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1 Supporting information Sensitizing Tb(III) and Eu(III) Emission with Triarylboron Functionalized 1,3-diketonato Ligands Larissa F. Smith, Barry A. Blight, Hee-Jun Park, and Suning Wang* Department of Chemistry, Queen's University, Kingston, Ontario, K7M 3N6, Canada S1

2 NMR spectra of 1-BF 2 BACACBF2proton.001.esp e 2.00 h i c f d b f 2.34 g a g Chemical Shift (ppm) Figure S1. 1 H NMR spectrum of 1-BF 2 in CDCl 3. BACACBF2CARBON.004.ESP a b c d e f Chemical Shift (ppm) Figure S2. 13 C NMR spectrum NMR spectrum of 1-BF 2 in CDCl 3. S2

3 BACACBF2FLUORINE.002.ESP Chemical Shift (ppm) Figure S3. 19 F NMR spectrum of NMR spectrum of 1-BF 2 in CDCl 3. BACACBF2BORON.003.ESP Chemical Shift (ppm) Figure S4. 11 B NMR spectrum of 1-BF 2 in CDCl 3. S3

4 NMR spectra of 2-BF 2 BACBACBF2proton.001.esp 1.99 f d j 6.86 fd c a a k j k 2.32 g h Figure S5. 1 H 11 NMR spectrum of 2-BF 2. BACBACBF2CARBON.005.ESP i Chemical Shift (ppm) Chemical Shift (ppm) S5a. 13 C NMR spectrum of 2-BF 2 in CDCl 3. Figure S4

5 BACBACBF2FLUORINE.002.ESP Chemical Shift (ppm) S6. 19 F NMR spectrum of 2-BF 2 in CDCl 3. BACBACBF2FLUORINE.002.ESP Figure Chemical Shift (ppm) S7. 11 B NMR spectrum of 2-BF 2 in CDCl 3. Figure S5

6 LS BARRY EU BACAC R.ESP Chemical Shift (ppm) Figure S8. 1 H NMR spectrum of 1Eu in CDCl Chemical Shift (ppm) Figure S9. 1 H NMR spectrum of 2Eu in CDCl 3. S6

7 Fluoride titration data of 1-BF A Wavelength/nm Figure S10. The absorption spectral change of 1-BF 2 with the addition of TBAF in CH 2 Cl 2. 0 A at 386 nm experimental data fit [F - ] (M) Figure S11. The Stern-Volmer plot at 386 nm and the fit (K = ~7.5 x 10 6 M -1 ) for 1-BF 2 titration by TBAF. S7

8 Figure S12. Fluorescence spectral change of 1-BF 2 with the addition of TBAF in CH 2 Cl 2. S8

9 Fluoride titration data of 2-BF 2 Figure S13. The absorption spectral change of 2-BF 2 with the addition of TBAF in CH 2 Cl 2. Change in [F - ] (M) Figure S14. The Stern-Volmer plot at 432 nm for 2-BF 2 titration by TBAF (K 1 = ~4.5 x 10 5 M -1 ). S9

10 Figure S15. Fluorescence spectral change of 2-BF 2 with the addition of TBAF in CH 2 Cl 2. Figure S16. The fluorescence spectral change 1-BF 2 with concentration in CH 2 Cl 2 (λ ex = 405 nm). S10

11 Figure S17. The fluorescence spectral change 2-BF 2 with concentration in CH 2 Cl 2 (λ ex = 394 nm). Figure S18. The phosphorescent spectra of 1Gd (λ ex =357 nm) and its fluoride adduct in CH 2 Cl 2 at 77K. S11

12 Figure S19. The phosphorescent spectra of 2Gd and its fluoride adduct (λ ex = 397nm) in CH 2 Cl 2 at 77K. Figure S20. The phosphorescent spectra of 3Gd and its fluoride adduct (λ ex = 306 nm), in CH 2 Cl 2 at 77K. S12

13 Figure S21. The phosphorescent spectra of 4Gd and its fluoride adduct (λ ex =310 nm ) in CH 2 Cl 2 at 77K. Figure S22. The phosphorescent spectrum of 1Eu in Me-THF at 77K (λ ex = 380 nm). S13

14 Figure S23. The phosphorescent decay curve of the 612 nm peak of u1eu in Me-THF at 77K and its fitting curve. The decay lifetime was found to be 534 μs (λ ex = 380 nm). Figure S24. The emission spectrum of 2Eu in Me-THF (λ ex = 395 nm) at 77K. S14

15 Figure S25. The phosphorescence decay diagram of 2Eu in Me-THF (λ ex =395 nm) and the fitting curve at 77K. The lifetime was found to be 452 μs. Figure S26. The normalized absorption spectrum of 3Tb in THF, the emission spectrum in THF (λ ex = 323 nm) and and in 20 wt% PMMA film ((λ ex = 323 nm). S15

16 Figure S27. The emission spectrum of 3Tb in Me-THF at 77K (λ ex = 323nm). Figure S28. The phosphorescent decay diagram of the 547nm peak (λ ex =323nm) of 3Tb in Me-THF at 77K and its fitting curve. The decay lifetime was calculated to be 920 μs. S16

17 Figure S29. The emission spectrum of 4Tb in Me-THF at 77K (λ ex =330 nm). Figure S30. The phosphorescent decay diagram of the 547 nm peak of 4Tb in Me-THF at 77K and its fitting curve. The decay lifetime was found to be 688μs (λ ex = 330nm). S17

18 Figure S31. Comparison of the emission spectra of 4Tb (boron) and the duryl-acac-tb(iii) compound that does not have the BMes 2 group on the ligand (no boron) in THF, (1x10-5 M, 298K, λ ex = 330 nm). Figure S32. The normalized absorption (λ max = 319 nm) and emission (λ ex = 336 nm, λ max = 391 nm) spectra of a 1x10-5 M solution of 3Eu at 298K in THF showing that L3 is not effective in sensitizing Eu(III) emission. S18

19 Table S1. TD-DFT Computational Data Compound Transition Major Orbital contributions Wavelength Oscillator strength 1(BF 2 ) S 1 HOMO->LUMO (84%) S 2 HOMO-1->LUMO (81%) HOMO-1 -> LUMO+1 (19%) S 3 HOMO-2 -> LUMO (80%) HOMO-2 -> LUMO+1 (20%) S 4 HOMO-3 -> LUMO (86%) HOMO-3 -> LUMO+1 (13%) S 5 HOMO-4 -> LUMO (100%) S 6 HOMO-5 -> LUMO (19%) HOMO-> LUMO+1(67%) S 7 HOMO-5 -> LUMO (78%) HOMO-> LUMO+1 (22%) S 8 HOMO-2->LUMO+1 (15%) HOMO-1-> LUMO+1(72%) S 9 HOMO-7->LUMO (82%) S 10 HOMO-3->LUMO+1 (13%) HOMO-2->LUMO+1 (64%) S 11 HOMO-3->LUMO (11%) HOMO-3->LUMO+1 (67%) HOMO-3->LUMO+2 (10%) HOMO-2->LUMO+1 (12%) S 12 HOMO-7->LUMO (69%) HOMO-6->LUMO (14%) HOMO-4->LUMO+1 (17%) S 13 HOMO-8->LUMO (86%) S 14 HOMO-4->LUMO+1 (72%) S 15 HOMO-11->LUMO (59%) HOMO-10->LUMO (19%) T 1 HOMO-4 -> LUMO (59%) HOMO-2 -> LUMO (16%) HOMO-1 -> LUMO (16%) T 2 HOMO-> LUMO (72%) HOMO-> LUMO+1 (28%) 2(BF 2 ) S 1 HOMO->LUMO (83%) S 2 HOMO-1->LUMO (83%) S 3 HOMO-2->LUMO (73%) S 4 HOMO-3->LUMO (85%) S 5 HOMO-4->LUMO (74%) S 6 HOMO-5->LUMO (86%) S 7 HOMO-7->LUMO (85%) S 8 HOMO-7-> LUMO (76%) S19

20 S 9 HOMO-8->LUMO (100%) S 10 HOMO-1->LUMO+1 (65%) HOMO->LUMO+2 (20%) S 11 HOMO-1->LUMO+2 (20%) HOMO->LUMO+1 (65%) S 12 HOMO-10->LUMO (78%) HOMO-3->LUMO+1 (22%) S 13 HOMO-9->LUMO (63%) HOMO-2->LUMO+1 (24%) S 14 HOMO-9->LUMO (22%) HOMO-2->LUMO+1 (53%) S 15 HOMO-10->LUMO (17%) HOMO-2->LUMO+1 (57%) T 1 HOMO-8->LUMO (53%) HOMO-2->LUMO (22%) T 2 HOMO-1-> LUMO (62%) HOMO->LUMO+1 (24%) 3(BF 2 ) S 1 HOMO -> LUMO (24%) HOMO -> LUMO+1 (76%) S 2 HOMO-1 -> LUMO (31%) HOMO-1 -> LUMO+1 (69%) S 3 HOMO-> LUMO (76%) HOMO-> LUMO+1 (24%) S 4 HOMO-2->LUMO (34%) HOMO-2->LUMO+1 (66%) S 5 HOMO-1->LUMO (52%) HOMO-1->LUMO+1 (23%) S 6 HOMO-3 -> LUMO (31%) HOMO-3 -> LUMO+1 (69%) S 7 HOMO-2->LUMO (56%) HOMO-2->LUMO+1 (27%) S 8 HOMO-3->LUMO (70%) HOMO-3->LUMO+1 (30%) S 9 HOMO-5->LUMO (36%) HOMO-4->LUMO (45%) S 10 HOMO-6->LUMO (100%) S 11 HOMO-5->LUMO (19%) HOMO-5->LUMO+1 (33%) HOMO-4->LUMO+1 (32%) S 12 HOMO-6->LUMO+1 (70%) HOMO-4->LUMO+2 (16%) S 13 HOMO-5->LUMO (18%) HOMO-5-> LUMO+1 (24%) HOMO-4->LUMO+1 (40%) S 14 HOMO-5->LUMO (35%) HOMO-5->LUMO+1 (34%) S20

21 S 15 HOMO-3->LUMO+4 (15%) HOMO-1->LUMO+3 (19%) HOMO->LUMO+2 (66%) T 1 HOMO-5->LUMO (53%) HOMO-4->LUMO (47%) T 2 HOMO-1->LUMO+1 (13%) HOMO-1->LUMO+4 (11%) HOMO->LUMO+1 (42%) HOMO->LUMO+3 (11%) 4(BF 2 ) S 1 HOMO-1-> LUMO (69%) HOMO->LUMO (31%) S 2 HOMO-5->LUMO (46%) HOMO-2->LUMO (54%) S 3 HOMO-1->LUMO+1 (17%) HOMO->LUMO (15%) HOMO->LUMO+1 (67%) S 4 HOMO-1->LUMO (26%) HOMO->LUMO (59%) HOMO->LUMO+1 (16%) S 5 HOMO-5->LUMO+1 (18%) HOMO-2->LUMO+1 (82%) S 6 HOMO-1->LUMO+1 (81%) HOMO->LUMO+1 (19%) S 7 HOMO-3->LUMO (29%) HOMO-3->LUMO+1 (71%) S 8 HOMO-5->LUMO (42%) HOMO-2->LUMO (37%) S 9 HOMO-3->LUMO (64%) HOMO-3->LUMO+1 (25%) S 10 HOMO-5->LUMO+1 (12%) HOMO-4->LUMO (21%) HOMO-4->LUMO+1 (57%) S 11 HOMO-4->LUMO (74%) HOMO-4->LUMO+1 (26%) S 12 HOMO-5->LUMO+1 (68%) HOMO-4->LUMO+1 (15%) HOMO-2->LUMO+1 (16%) S 13 HOMO-6->LUMO (100%) S 14 HOMO-6-> LUMO+1 (100%) S 15 HOMO-9->LUMO (21%) HOMO-7-> LUMO (15%) HOMO-1->LUMO+2 (20%) HOMO-> LUMO+2 (11%) T 1 HOMO-6->LUMO (100%) T 2 HOMO-2-> LUMO+3 (12%) HOMO-1-> LUMO+1 (13%) HOMO->LUMO+1 (50%) S21

22 Table S2. TD-DFT data with the solvent (CH 2 Cl 2 ) parameters included. 1-BF 2 T 1 HOMO 8 > LUMO (10%) HOMO 4 > LUMO (57%) HOMO 3 > L UMO (14%) HOMO 1 > LUMO (18%) T 2 HOMO > LUMO (75%) HOMO > LUMO +1 (25%) S 1 HOMO > LUMO (86%) HOMO > LUMO +1 (14%) S 2 HOMO 1 > LUMO (87%) HOMO 1 > LUMO +1 (13%) 3 BF nm nm nm nm T 1 HOMO 6 > LUMO (100%) nm T 2 HOMO 3 >LUMO+6 (9%) nm HOMO 2 >LUMO +5 (10%) HOMO 1 > LUMO+4 (15%) HOMO > LUMO+1 (52%) HOMO > LUMO+3 (13%) S 1 HOMO > LUMO (58%) nm HOMO > LUMO +1 (42%) S 2 HOMO 1 > LUMO (42%) nm HOMO 1 > LUMO +1 (58%) 4 BF 2 T 1 HOMO 6 > LUMO (100%) nm T 2 HOMO 5 >LUMO +3(10%) nm HOMO 3 >LUMO +6 (9%) HOMO 2 > LUMO+3 (11%) HOMO 1 > LUMO+1 (32%) HOMO > LUMO+1 (37%) S 1 HOMO 1 > LUMO (46%) nm HOMO > LUMO (54%) S 2 HOMO 5 > LUMO (41%) HOMO 2 > LUMO +1 (59%) nm S22

23 Figure S33. MO diagrams for the major Contributing Orbitals 1(BF 2 ) HOMO-11 HOMO-10 HOMO-9 HOMO-8 HOMO-7 HOMO-6 HOMO-5 HOMO-4 HOMO-3 HOMO-2 HOMO-1 HOMO S23

24 2(BF 2 ) LUMO LUMO+1 LUMO+2 HOMO-12 HOMO-11 HOMO-10 HOMO-9 HOMO-8 HOMO-7 HOMO-6 HOMO-5 HOMO-4 HOMO-3 HOMO-2 HOMO-1 HOMO LUMO LUMO+1 S24

25 3(BF 2 ) LUMO+2 HOMO-9 HOMO-7 HOMO-6 HOMO-5 HOMO-4 HOMO-3 HOMO-2 HOMO-1 HOMO LUMO LUMO+1 LUMO+2 S25

26 4(BF 2 ) LUMO+3 LUMO+4 HOMO-9 HOMO-7 HOMO-6 HOMO-5 HOMO-3 HOMO-2 HOMO-1 HOMO LUMO LUMO+1 LUMO+2 LUMO+3 S26

27 LUMO+4 LUMO+6 LUMO+7 S27

28 Table S3. Crystal structural data of 1-BF2 Table S3a. Crystal data and structure refinement for 1-BF2. Identification code 1-BF2 Empirical formula C33.50 H33 B2 Cl F2 O2 Formula weight Temperature 180(2) K Wavelength Å Crystal system Triclinic Space group P-1 Unit cell dimensions a = (9) Å = (10). b = (13) Å = (10). c = (19) Å = (10). Volume (5) Å 3 Z 4 Density (calculated) Mg/m 3 Absorption coefficient mm -1 F(000) 1180 Crystal size 0.02 x 0.02 x 0.01 mm 3 Theta range for data collection 1.45 to Index ranges -12<=h<=12, -17<=k<=19, -27<=l<=26 Reflections collected Independent reflections [R(int) = ] Completeness to theta = % Absorption correction Semi-empirical from equivalents Max. and min. transmission and Refinement method Full-matrix least-squares on F 2 Data / restraints / parameters / 0 / 742 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 S28

29 Table S3b. Atomic coordinates ( x 10 4 ) and equivalent isotropic displacement parameters (Å 2 x 10 3 ) for 1-BF2. U(eq) is defined as one third of the trace of the orthogonalized U ij tensor. x y z U(eq) B(1) 7337(3) 10908(2) 4459(2) 40(1) B(2) 4050(4) 5561(3) 2385(2) 42(1) B(3) 7124(4) 11333(3) -280(2) 55(1) B(4) 10356(4) 9106(2) 2257(2) 38(1) F(1) 8067(2) 10953(1) 5027(1) 54(1) F(2) 8166(2) 11299(1) 4063(1) 54(1) F(3) 6747(2) 10695(2) -899(1) 70(1) F(4) 8069(2) 12083(2) -305(1) 84(1) O(1) 6218(2) 11442(1) 4620(1) 47(1) O(2) 6756(2) 9898(1) 4109(1) 51(1) O(3) 5847(2) 11647(2) -35(1) 59(1) O(4) 7686(2) 10829(2) 141(1) 59(1) C(1) 4904(3) 11048(2) 4519(1) 31(1) C(2) 4488(3) 10086(2) 4229(1) 34(1) C(3) 5439(3) 9523(2) 4017(1) 32(1) C(4) 5075(3) 8511(2) 3654(1) 33(1) C(5) 3741(3) 7972(2) 3601(1) 37(1) C(6) 3438(3) 7029(2) 3220(1) 38(1) C(7) 4432(3) 6596(2) 2870(1) 38(1) C(8) 5776(3) 7148(2) 2952(2) 44(1) C(9) 6099(3) 8078(2) 3339(2) 42(1) C(10) 3967(3) 11705(2) 4710(1) 32(1) C(11) 2552(3) 11386(2) 4700(1) 42(1) C(12) 1684(3) 12024(2) 4849(2) 51(1) C(13) 2219(3) 12981(3) 5020(2) 56(1) C(14) 3619(4) 13309(2) 5047(2) 67(1) C(15) 4500(3) 12674(2) 4900(2) 53(1) C(16) 2691(3) 4881(2) 2476(1) 39(1) C(17) 1571(3) 4584(2) 1981(2) 45(1) C(18) 356(3) 4003(2) 2067(2) 54(1) C(19) 208(3) 3674(2) 2607(2) 54(1) S29

30 C(20) 1296(4) 3954(2) 3091(2) 53(1) C(21) 2531(3) 4567(2) 3038(2) 45(1) C(22) 3676(4) 4847(3) 3594(2) 61(1) C(23) -1135(4) 3035(3) 2670(2) 76(1) C(24) 1639(4) 4918(3) 1375(2) 63(1) C(25) 5002(3) 5248(2) 1817(1) 41(1) C(26) 5540(3) 4411(2) 1735(2) 44(1) C(27) 6379(3) 4152(2) 1238(2) 51(1) C(28) 6681(3) 4657(3) 791(2) 54(1) C(29) 6121(3) 5451(2) 857(2) 53(1) C(30) 5331(3) 5766(2) 1364(2) 45(1) C(31) 4812(4) 6665(2) 1382(2) 60(1) C(32) 7615(4) 4362(3) 255(2) 79(1) C(33) 5270(3) 3800(2) 2198(2) 55(1) C(34) 5243(3) 11411(2) 447(1) 41(1) C(35) 5840(3) 10889(2) 783(2) 46(1) C(36) 7063(3) 10618(2) 623(1) 41(1) C(37) 7809(3) 10126(2) 987(1) 39(1) C(38) 7189(3) 9682(2) 1431(1) 45(1) C(39) 7968(3) 9289(2) 1794(2) 45(1) C(40) 9395(3) 9370(2) 1755(1) 38(1) C(41) 9984(3) 9785(2) 1291(1) 40(1) C(42) 9198(3) 10134(2) 898(1) 42(1) C(43) 3954(3) 11736(2) 588(1) 40(1) C(44) 3287(3) 11644(2) 1139(2) 44(1) C(45) 2074(3) 11956(2) 1258(2) 54(1) C(46) 1486(4) 12341(2) 824(2) 57(1) C(47) 2131(4) 12431(3) 277(2) 65(1) C(48) 3367(4) 12149(2) 161(2) 55(1) C(49) 11793(3) 9815(2) 2500(1) 36(1) C(50) 13043(3) 9482(2) 2415(1) 39(1) C(51) 14300(3) 10129(3) 2586(2) 49(1) C(52) 14393(4) 11099(3) 2838(2) 54(1) C(53) 13166(4) 11411(2) 2934(1) 51(1) C(54) 11878(3) 10797(2) 2769(1) 41(1) C(55) 10605(3) 11218(2) 2915(2) 55(1) S30

31 C(56) 15775(4) 11782(3) 3002(2) 84(1) C(57) 13060(3) 8453(2) 2120(2) 51(1) C(58) 9872(3) 8200(2) 2489(1) 35(1) C(59) 9472(3) 7287(2) 2036(1) 40(1) C(60) 9105(3) 6493(2) 2255(1) 40(1) C(61) 9094(3) 6560(2) 2918(2) 40(1) C(62) 9471(3) 7453(2) 3362(1) 37(1) C(63) 9856(3) 8268(2) 3166(1) 35(1) C(64) 10167(3) 9223(2) 3682(1) 44(1) C(65) 8635(4) 5686(2) 3145(2) 57(1) C(66) 9482(4) 7143(2) 1303(1) 64(1) C(67) 8517(4) 3672(3) 4519(2) 84(1) Cl(1) 7325(2) 4302(1) 4323(1) 106(1) Cl(2) 8780(1) 3838(1) 5362(1) 121(1) Table S3c. Bond lengths [Å] and angles [ ] for 1-BF2. B(1)-F(1) 1.362(4) B(1)-F(2) 1.366(4) B(1)-O(1) 1.479(4) B(1)-O(2) 1.479(4) B(2)-C(7) 1.573(4) B(2)-C(16) 1.576(5) B(2)-C(25) 1.583(5) B(3)-F(4) 1.331(5) B(3)-F(3) 1.387(5) B(3)-O(4) 1.472(4) B(3)-O(3) 1.489(4) B(4)-C(58) 1.564(4) B(4)-C(49) 1.575(4) B(4)-C(40) 1.579(4) O(1)-C(1) 1.303(3) O(2)-C(3) 1.299(3) O(3)-C(34) 1.302(3) O(4)-C(36) 1.295(3) C(1)-C(2) 1.375(4) C(1)-C(10) 1.463(4) C(2)-C(3) 1.383(4) C(3)-C(4) 1.466(4) C(4)-C(5) 1.390(4) C(4)-C(9) 1.396(4) C(5)-C(6) 1.389(4) C(6)-C(7) 1.402(4) C(7)-C(8) 1.401(4) C(8)-C(9) 1.377(4) C(10)-C(15) 1.384(4) C(10)-C(11) 1.385(4) C(11)-C(12) 1.382(4) C(12)-C(13) 1.368(4) C(13)-C(14) 1.370(5) C(14)-C(15) 1.386(4) S31

32 C(16)-C(21) 1.401(4) C(16)-C(17) 1.415(4) C(17)-C(18) 1.392(4) C(17)-C(24) 1.504(4) C(18)-C(19) 1.371(5) C(19)-C(20) 1.378(5) C(19)-C(23) 1.514(5) C(20)-C(21) 1.408(4) C(21)-C(22) 1.517(4) C(25)-C(30) 1.403(4) C(25)-C(26) 1.420(4) C(26)-C(27) 1.384(4) C(26)-C(33) 1.515(4) C(27)-C(28) 1.376(5) C(28)-C(29) 1.378(5) C(28)-C(32) 1.516(4) C(29)-C(30) 1.384(4) C(30)-C(31) 1.518(4) C(34)-C(35) 1.384(4) C(34)-C(43) 1.458(4) C(35)-C(36) 1.370(4) C(36)-C(37) 1.469(4) C(37)-C(42) 1.389(4) C(37)-C(38) 1.393(4) C(38)-C(39) 1.381(4) C(39)-C(40) 1.398(4) C(40)-C(41) 1.392(4) C(41)-C(42) 1.384(4) C(43)-C(44) 1.393(4) C(43)-C(48) 1.395(4) C(44)-C(45) 1.373(4) C(45)-C(46) 1.378(4) C(46)-C(47) 1.372(5) C(47)-C(48) 1.374(4) C(49)-C(54) 1.408(4) C(49)-C(50) 1.415(4) C(50)-C(51) 1.389(4) C(50)-C(57) 1.497(4) C(51)-C(52) 1.385(5) C(52)-C(53) 1.381(5) C(52)-C(56) 1.507(5) C(53)-C(54) 1.389(4) C(54)-C(55) 1.514(4) C(58)-C(59) 1.412(4) C(58)-C(63) 1.415(4) C(59)-C(60) 1.382(4) C(59)-C(66) 1.513(4) C(60)-C(61) 1.387(4) C(61)-C(62) 1.381(4) C(61)-C(65) 1.512(4) C(62)-C(63) 1.385(4) C(63)-C(64) 1.513(4) C(67)-Cl(2) 1.743(4) C(67)-Cl(1) 1.744(4) F(1)-B(1)-F(2) 111.1(3) F(1)-B(1)-O(1) 108.9(3) F(2)-B(1)-O(1) 108.5(3) F(1)-B(1)-O(2) 108.7(3) F(2)-B(1)-O(2) 108.8(3) O(1)-B(1)-O(2) 110.7(2) C(7)-B(2)-C(16) 118.0(3) C(7)-B(2)-C(25) 119.6(3) C(16)-B(2)-C(25) 122.4(3) F(4)-B(3)-F(3) 111.1(3) F(4)-B(3)-O(4) 110.1(3) F(3)-B(3)-O(4) 107.6(3) F(4)-B(3)-O(3) 109.7(3) F(3)-B(3)-O(3) 107.0(3) O(4)-B(3)-O(3) 111.2(3) C(58)-B(4)-C(49) 123.7(3) C(58)-B(4)-C(40) 120.9(3) S32

33 C(49)-B(4)-C(40) 115.4(2) C(1)-O(1)-B(1) 123.7(2) C(3)-O(2)-B(1) 123.8(2) C(34)-O(3)-B(3) 123.4(2) C(36)-O(4)-B(3) 123.3(3) O(1)-C(1)-C(2) 120.1(2) O(1)-C(1)-C(10) 115.1(2) C(2)-C(1)-C(10) 124.8(2) C(1)-C(2)-C(3) 121.2(3) O(2)-C(3)-C(2) 120.0(3) O(2)-C(3)-C(4) 115.4(2) C(2)-C(3)-C(4) 124.5(3) C(5)-C(4)-C(9) 118.9(3) C(5)-C(4)-C(3) 122.4(2) C(9)-C(4)-C(3) 118.7(3) C(6)-C(5)-C(4) 119.9(3) C(5)-C(6)-C(7) 122.1(3) C(8)-C(7)-C(6) 116.5(3) C(8)-C(7)-B(2) 121.5(3) C(6)-C(7)-B(2) 122.0(3) C(9)-C(8)-C(7) 121.9(3) C(8)-C(9)-C(4) 120.5(3) C(15)-C(10)-C(11) 118.8(3) C(15)-C(10)-C(1) 119.3(3) C(11)-C(10)-C(1) 121.9(3) C(12)-C(11)-C(10) 120.5(3) C(13)-C(12)-C(11) 120.2(3) C(12)-C(13)-C(14) 120.0(3) C(13)-C(14)-C(15) 120.3(3) C(10)-C(15)-C(14) 120.2(3) C(21)-C(16)-C(17) 118.1(3) C(21)-C(16)-B(2) 122.6(3) C(17)-C(16)-B(2) 119.3(3) C(18)-C(17)-C(16) 119.5(3) C(18)-C(17)-C(24) 119.0(3) C(16)-C(17)-C(24) 121.5(3) C(19)-C(18)-C(17) 122.6(3) C(18)-C(19)-C(20) 118.4(3) C(18)-C(19)-C(23) 120.1(3) C(20)-C(19)-C(23) 121.5(3) C(19)-C(20)-C(21) 121.2(3) C(16)-C(21)-C(20) 120.2(3) C(16)-C(21)-C(22) 121.8(3) C(20)-C(21)-C(22) 118.0(3) C(30)-C(25)-C(26) 117.0(3) C(30)-C(25)-B(2) 122.0(3) C(26)-C(25)-B(2) 121.0(3) C(27)-C(26)-C(25) 120.2(3) C(27)-C(26)-C(33) 118.0(3) C(25)-C(26)-C(33) 121.7(3) C(28)-C(27)-C(26) 122.5(3) C(27)-C(28)-C(29) 117.3(3) C(27)-C(28)-C(32) 121.4(3) C(29)-C(28)-C(32) 121.3(3) C(28)-C(29)-C(30) 122.4(3) C(29)-C(30)-C(25) 120.6(3) C(29)-C(30)-C(31) 116.5(3) C(25)-C(30)-C(31) 122.9(3) O(3)-C(34)-C(35) 119.6(3) O(3)-C(34)-C(43) 115.3(3) C(35)-C(34)-C(43) 125.1(3) C(36)-C(35)-C(34) 121.5(3) O(4)-C(36)-C(35) 120.7(3) O(4)-C(36)-C(37) 114.7(3) C(35)-C(36)-C(37) 124.5(3) C(42)-C(37)-C(38) 119.1(3) C(42)-C(37)-C(36) 118.3(3) C(38)-C(37)-C(36) 122.5(3) C(39)-C(38)-C(37) 119.9(3) C(38)-C(39)-C(40) 121.6(3) C(41)-C(40)-C(39) 117.5(3) C(41)-C(40)-B(4) 119.8(3) S33

34 C(39)-C(40)-B(4) 122.5(2) C(42)-C(41)-C(40) 121.4(3) C(41)-C(42)-C(37) 120.2(3) C(44)-C(43)-C(48) 118.8(3) C(44)-C(43)-C(34) 121.7(3) C(48)-C(43)-C(34) 119.5(3) C(45)-C(44)-C(43) 120.4(3) C(44)-C(45)-C(46) 120.2(3) C(47)-C(46)-C(45) 119.9(3) C(46)-C(47)-C(48) 120.6(3) C(47)-C(48)-C(43) 120.0(3) C(54)-C(49)-C(50) 118.2(3) C(54)-C(49)-B(4) 121.4(3) C(50)-C(49)-B(4) 120.4(3) C(51)-C(50)-C(49) 119.4(3) C(51)-C(50)-C(57) 118.4(3) C(49)-C(50)-C(57) 122.1(3) C(52)-C(51)-C(50) 122.8(3) C(53)-C(52)-C(51) 117.2(3) C(53)-C(52)-C(56) 121.5(4) C(51)-C(52)-C(56) 121.3(4) C(52)-C(53)-C(54) 122.6(3) C(53)-C(54)-C(49) 119.9(3) C(53)-C(54)-C(55) 117.8(3) C(49)-C(54)-C(55) 122.2(3) C(59)-C(58)-C(63) 117.8(2) C(59)-C(58)-B(4) 121.5(2) C(63)-C(58)-B(4) 120.7(3) C(60)-C(59)-C(58) 120.3(3) C(60)-C(59)-C(66) 118.2(3) C(58)-C(59)-C(66) 121.5(3) C(59)-C(60)-C(61) 121.9(3) C(62)-C(61)-C(60) 117.9(3) C(62)-C(61)-C(65) 121.2(3) C(60)-C(61)-C(65) 120.9(3) C(61)-C(62)-C(63) 122.3(3) C(62)-C(63)-C(58) 119.9(3) C(62)-C(63)-C(64) 118.8(2) C(58)-C(63)-C(64) 121.2(2) Cl(2)-C(67)-Cl(1) 112.5(2) Table S3d. Anisotropic displacement parameters (Å 2 x 10 3 ) for 1-BF2. 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 B(1) 25(2) 34(2) 55(2) 6(2) 5(2) 5(2) B(2) 38(2) 36(2) 51(2) 11(2) -6(2) 11(2) B(3) 61(3) 65(3) 54(2) 33(2) 17(2) 25(2) B(4) 41(2) 40(2) 36(2) 11(2) 9(2) 13(2) F(1) 51(1) 55(1) 54(1) 11(1) -5(1) 13(1) F(2) 48(1) 54(1) 66(1) 21(1) 20(1) 14(1) F(3) 79(2) 88(2) 54(1) 27(1) 14(1) 35(1) F(4) 72(2) 73(2) 125(2) 56(2) 17(1) 16(1) O(1) 24(1) 34(1) 72(1) 3(1) 2(1) 2(1) S34

35 O(2) 25(1) 39(1) 79(2) -1(1) 3(1) 6(1) O(3) 72(2) 74(2) 55(1) 40(1) 24(1) 39(1) O(4) 62(2) 88(2) 52(1) 43(1) 23(1) 40(1) C(1) 28(2) 35(2) 31(1) 11(1) 2(1) 3(1) C(2) 24(2) 33(2) 42(2) 10(1) 3(1) 3(1) C(3) 30(2) 35(2) 33(1) 12(1) 1(1) 7(1) C(4) 32(2) 30(2) 34(1) 8(1) -2(1) 7(1) C(5) 33(2) 35(2) 42(2) 9(1) 7(1) 10(1) C(6) 32(2) 35(2) 47(2) 13(1) 6(1) 4(1) C(7) 32(2) 35(2) 46(2) 10(1) 3(1) 7(1) C(8) 33(2) 40(2) 59(2) 7(2) 5(1) 15(2) C(9) 30(2) 35(2) 56(2) 5(2) 2(1) 5(1) C(10) 30(2) 34(2) 33(1) 9(1) 4(1) 7(1) C(11) 34(2) 33(2) 51(2) 2(1) 1(1) 4(1) C(12) 29(2) 54(2) 62(2) 3(2) 5(2) 10(2) C(13) 43(2) 51(2) 75(2) 10(2) 10(2) 24(2) C(14) 50(2) 35(2) 113(3) 14(2) 18(2) 10(2) C(15) 30(2) 42(2) 87(2) 17(2) 12(2) 6(2) C(16) 36(2) 29(2) 51(2) 7(1) 4(1) 10(1) C(17) 38(2) 38(2) 57(2) 10(2) 5(2) 11(2) C(18) 34(2) 49(2) 73(2) 6(2) 5(2) 9(2) C(19) 43(2) 34(2) 85(3) 15(2) 20(2) 12(2) C(20) 51(2) 42(2) 72(2) 22(2) 18(2) 14(2) C(21) 42(2) 36(2) 58(2) 14(2) 6(2) 10(2) C(22) 58(2) 67(3) 62(2) 27(2) 6(2) 10(2) C(23) 45(2) 60(3) 128(4) 32(2) 26(2) 12(2) C(24) 45(2) 72(3) 69(2) 19(2) -8(2) 8(2) C(25) 37(2) 32(2) 47(2) 4(1) 0(1) 4(1) C(26) 36(2) 33(2) 52(2) -1(1) -7(2) 2(2) C(27) 46(2) 36(2) 58(2) -6(2) -2(2) 9(2) C(28) 46(2) 52(2) 49(2) -6(2) 4(2) 2(2) C(29) 51(2) 52(2) 48(2) 8(2) 0(2) 0(2) C(30) 43(2) 40(2) 46(2) 6(2) 1(2) 4(2) C(31) 67(2) 52(2) 63(2) 22(2) 5(2) 9(2) C(32) 75(3) 84(3) 62(2) -7(2) 17(2) 18(2) C(33) 51(2) 41(2) 71(2) 12(2) 1(2) 14(2) S35

36 C(34) 47(2) 38(2) 37(2) 10(1) 2(1) 6(2) C(35) 44(2) 59(2) 45(2) 28(2) 6(2) 13(2) C(36) 46(2) 39(2) 39(2) 15(1) 5(1) 6(2) C(37) 39(2) 43(2) 36(2) 16(1) 0(1) 8(2) C(38) 34(2) 56(2) 51(2) 26(2) 5(1) 8(2) C(39) 44(2) 49(2) 50(2) 30(2) 5(2) 3(2) C(40) 35(2) 39(2) 43(2) 17(1) 2(1) 4(1) C(41) 35(2) 44(2) 46(2) 20(2) 5(1) 7(2) C(42) 40(2) 49(2) 40(2) 17(2) 8(1) 9(2) C(43) 46(2) 34(2) 37(2) 7(1) -2(1) 11(2) C(44) 43(2) 45(2) 48(2) 17(2) 6(2) 10(2) C(45) 50(2) 56(2) 57(2) 16(2) 11(2) 14(2) C(46) 51(2) 57(2) 64(2) 12(2) 3(2) 24(2) C(47) 78(3) 73(3) 53(2) 19(2) -2(2) 41(2) C(48) 71(2) 62(2) 41(2) 18(2) 6(2) 30(2) C(49) 40(2) 36(2) 37(2) 18(1) 5(1) 9(1) C(50) 39(2) 50(2) 33(2) 21(1) 3(1) 11(2) C(51) 36(2) 73(3) 48(2) 37(2) 6(2) 10(2) C(52) 48(2) 71(3) 47(2) 37(2) -7(2) -9(2) C(53) 66(2) 40(2) 45(2) 19(2) -3(2) -4(2) C(54) 50(2) 36(2) 39(2) 18(1) 4(1) 6(2) C(55) 67(2) 39(2) 63(2) 14(2) 13(2) 17(2) C(56) 63(3) 100(3) 87(3) 59(3) -19(2) -30(2) C(57) 56(2) 57(2) 52(2) 23(2) 11(2) 26(2) C(58) 32(2) 35(2) 40(2) 15(1) 1(1) 5(1) C(59) 44(2) 36(2) 40(2) 14(1) 2(1) 3(2) C(60) 43(2) 29(2) 44(2) 6(1) 5(1) 3(1) C(61) 37(2) 36(2) 52(2) 20(2) 8(1) 10(1) C(62) 37(2) 41(2) 37(2) 17(1) 4(1) 10(1) C(63) 28(2) 38(2) 42(2) 14(1) 1(1) 9(1) C(64) 47(2) 42(2) 40(2) 11(1) 3(1) 4(2) C(65) 74(3) 41(2) 64(2) 28(2) 11(2) 12(2) C(66) 100(3) 44(2) 41(2) 11(2) 2(2) 0(2) C(67) 81(3) 74(3) 89(3) 6(2) 21(2) 19(2) Cl(1) 136(1) 72(1) 126(1) 49(1) 32(1) 31(1) Cl(2) 76(1) 188(2) 84(1) 8(1) 2(1) 42(1) S36

37 Table S3e. Hydrogen coordinates ( x 10 4 ) and isotropic displacement parameters (Å 2 x 10 3 ) for 1-BF2. x y z U(eq) H(2A) H(5A) H(6A) H(8A) H(9A) H(11A) H(12A) H(13A) H(14A) H(15A) H(18A) H(20A) H(22A) H(22B) H(22C) H(23A) H(23B) H(23C) H(24A) H(24B) H(24C) H(27A) H(29A) H(31A) H(31B) H(31C) H(32A) H(32B) H(32C) H(33A) H(33B) S37

38 H(33C) H(35A) H(38A) H(39A) H(41A) H(42A) H(44A) H(45A) H(46A) H(47A) H(48A) H(51A) H(53A) H(55A) H(55B) H(55C) H(56A) H(56B) H(56C) H(57A) H(57B) H(57C) H(60A) H(62A) H(64A) H(64B) H(64C) H(65A) H(65B) H(65C) H(66A) H(66B) H(66C) H(67A) H(67B) S38

39 Table S4. Crystal structural data of 2-BF2 Table S4a. Crystal data and structure refinement for 2-BF2. Identification code 2-BF2 Empirical formula C51 H53 B3 F2 O2 Formula weight Temperature 185(2) K Wavelength Å Crystal system Monoclinic Space group P2(1) Unit cell dimensions a = (16) Å = 90. b = (3) Å = (3). c = (2) Å = 90. Volume (6) Å 3 Z 2 Density (calculated) Mg/m 3 Absorption coefficient mm -1 F(000) 816 Crystal size 0.03 x 0.02 x 0.02 mm 3 Theta range for data collection 1.96 to Index ranges -11<=h<=11, -16<=k<=20, -17<=l<=16 Reflections collected Independent reflections 5839 [R(int) = ] Completeness to theta = % Absorption correction Semi-empirical from equivalents Max. and min. transmission and Refinement method Full-matrix least-squares on F 2 Data / restraints / parameters 5839 / 1 / 487 Goodness-of-fit on F Final R indices [I>2sigma(I)] R1 = , wr2 = R indices (all data) R1 = , wr2 = Absolute structure parameter cannot be reliably determined Largest diff. peak and hole and e.å -3 S39

40 Table S4b. Atomic coordinates ( x 10 4 ) and equivalent isotropic displacement parameters (Å 2 x 10 3 ) for 2-BF2. U(eq) is defined as one third of the trace of the orthogonalized U ij tensor. x y z U(eq) B(1) -1685(11) 8345(7) 4388(8) 75(3) B(2) 5615(7) 10815(5) 6055(6) 50(2) B(3) -1882(8) 5276(5) -13(5) 53(2) F(1) -2809(5) 8855(3) 4051(4) 120(2) F(2) -1749(6) 7899(4) 5149(4) 132(2) O(1) -1758(5) 7798(3) 3531(4) 80(2) O(2) -353(5) 8806(3) 4695(3) 74(2) C(1) -740(7) 7715(4) 3172(5) 46(2) C(2) 482(6) 8172(4) 3520(5) 54(2) C(3) 636(7) 8724(5) 4293(5) 59(2) C(4) 1904(7) 9244(4) 4714(5) 50(2) C(5) 2032(7) 9698(4) 5569(5) 60(2) C(6) 3193(7) 10178(5) 5983(5) 66(2) C(7) 4273(6) 10248(4) 5578(5) 53(2) C(8) 4127(7) 9796(4) 4714(5) 62(2) C(9) 2965(7) 9286(4) 4290(4) 60(2) C(10) 6074(4) 10980(3) 7250(2) 46(2) C(11) 6327(4) 10327(2) 7903(3) 55(2) C(12) 6578(4) 10451(3) 8923(3) 60(2) C(13) 6578(4) 11228(3) 9289(2) 59(2) C(14) 6326(4) 11882(2) 8636(3) 53(2) C(15) 6074(4) 11758(2) 7616(3) 51(2) C(16) 5794(7) 12487(4) 6954(5) 62(2) C(17) 6771(7) 11374(5) 10406(4) 87(3) C(18) 6399(8) 9455(4) 7603(5) 80(2) C(19) 6356(5) 11211(3) 5348(3) 52(2) C(20) 5580(4) 11725(3) 4579(4) 70(2) C(21) 6242(7) 12098(3) 3973(3) 81(3) C(22) 7681(7) 11956(3) 4135(4) 82(3) C(23) 8458(4) 11442(4) 4903(4) 71(2) C(24) 7796(5) 11070(3) 5510(3) 57(2) S40

41 C(25) 8656(6) 10451(4) 6267(4) 63(2) C(26) 4022(8) 11911(6) 4344(6) 117(3) C(27) 8418(10) 12375(6) 3467(6) 125(4) C(28) -1005(6) 7109(4) 2362(4) 42(2) C(29) -2317(6) 6690(4) 2040(4) 45(2) C(30) -2566(6) 6114(4) 1303(4) 51(2) C(31) -1581(6) 5946(4) 806(4) 45(2) C(32) -304(6) 6393(4) 1124(5) 49(2) C(33) -23(6) 6958(4) 1887(5) 47(2) C(34) -1058(4) 5262(3) -798(3) 52(2) C(35) -1118(5) 5926(2) -1412(4) 58(2) C(36) -394(5) 5913(3) -2099(3) 69(2) C(37) 389(5) 5236(4) -2172(3) 65(2) C(38) 448(5) 4572(3) -1559(4) 68(2) C(39) -275(5) 4585(2) -872(3) 58(2) C(40) -208(8) 3832(5) -249(6) 83(2) C(41) -1967(8) 6699(5) -1412(5) 81(2) C(42) 1269(9) 5235(6) -2863(6) 106(3) C(43) -3029(4) 4596(3) -19(4) 53(2) C(44) -4240(5) 4485(3) -864(3) 59(2) C(45) -5303(4) 3954(3) -829(3) 65(2) C(46) -5153(5) 3533(3) 53(4) 72(2) C(47) -3941(6) 3644(3) 898(3) 72(2) C(48) -2879(4) 4175(3) 862(3) 63(2) C(49) -1540(7) 4229(5) 1805(5) 78(2) C(50) -4458(7) 4913(5) -1859(5) 82(2) C(51) -6291(8) 2970(5) 145(6) 95(3) Table S4c. Bond lengths [Å] and angles [ ] for 2-BF2. B(1)-F(2) 1.324(11) B(1)-F(1) 1.353(11) B(1)-O(2) 1.461(9) B(1)-O(1) 1.494(10) B(2)-C(19) 1.572(8) B(2)-C(7) 1.583(9) S41 B(2)-C(10) 1.615(8) B(3)-C(31) 1.559(9) B(3)-C(34) 1.587(8) B(3)-C(43) 1.602(8) O(1)-C(1) 1.283(6) O(2)-C(3) 1.298(7)

42 C(1)-C(2) 1.374(8) C(1)-C(28) 1.478(8) C(2)-C(3) 1.392(8) C(3)-C(4) 1.476(8) C(4)-C(9) 1.380(8) C(4)-C(5) 1.391(8) C(5)-C(6) 1.359(8) C(6)-C(7) 1.383(8) C(7)-C(8) 1.397(8) C(8)-C(9) 1.393(8) C(10)-C(11) C(10)-C(15) C(11)-C(12) C(11)-C(18) 1.517(8) C(12)-C(13) C(13)-C(14) C(13)-C(17) 1.542(7) C(14)-C(15) C(15)-C(16) 1.496(7) C(19)-C(20) C(19)-C(24) C(20)-C(21) C(20)-C(26) 1.500(8) C(21)-C(22) C(22)-C(23) C(22)-C(27) 1.543(8) C(23)-C(24) C(24)-C(25) 1.518(7) C(28)-C(33) 1.382(7) C(28)-C(29) 1.409(7) C(29)-C(30) 1.372(8) C(30)-C(31) 1.412(7) C(31)-C(32) 1.406(8) C(32)-C(33) 1.383(8) C(34)-C(35) C(34)-C(39) C(35)-C(36) C(35)-C(41) 1.535(8) C(36)-C(37) C(37)-C(38) C(37)-C(42) 1.515(8) C(38)-C(39) C(39)-C(40) 1.517(8) C(43)-C(44) C(43)-C(48) C(44)-C(45) C(44)-C(50) 1.522(7) C(45)-C(46) C(46)-C(47) C(46)-C(51) 1.506(8) C(47)-C(48) C(48)-C(49) 1.532(7) F(2)-B(1)-F(1) 111.9(9) F(2)-B(1)-O(2) 109.9(8) F(1)-B(1)-O(2) 109.5(8) F(2)-B(1)-O(1) 108.3(8) F(1)-B(1)-O(1) 106.7(8) O(2)-B(1)-O(1) 110.3(7) C(19)-B(2)-C(7) 119.2(6) C(19)-B(2)-C(10) 124.4(5) C(7)-B(2)-C(10) 116.3(6) C(31)-B(3)-C(34) 121.0(6) C(31)-B(3)-C(43) 117.6(5) C(34)-B(3)-C(43) 121.4(5) C(1)-O(1)-B(1) 123.9(6) C(3)-O(2)-B(1) 124.1(6) O(1)-C(1)-C(2) 121.3(6) O(1)-C(1)-C(28) 115.0(6) C(2)-C(1)-C(28) 123.8(6) C(1)-C(2)-C(3) 119.4(6) O(2)-C(3)-C(2) 120.9(6) S42

43 O(2)-C(3)-C(4) 115.6(6) C(2)-C(3)-C(4) 123.5(6) C(9)-C(4)-C(5) 119.4(6) C(9)-C(4)-C(3) 121.9(6) C(5)-C(4)-C(3) 118.7(6) C(6)-C(5)-C(4) 120.3(6) C(5)-C(6)-C(7) 122.4(6) C(6)-C(7)-C(8) 116.8(6) C(6)-C(7)-B(2) 122.3(6) C(8)-C(7)-B(2) 120.9(6) C(9)-C(8)-C(7) 121.7(6) C(4)-C(9)-C(8) 119.3(6) C(11)-C(10)-C(15) C(11)-C(10)-B(2) 119.0(4) C(15)-C(10)-B(2) 120.7(4) C(10)-C(11)-C(12) C(10)-C(11)-C(18) 125.0(4) C(12)-C(11)-C(18) 115.0(4) C(11)-C(12)-C(13) C(14)-C(13)-C(12) C(14)-C(13)-C(17) 119.2(5) C(12)-C(13)-C(17) 120.7(5) C(13)-C(14)-C(15) C(14)-C(15)-C(10) C(14)-C(15)-C(16) 117.2(4) C(10)-C(15)-C(16) 122.8(4) C(20)-C(19)-C(24) C(20)-C(19)-B(2) 119.8(4) C(24)-C(19)-B(2) 120.2(4) C(19)-C(20)-C(21) C(19)-C(20)-C(26) 123.8(5) C(21)-C(20)-C(26) 116.2(5) C(20)-C(21)-C(22) C(23)-C(22)-C(21) C(23)-C(22)-C(27) 120.1(6) C(21)-C(22)-C(27) 119.9(6) C(24)-C(23)-C(22) C(23)-C(24)-C(19) C(23)-C(24)-C(25) 117.6(4) C(19)-C(24)-C(25) 122.1(4) C(33)-C(28)-C(29) 118.8(6) C(33)-C(28)-C(1) 122.0(6) C(29)-C(28)-C(1) 119.2(5) C(30)-C(29)-C(28) 119.8(6) C(29)-C(30)-C(31) 122.5(6) C(32)-C(31)-C(30) 116.1(6) C(32)-C(31)-B(3) 122.5(6) C(30)-C(31)-B(3) 121.3(6) C(33)-C(32)-C(31) 121.8(6) C(28)-C(33)-C(32) 120.8(6) C(35)-C(34)-C(39) C(35)-C(34)-B(3) 120.1(5) C(39)-C(34)-B(3) 119.9(5) C(34)-C(35)-C(36) C(34)-C(35)-C(41) 124.7(5) C(36)-C(35)-C(41) 115.3(5) C(37)-C(36)-C(35) C(36)-C(37)-C(38) C(36)-C(37)-C(42) 120.6(6) C(38)-C(37)-C(42) 119.2(6) C(39)-C(38)-C(37) C(38)-C(39)-C(34) C(38)-C(39)-C(40) 117.4(5) C(34)-C(39)-C(40) 122.6(5) C(44)-C(43)-C(48) C(44)-C(43)-B(3) 120.3(4) C(48)-C(43)-B(3) 119.3(4) C(45)-C(44)-C(43) C(45)-C(44)-C(50) 117.3(4) C(43)-C(44)-C(50) 122.7(4) C(44)-C(45)-C(46) C(47)-C(46)-C(45) S43

44 C(47)-C(46)-C(51) 117.7(5) C(47)-C(48)-C(43) C(45)-C(46)-C(51) 122.3(5) C(47)-C(48)-C(49) 116.8(4) C(46)-C(47)-C(48) C(43)-C(48)-C(49) 123.1(4) Table S4d. Anisotropic displacement parameters (Å 2 x 10 3 ) for 2-BF2. 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 B(1) 74(7) 78(8) 76(7) -29(6) 31(6) -36(6) B(2) 30(4) 57(5) 60(5) -7(4) 12(4) 7(4) B(3) 46(5) 62(6) 45(5) 2(4) 7(4) 3(4) F(1) 64(3) 107(4) 180(5) -65(4) 29(3) -13(3) F(2) 144(5) 171(5) 98(4) -28(4) 63(3) -92(4) O(1) 56(3) 110(4) 90(4) -56(3) 44(3) -41(3) O(2) 55(3) 101(4) 76(3) -40(3) 36(3) -17(3) C(1) 39(4) 60(5) 48(4) 0(4) 27(3) 2(4) C(2) 41(4) 67(5) 55(4) -18(4) 19(3) -12(4) C(3) 49(4) 72(6) 59(5) -4(4) 22(4) -4(4) C(4) 40(4) 70(5) 46(4) -13(4) 21(3) -10(4) C(5) 48(4) 76(6) 62(5) -26(4) 28(4) -16(4) C(6) 55(5) 91(6) 58(4) -36(4) 26(4) -15(4) C(7) 38(4) 64(5) 60(4) -17(4) 21(3) -12(4) C(8) 57(4) 75(6) 60(5) -25(4) 27(4) -15(4) C(9) 50(4) 93(6) 43(4) -29(4) 23(3) -30(4) C(10) 36(3) 54(5) 49(4) 2(4) 16(3) -1(3) C(11) 52(4) 57(5) 54(4) 3(4) 17(3) 2(4) C(12) 59(5) 64(5) 50(4) 5(4) 12(4) 3(4) C(13) 30(3) 99(6) 46(4) -3(5) 9(3) 7(4) C(14) 41(4) 57(5) 57(4) -11(4) 13(3) -1(3) C(15) 37(4) 60(5) 56(4) -7(4) 17(3) 5(4) C(16) 69(5) 52(5) 65(5) 3(4) 21(4) 8(4) C(17) 88(5) 113(7) 47(4) -14(5) 8(4) 23(5) C(18) 107(6) 55(5) 76(5) 1(4) 29(5) -4(5) C(19) 55(4) 53(5) 50(4) -6(4) 20(4) 0(4) C(20) 83(6) 90(6) 50(4) 5(4) 37(4) 8(5) S44

45 C(21) 119(7) 82(6) 46(5) 0(4) 32(5) 20(6) C(22) 116(7) 84(6) 65(6) -16(5) 53(5) -38(6) C(23) 79(5) 79(6) 60(5) -15(4) 31(5) -14(5) C(24) 61(5) 64(5) 52(4) -13(4) 26(4) -22(4) C(25) 53(4) 76(5) 55(4) -8(4) 12(3) 15(4) C(26) 85(6) 160(10) 87(6) 25(6) 6(5) 53(6) C(27) 171(9) 136(9) 96(7) 2(6) 83(7) -44(8) C(28) 36(4) 48(4) 46(4) -4(3) 19(3) -1(3) C(29) 38(4) 55(4) 49(4) -7(4) 24(3) -14(3) C(30) 44(4) 61(5) 47(4) -11(4) 12(3) -9(4) C(31) 42(4) 52(4) 43(4) -4(3) 18(3) -7(3) C(32) 46(4) 57(5) 50(4) -1(4) 23(3) 2(4) C(33) 44(4) 45(4) 54(4) -4(4) 18(3) -8(3) C(34) 43(4) 54(5) 55(4) -7(4) 10(3) 1(4) C(35) 52(4) 75(6) 46(4) -10(4) 16(3) -8(4) C(36) 68(5) 81(6) 63(5) -5(5) 27(4) -6(5) C(37) 51(4) 96(7) 55(5) -18(5) 26(4) -22(5) C(38) 59(5) 74(6) 74(5) -13(5) 27(4) -1(4) C(39) 44(4) 67(5) 62(5) -10(4) 17(4) -1(4) C(40) 85(5) 56(5) 115(6) 0(5) 43(5) 14(5) C(41) 99(6) 78(6) 75(5) 6(4) 41(5) 16(5) C(42) 101(7) 140(9) 88(6) -24(6) 45(5) -18(6) C(43) 46(4) 68(5) 49(4) -16(4) 21(3) -2(4) C(44) 45(4) 63(5) 65(5) -22(4) 15(4) -10(4) C(45) 54(5) 70(6) 70(5) -22(5) 18(4) -5(4) C(46) 63(5) 53(5) 107(7) -33(5) 39(5) -16(4) C(47) 74(5) 53(5) 93(6) -9(4) 33(5) -15(4) C(48) 67(5) 60(5) 59(5) -9(4) 20(4) -8(4) C(49) 84(5) 76(6) 64(5) 7(4) 13(4) -15(5) C(50) 59(5) 116(7) 62(5) -5(5) 7(4) -10(5) C(51) 84(6) 73(6) 129(7) -17(6) 36(5) -27(5) S45

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