15) O(1)-B(1)-C(19) (14) N(1)-B(1)-C(19) (16) C(13)-B(1)-C(19) (16) Symmetry transformations used to generate equivalent atoms: Table S34. Anisotropic displacement parameters (Å 2 x 10 3 ) for 15. The anisotropic displacement factor exponent takes the form: -2 2 [ h 2 a* 2 U h k a* b* U 12 ] U 11 U 22 U 33 U 23 U 13 U 12 C(1) 51(1) 46(1) 44(1) 2(1) 15(1) 6(1) C(2) 55(1) 52(1) 43(1) 2(1) 16(1) -1(1) C(3) 45(1) 48(1) 44(1) 1(1) 14(1) 6(1) C(4) 51(1) 54(1) 44(1) -1(1) 12(1) 2(1) C(5) 58(1) 61(1) 54(1) 5(1) 18(1) -4(1) C(6) 52(1) 43(1) 50(1) 2(1) 15(1) 4(1) C(7) 69(1) 53(1) 46(1) -1(1) 18(1) -2(1) C(8) 64(1) 58(1) 54(1) -9(1) 12(1) -3(1) C(9) 53(1) 48(1) 63(1) 0(1) 12(1) 2(1) C(10) 78(1) 60(1) 56(1) 14(1) 7(1) -12(1) C(11) 70(1) 58(1) 50(1) 6(1) 4(1) -9(1) C(12) 43(1) 54(1) 56(1) -6(1) 7(1) 6(1)

49 C(19) 56(1) 58(1) 45(1) -6(1) 17(1) -9(1) C(24) 82(2) 66(1) 69(1) -12(1) 34(1) -5(1) C(23) 90(2) 89(2) 93(2) -34(2) 47(2) -9(1) C(22) 76(2) 115(2) 53(1) -25(1) 31(1) -34(1) C(21) 91(2) 97(2) 54(1) 4(1) 29(1) -20(1) C(20) 84(2) 71(1) 57(1) 5(1) 29(1) -4(1) C(13) 54(1) 55(1) 35(1) 5(1) 14(1) -3(1) C(14) 67(1) 64(1) 48(1) -1(1) 6(1) -8(1) C(15) 56(1) 94(2) 59(1) 3(1) 1(1) -11(1) C(16) 57(1) 82(2) 73(2) 9(1) 10(1) 8(1) C(17) 66(1) 62(1) 76(1) 2(1) 17(1) 6(1) C(18) 54(1) 55(1) 54(1) 2(1) 12(1) -4(1) C(25) 79(2) 70(2) 105(2) 24(1) 19(1) -12(1) C(26) 67(1) 74(2) 113(2) -11(1) 1(1) -12(1) N(1) 48(1) 49(1) 45(1) 0(1) 14(1) 0(1) N(2) 55(1) 65(1) 56(1) 0(1) 12(1) -9(1) N(3) 70(1) 61(1) 83(1) 5(1) 11(1) -17(1) O(1) 69(1) 48(1) 44(1) -2(1) 21(1) -4(1) Cl(1) 65(1) 76(1) 64(1) -13(1) 3(1) -9(1) B(1) 60(1) 48(1) 41(1) 1(1) 16(1) -4(1) Table S35. Hydrogen coordinates ( x 10 4 ) and isotropic displacement parameters (Å 2 x 10 3 ) for 15. x y z U(eq) H(2) H(4) H(5) H(7) H(8) H(10) H(11) H(24) H(23) H(22) H(21)

50 H(20) H(14) H(15) H(16) H(17) H(18) H(25) H(25A) H(25B) H(26) H(26A) H(26B) Table S36. Torsion angles [ ] for 15. O(1)-C(1)-C(2)-C(3) 5.5(3) C(6)-C(1)-C(2)-C(3) (16) C(1)-C(2)-C(3)-N(1) -13.0(3) C(1)-C(2)-C(3)-C(4) (17) N(1)-C(3)-C(4)-C(12) 1.0(2) C(2)-C(3)-C(4)-C(12) (16) O(1)-C(1)-C(6)-C(7) 16.4(2) C(2)-C(1)-C(6)-C(7) (18) O(1)-C(1)-C(6)-C(11) (17) C(2)-C(1)-C(6)-C(11) 13.9(3) C(11)-C(6)-C(7)-C(8) -0.9(3) C(1)-C(6)-C(7)-C(8) (17) C(6)-C(7)-C(8)-C(9) 2.1(3) C(7)-C(8)-C(9)-N(3) (18) C(7)-C(8)-C(9)-C(10) -2.0(3) N(3)-C(9)-C(10)-C(11) (2) C(8)-C(9)-C(10)-C(11) 0.7(3) C(9)-C(10)-C(11)-C(6) 0.5(3) C(7)-C(6)-C(11)-C(10) -0.4(3) C(1)-C(6)-C(11)-C(10) (19) C(3)-C(4)-C(12)-N(2) 1.8(3) C(3)-C(4)-C(12)-Cl(1) (13) C(20)-C(19)-C(24)-C(23) 0.5(3)