Supporting Information for Substituent Effects on the Properties of Borafluorenes Mallory F. Smith, S. Joel Cassidy, Ian A. Adams, Monica Vasiliu, Deidra L. Gerlach, David Dixon*, Paul A. Rupar* Department of Chemistry, The University of Alabama, Tuscaloosa, Alabama, 35487-0036 dadixon@ua.edu, parupar@ua.edu Table of Contents: NMR Spectra Cyclic Voltammograms DCM Excitation Spectra Plot of Fluoride Affinities vs LUMOs Frontier Molecular Orbitals List of first 20 calculated Singlet Excited States Optimized DFT Geometries Table of Optical Data Crystallographic Data S2 S8 S8 S9 S10 S12 S27 S37 S38 S1
Figure S1. 1 H NMR spectra of Mes F BF in CDCl 3 Figure S2. 13 C NMR Spectrum of Mes F BF in CDCl 3. S2
Figure S3. 19 F{ 1 H} NMR Spectrum of Mes F BF in CDCl 3 Figure S4. 11 B NMR Spectrum of Mes F BF in CDCl 3 S3
Figure S5. 1 H NMR Spectrum of TipBF(OMe) 2 in CDCl 3 Figure S6. 13 C NMR Spectrum of TipBF(OMe) 2 in CDCl 3 S4
Figure S7. 11 B NMR of TipBF(OMe) 2 in CDCl 3 Figure S8. 1 H NMR spectrum of ipr 2 NBF at room temperature in in CDCl 3 S5
Figure S9. 1 H NMR spectrum of ipr 2 NBF at 223K in CDCl 3 Figure S10. 1 H NMR spectrum of ipr 2 NBF at 323K in CDCl 3 S6
Figure S11. 13 C NMR Spectra of i Pr 2 NBF at room temperature in in CDCl 3 Figure S12. 11 B NMR Spectra of i Pr 2 NBF at room temperature in in CDCl 3 S7
Figure S13. Cyclic voltammograms of the borafluorenes in 0.1 M solution of Bu 4 NPF 6 in DCM. Measurements were taken at a scan rate of 0.1 V s -1. Figure S14. Absorption (solid black lines) and excitation spectra (dashed blue lines) of the borafluorenes. All measurements were carried out in DCM under a N 2 atmosphere. Excitation spectra were recorded at the most intense emission peak (See Table 1) S8
Figure S15. Plot of fluoride affinities vs. LUMO values. S9
S10
Figure S16. Frontier Molecular Orbitals of the Borafluorenes S11
Vertical singlet 7.3 kcal/mol 2.85 ev 435 nm ClBF, 1 st excited state 2.53 ev 490 nm Relaxed singlet 2.20 ev 565 nm Vertical singlet 7.6 kcal/mol 2.85 ev 435 nm TipBF, 1 st excited state 2.52 ev 492 nm Relaxed singlet 2.18 ev 570 nm Vertical singlet 9.3 kcal/mol 2.78 ev 445 nm Mes F BF, 1 st excited state 2.38 ev 521 nm Relaxed singlet 2.00 ev 619 nm Singlet g.s. Singlet at the excited singlet geometry 7.7 kcal/mol Singlet g.s. Singlet at the excited singlet geometry 7.9 kcal/mol Singlet g.s. Singlet at the excited singlet geometry 8.6 kcal/mol TipBF(OME) 2, 1 st excited state ipr 2 NBF, 1 st excited state t BuOBF, 1 st excited state Vertical singlet 7.5 kcal/mol 2.96 ev 419 nm 2.63 ev 471 nm Relaxed singlet 2.30 ev 538 nm Vertical singlet 8.3 kcal/mol 3.43 ev 361 nm 3.07 ev 404 nm Relaxed singlet 2.68 ev 463 nm Vertical singlet 8.1 kcal/mol 3.28 ev 378 nm 2.93 ev 424 nm Relaxed singlet 2.55 ev 485 nm Singlet g.s. Singlet at the excited singlet geometry 7.6 kcal/mol Singlet g.s. Singlet at the excited singlet geometry 9.0 kcal/mol Singlet g.s. Singlet at the excited singlet geometry 8.6 kcal/mol Figure S17. Calculated vertical and adiabatic absorption and emission spectra of the Borafluorenes for the HOMO LUMO transition. S12
Table S1. List of first 20 calculated singlet excited states at B3LYP/DZVP2 level. ClBF HOMO = 51, LUMO = 52 Excited State 1: Singlet-B2 2.8496 ev 435.09 nm f=0.0014 51 -> 52 0.70368 Excited State 2: Singlet-B2 3.8155 ev 324.95 nm f=0.0347 50 -> 52 0.62000 51 -> 53-0.32909 Excited State 3: Singlet-A2 4.3012 ev 288.25 nm f=0.0000 48 -> 52 0.70384 Excited State 4: Singlet-A1 4.3414 ev 285.58 nm f=0.0365 47 -> 52-0.13054 49 -> 52 0.65851 51 -> 54-0.16766 Excited State 5: Singlet-B2 4.8516 ev 255.56 nm f=0.9179 50 -> 52 0.33322 51 -> 53 0.61490 Excited State 6: Singlet-A1 4.9086 ev 252.59 nm f=0.0587 47 -> 52 0.65479 49 -> 52 0.10886 49 -> 53-0.11479 51 -> 54-0.18318 Excited State 7: Singlet-A1 5.2933 ev 234.23 nm f=0.0365 49 -> 52 0.17954 49 -> 53-0.41862 50 -> 54 0.11501 51 -> 54 0.51390 Excited State 8: Singlet-B2 5.3565 ev 231.46 nm f=0.0039 50 -> 53 0.68079 Excited State 9: Singlet-B1 5.6297 ev 220.23 nm f=0.0002 46 -> 52 0.70261 Excited State 10: Singlet-A2 5.7986 ev 213.82 nm f=0.0000 44 -> 52 0.52159 S13
48 -> 53-0.46826 Excited State 11: Singlet-A2 5.8637 ev 211.44 nm f=0.0000 44 -> 52 0.47029 48 -> 53 0.51835 Excited State 12: Singlet-A1 5.9370 ev 208.83 nm f=0.1351 45 -> 52-0.11711 47 -> 53 0.30005 49 -> 53 0.40947 50 -> 55-0.12707 51 -> 54 0.29294 51 -> 55 0.32765 Excited State 13: Singlet-B1 6.0515 ev 204.88 nm f=0.0009 43 -> 52 0.70158 Excited State 14: Singlet-A1 6.0964 ev 203.37 nm f=0.1497 45 -> 52 0.27757 47 -> 52-0.11225 47 -> 53 0.30002 49 -> 53-0.22859 50 -> 54 0.23714 50 -> 55 0.16324 51 -> 54-0.14818 51 -> 55 0.39728 Excited State 15: Singlet-A1 6.1722 ev 200.88 nm f=0.0160 45 -> 52-0.16489 47 -> 53-0.39954 49 -> 53 0.13545 50 -> 54 0.45818 50 -> 55-0.12519 51 -> 55 0.24189 Excited State 16: Singlet-A1 6.2376 ev 198.77 nm f=0.0005 45 -> 52 0.59370 47 -> 53-0.10694 49 -> 53 0.18444 50 -> 55-0.21475 51 -> 54 0.13150 51 -> 55-0.12694 Excited State 17: Singlet-A2 6.3374 ev 195.64 nm f=0.0000 41 -> 52 0.69655 Excited State 18: Singlet-B2 6.5753 ev 188.56 nm f=0.0420 42 -> 52 0.63691 49 -> 54 0.16073 51 -> 56 0.22924 Excited State 19: Singlet-B2 6.6976 ev 185.12 nm f=0.0236 49 -> 54 0.56087 51 -> 56-0.40556 Excited State 20: Singlet-B1 6.7821 ev 182.81 nm f=0.0014 S14
46 -> 53-0.18829 48 -> 54 0.66501 TipBF HOMO = 75, LUMO = 76 Excited State 1: Singlet-A 2.8510 ev 434.88 nm f=0.0009 75 -> 76 0.70342 Excited State 2: Singlet-A 2.9251 ev 423.86 nm f=0.0115 74 -> 76 0.70277 Excited State 3: Singlet-A 3.2647 ev 379.77 nm f=0.0005 73 -> 76 0.70561 Excited State 4: Singlet-A 3.8119 ev 325.26 nm f=0.0267 72 -> 76 0.61248 75 -> 77 0.34273 Excited State 5: Singlet-A 4.3797 ev 283.09 nm f=0.0378 70 -> 76-0.10981 71 -> 76 0.59263 74 -> 77-0.29909 75 -> 79 0.15998 Excited State 6: Singlet-A 4.4110 ev 281.08 nm f=0.0078 71 -> 76 0.28330 74 -> 77 0.63699 Excited State 7: Singlet-A 4.6980 ev 263.91 nm f=0.0184 73 -> 77 0.69235 75 -> 77 0.12651 Excited State 8: Singlet-A 4.7606 ev 260.44 nm f=0.0048 69 -> 76 0.69008 Excited State 9: Singlet-A 4.8209 ev 257.18 nm f=0.8284 72 -> 76-0.34075 73 -> 77-0.13869 75 -> 77 0.59039 S15
Excited State 10: Singlet-A 4.9094 ev 252.54 nm f=0.0104 66 -> 76 0.14292 68 -> 76 0.64862 70 -> 76-0.21585 Excited State 11: Singlet-A 4.9506 ev 250.44 nm f=0.0514 68 -> 76 0.21990 70 -> 76 0.61478 75 -> 79 0.20983 Excited State 12: Singlet-A 5.0301 ev 246.49 nm f=0.0008 73 -> 78 0.48102 74 -> 78-0.11892 74 -> 80-0.47929 Excited State 13: Singlet-A 5.3175 ev 233.16 nm f=0.0975 71 -> 76-0.18223 71 -> 77 0.38375 72 -> 77 0.12221 72 -> 79-0.10761 74 -> 78-0.11974 75 -> 78-0.17213 75 -> 79 0.47394 Excited State 14: Singlet-A 5.3221 ev 232.96 nm f=0.0049 72 -> 77 0.58062 75 -> 78-0.30313 75 -> 79-0.15783 Excited State 15: Singlet-A 5.3847 ev 230.25 nm f=0.0032 72 -> 77 0.33637 74 -> 79-0.13795 75 -> 78 0.58734 Excited State 16: Singlet-A 5.4011 ev 229.55 nm f=0.0033 74 -> 79 0.67175 75 -> 78 0.15026 Excited State 17: Singlet-A 5.5475 ev 223.49 nm f=0.0864 71 -> 77 0.11231 73 -> 80 0.30327 74 -> 78 0.57374 74 -> 80-0.10136 75 -> 80 0.10627 Excited State 18: Singlet-A 5.6076 ev 221.10 nm f=0.0023 75 -> 80 0.69321 Excited State 19: Singlet-A 5.7003 ev 217.50 nm f=0.0002 73 -> 79 0.69140 Excited State 20: Singlet-A 5.8017 ev 213.71 nm f=0.0018 64 -> 76-0.11785 65 -> 76 0.68835 S16
Mes F BF HOMO = 111, LUMO = 112 Excited State 1: Singlet-A 2.7840 ev 445.35 nm f=0.0011 111 ->112 0.70225 Excited State 2: Singlet-A 3.6491 ev 339.77 nm f=0.0009 111 ->113 0.52505 111 ->114-0.46606 Excited State 3: Singlet-A 3.6778 ev 337.11 nm f=0.0010 111 ->113 0.47240 111 ->114 0.52139 Excited State 4: Singlet-A 3.7730 ev 328.61 nm f=0.0369 110 ->112 0.62480 111 ->115 0.30946 Excited State 5: Singlet-A 4.3228 ev 286.81 nm f=0.0576 107 ->112-0.14796 109 ->112 0.65659 111 ->116 0.15292 Excited State 6: Singlet-A 4.4765 ev 276.97 nm f=0.0132 108 ->112-0.17020 110 ->112 0.10558 110 ->113-0.40386 110 ->114 0.51281 111 ->115-0.15793 Excited State 7: Singlet-A 4.4812 ev 276.68 nm f=0.0074 105 ->112 0.13192 107 ->112 0.20310 108 ->112 0.61710 110 ->114 0.17654 Excited State 8: Singlet-A 4.5142 ev 274.66 nm f=0.0069 S17
110 ->113 0.57345 110 ->114 0.39651 Excited State 9: Singlet-A 4.8466 ev 255.82 nm f=0.7631 109 ->113 0.17557 110 ->112-0.28458 110 ->114 0.20531 111 ->115 0.57659 Excited State 10: Singlet-A 4.8675 ev 254.72 nm f=0.0632 107 ->112 0.60747 108 ->112-0.22139 109 ->114 0.13167 111 ->116 0.17827 Excited State 11: Singlet-A 4.9197 ev 252.02 nm f=0.0304 109 ->113 0.52093 109 ->114-0.40075 111 ->115-0.10896 111 ->116 0.11845 Excited State 12: Singlet-A 4.9420 ev 250.88 nm f=0.0212 106 ->112-0.15470 106 ->114-0.11714 108 ->113-0.15496 109 ->113 0.34743 109 ->114 0.53425 Excited State 13: Singlet-A 5.0030 ev 247.82 nm f=0.0081 106 ->112 0.39091 106 ->114 0.24199 107 ->113 0.15408 108 ->113 0.39222 109 ->113 0.26744 109 ->114 0.12280 Excited State 14: Singlet-A 5.2276 ev 237.17 nm f=0.0063 106 ->112 0.55340 106 ->114-0.28813 107 ->113-0.10715 108 ->113-0.28688 Excited State 15: Singlet-A 5.3225 ev 232.94 nm f=0.1293 108 ->114 0.16647 109 ->112-0.16719 109 ->114 0.11176 109 ->115 0.37080 110 ->116-0.10258 111 ->116 0.50789 Excited State 16: Singlet-A 5.3587 ev 231.37 nm f=0.0016 110 ->115 0.67817 Excited State 17: Singlet-A 5.4132 ev 229.04 nm f=0.0019 104 ->112 0.69508 S18
Excited State 18: Singlet-A 5.4937 ev 225.68 nm f=0.0068 105 ->112 0.52514 107 ->113 0.22942 107 ->114-0.20047 108 ->113-0.15116 108 ->114 0.29958 Excited State 19: Singlet-A 5.5104 ev 225.00 nm f=0.0011 105 ->112-0.37024 107 ->113 0.51702 107 ->114-0.20419 108 ->113-0.19877 Excited State 20: Singlet-A 5.5317 ev 224.13 nm f=0.0200 105 ->112-0.21142 107 ->113-0.32998 107 ->114-0.38352 108 ->114 0.39144 109 ->115-0.11941 S19
TipBF(OMe) 2 HOMO = 91, LUMO = 92 Excited State 1: Singlet-A 2.9711 ev 417.30 nm f=0.0240 88 -> 92 0.11868 91 -> 92 0.69297 Excited State 2: Singlet-A 3.1758 ev 390.40 nm f=0.0013 90 -> 92 0.70295 Excited State 3: Singlet-A 3.5420 ev 350.04 nm f=0.0002 89 -> 92 0.70451 Excited State 4: Singlet-A 3.6748 ev 337.39 nm f=0.0181 88 -> 92 0.57017 91 -> 93-0.40267 Excited State 5: Singlet-A 4.2092 ev 294.55 nm f=0.2027 87 -> 92 0.66852 91 -> 96-0.17409 Excited State 6: Singlet-A 4.3134 ev 287.44 nm f=0.0000 90 -> 93 0.70433 Excited State 7: Singlet-A 4.4798 ev 276.76 nm f=0.7868 88 -> 92 0.38171 88 -> 93-0.15745 91 -> 93 0.55611 Excited State 8: Singlet-A 4.6299 ev 267.79 nm f=0.0177 89 -> 93 0.70150 Excited State 9: Singlet-A 4.7713 ev 259.85 nm f=0.0192 86 -> 92 0.46008 87 -> 92-0.13576 87 -> 93 0.48635 91 -> 96-0.12877 Excited State 10: Singlet-A 4.9847 ev 248.73 nm f=0.0009 85 -> 92 0.58314 S20
89 -> 94 0.22088 90 -> 95-0.28711 Excited State 11: Singlet-A 5.0341 ev 246.29 nm f=0.2874 88 -> 92 0.10454 88 -> 93 0.67517 91 -> 93 0.12331 Excited State 12: Singlet-A 5.0405 ev 245.98 nm f=0.0035 85 -> 92-0.37259 89 -> 94 0.42837 90 -> 95-0.38539 Excited State 13: Singlet-A 5.1291 ev 241.73 nm f=0.0156 86 -> 92 0.47423 87 -> 93-0.47196 88 -> 96 0.12270 91 -> 97 0.15570 Excited State 14: Singlet-A 5.1706 ev 239.79 nm f=0.0011 91 -> 94 0.69781 Excited State 15: Singlet-A 5.2683 ev 235.34 nm f=0.0000 81 -> 92 0.18042 84 -> 92 0.67635 Excited State 16: Singlet-A 5.3902 ev 230.02 nm f=0.0079 91 -> 95 0.69119 91 -> 96 0.11739 Excited State 17: Singlet-A 5.4508 ev 227.46 nm f=0.2052 86 -> 92 0.14903 86 -> 93-0.13959 88 -> 97 0.10007 89 -> 95-0.11945 90 -> 94-0.32492 91 -> 96 0.54605 Excited State 18: Singlet-A 5.5518 ev 223.32 nm f=0.0002 90 -> 95-0.17569 90 -> 96 0.68076 Excited State 19: Singlet-A 5.5829 ev 222.08 nm f=0.0144 86 -> 93-0.13495 89 -> 95 0.30030 90 -> 94 0.50632 91 -> 96 0.27648 Excited State 20: Singlet-A 5.8746 ev 211.05 nm f=0.0002 89 -> 95-0.18187 89 -> 96 0.68098 S21
ipr 2 NBF HOMO = 71, LUMO = 72 Excited State 1: Singlet-A 3.4313 ev 361.34 nm f=0.0111 71 -> 72 0.69700 Excited State 2: Singlet-A 4.1537 ev 298.49 nm f=0.0177 69 -> 72 0.49320 71 -> 73-0.49150 Excited State 3: Singlet-A 4.3449 ev 285.36 nm f=0.1940 70 -> 72 0.67529 71 -> 74-0.15232 Excited State 4: Singlet-A 4.8123 ev 257.64 nm f=0.0515 68 -> 72-0.35522 70 -> 72-0.14822 70 -> 73 0.51349 71 -> 74-0.24628 Excited State 5: Singlet-A 4.8913 ev 253.48 nm f=0.6639 69 -> 72 0.48389 70 -> 74 0.11268 71 -> 73 0.48060 Excited State 6: Singlet-A 5.0979 ev 243.21 nm f=0.0141 66 -> 72 0.21921 67 -> 72 0.16836 68 -> 72 0.45111 70 -> 73 0.41108 71 -> 74 0.12080 71 -> 75-0.11837 Excited State 7: Singlet-A 5.3035 ev 233.78 nm f=0.0315 66 -> 72 0.51294 67 -> 72 0.35430 68 -> 72-0.24094 S22
70 -> 73-0.10867 71 -> 75 0.12952 Excited State 8: Singlet-A 5.3276 ev 232.72 nm f=0.0214 66 -> 72 0.15434 67 -> 72-0.15459 68 -> 72 0.14084 68 -> 73-0.11023 69 -> 73 0.53157 71 -> 74-0.32558 Excited State 9: Singlet-A 5.3322 ev 232.52 nm f=0.0436 66 -> 72-0.24170 67 -> 72 0.17890 68 -> 72-0.13444 68 -> 73 0.13607 69 -> 73 0.42580 71 -> 74 0.39992 Excited State 10: Singlet-A 5.6486 ev 219.50 nm f=0.0003 66 -> 72-0.28297 67 -> 72 0.41806 68 -> 72 0.15848 68 -> 73-0.38792 69 -> 74-0.11588 71 -> 74-0.14290 71 -> 75 0.14665 Excited State 11: Singlet-A 5.9749 ev 207.51 nm f=0.1503 66 -> 73-0.15095 67 -> 73-0.21271 70 -> 74 0.59289 71 -> 75-0.18531 Excited State 12: Singlet-A 5.9967 ev 206.75 nm f=0.0741 66 -> 73 0.22118 67 -> 73 0.37341 68 -> 73 0.19859 70 -> 74 0.32283 71 -> 75 0.36983 Excited State 13: Singlet-A 6.1026 ev 203.16 nm f=0.0177 64 -> 72-0.12584 65 -> 72 0.36867 66 -> 73-0.33866 67 -> 72-0.16425 69 -> 74-0.25080 71 -> 75 0.31844 Excited State 14: Singlet-A 6.1211 ev 202.55 nm f=0.0112 64 -> 72-0.17720 65 -> 72 0.53001 66 -> 73 0.24550 S23
67 -> 72 0.10139 69 -> 74 0.20823 71 -> 75-0.19620 Excited State 15: Singlet-A 6.1601 ev 201.27 nm f=0.1758 67 -> 72 0.16088 67 -> 73-0.29098 68 -> 73 0.45189 69 -> 74-0.17585 69 -> 75-0.30902 70 -> 73-0.10557 71 -> 74-0.15261 Excited State 16: Singlet-A 6.1833 ev 200.52 nm f=0.0359 66 -> 73 0.47171 67 -> 72-0.11272 67 -> 73-0.25588 68 -> 73-0.13394 69 -> 74-0.39278 71 -> 74 0.12967 Excited State 17: Singlet-A 6.3687 ev 194.68 nm f=0.0009 63 -> 72-0.25075 64 -> 72 0.59719 65 -> 72 0.22626 Excited State 18: Singlet-A 6.5600 ev 189.00 nm f=0.0703 67 -> 74 0.14220 68 -> 74-0.24438 70 -> 75 0.62870 Excited State 19: Singlet-A 6.6298 ev 187.01 nm f=0.0012 60 -> 72-0.14997 62 -> 72-0.36433 63 -> 72 0.50739 64 -> 72 0.23618 Excited State 20: Singlet-A 6.7231 ev 184.42 nm f=0.0016 71 -> 76 0.59151 71 -> 77 0.33042 71 -> 78-0.12001 71 -> 79 0.11282 S24
MeOBF HOMO = 51, LUMO = 52 Excited State 1: Singlet-A' 3.2773 ev 378.31 nm f=0.0081 51 -> 52 0.70013 Excited State 2: Singlet-A' 4.0665 ev 304.89 nm f=0.0009 50 -> 52 0.54722 51 -> 53-0.43062 Excited State 3: Singlet-A' 4.5905 ev 270.09 nm f=0.0612 48 -> 52-0.10261 49 -> 52 0.58523 49 -> 53 0.10899 50 -> 52-0.18109 51 -> 53-0.15423 51 -> 54-0.24551 Excited State 4: Singlet-A" 4.7557 ev 260.70 nm f=0.0000 47 -> 52 0.70422 Excited State 5: Singlet-A' 4.9238 ev 251.81 nm f=0.8467 49 -> 52 0.20598 50 -> 52 0.39610 51 -> 53 0.52643 Excited State 6: Singlet-A' 5.2209 ev 237.48 nm f=0.0313 48 -> 52 0.61796 49 -> 52 0.11466 49 -> 53-0.20940 50 -> 53 0.12717 51 -> 54-0.15419 51 -> 55 0.12280 Excited State 7: Singlet-A' 5.2739 ev 235.09 nm f=0.0128 48 -> 52-0.11646 49 -> 52 0.17790 49 -> 53-0.23252 S25
50 -> 53 0.47998 50 -> 54 0.11252 51 -> 54 0.37162 Excited State 8: Singlet-A' 5.4104 ev 229.16 nm f=0.0546 49 -> 52-0.18250 49 -> 53 0.33804 50 -> 53 0.46936 51 -> 54-0.31678 Excited State 9: Singlet-A" 5.8105 ev 213.38 nm f=0.0000 47 -> 53 0.69928 Excited State 10: Singlet-A' 5.8657 ev 211.37 nm f=0.1119 48 -> 52 0.12720 48 -> 53 0.30611 49 -> 53 0.37918 50 -> 55-0.11727 51 -> 54 0.29557 51 -> 55 0.35735 Excited State 11: Singlet-A" 5.9978 ev 206.72 nm f=0.0007 45 -> 52 0.69708 Excited State 12: Singlet-A' 6.1184 ev 202.64 nm f=0.1453 46 -> 52-0.12340 48 -> 52-0.17564 48 -> 53 0.21110 49 -> 53-0.22098 50 -> 54 0.33280 50 -> 55 0.18697 51 -> 54-0.17756 51 -> 55 0.41248 Excited State 13: Singlet-A' 6.1721 ev 200.88 nm f=0.0570 48 -> 53 0.46816 49 -> 53-0.18477 50 -> 54-0.40161 50 -> 55 0.21474 51 -> 55-0.14435 Excited State 14: Singlet-A" 6.3366 ev 195.66 nm f=0.0014 44 -> 52 0.69748 Excited State 15: Singlet-A' 6.4254 ev 192.96 nm f=0.0190 46 -> 52 0.66745 50 -> 55 0.15290 Excited State 16: Singlet-A" 6.5591 ev 189.03 nm f=0.0003 43 -> 52 0.68842 Excited State 17: Singlet-A' 6.6744 ev 185.76 nm f=0.2243 49 -> 54 0.64610 50 -> 54-0.16789 Excited State 18: Singlet-A" 6.7739 ev 183.03 nm f=0.0013 41 -> 52 0.12166 S26
45 -> 53-0.21494 47 -> 54 0.61363 51 -> 56 0.17559 Excited State 19: Singlet-A" 6.7786 ev 182.90 nm f=0.0012 47 -> 54-0.15995 51 -> 56 0.67778 Excited State 20: Singlet-A' 6.8906 ev 179.93 nm f=0.0520 42 -> 52-0.12795 48 -> 54 0.40865 49 -> 55 0.47059 50 -> 55-0.17972 51 -> 57-0.17040 S27
Table S2. UV-Vis absorption and emission data of the borafluorenes. Compound Absorption λ max /nm (log ε) ClBF 252 (4.26) Absorption Onset λ max /nm Emission /nm (φ f ) [/cm -1 ] 420 438 (0.03) Calculated H-L /H-L+1 Calculated Emission /nm GAPs/eV a [/cm -1 ] 3.66, 4.98 565 Calculated Absorption /nm (oscillator strength) [transition] 256(0.92) (H L+1) 286 (4.06) [22,830] [17,700] 286(0.04) 364 (3.09) 325(0.03) 435(0.00) (H L) TipBF 262 (4.89) 464 517 (0.10) 3.66, 4.94 570 257(0.83) (H L+1) 266 (5.05) [19,340] [17,540] 264(0.02) 298 (3.81) 283(0.04) 323 (3.59) 325(0.03) 339 (3.54) 424(0.01) 358 (3.39) 435(0.00) (H L) 406 (2.75) Mes F BF 250(5920, 3.77) 272(5252, 3.72 ) 298 (2918, 3.46) 496 550 (0.06) [18,180] 3.60, 4.99 b 619 [16,160] 256(0.76) (H L+3) 277(0.01) 287(0.06) 329(0.04) 445(0.00) (H L) 326 (2418, 3.38) 340 (1928, 3.29) 414 (243, 2.39) TipBF(OMe) 2 272 (11040, 4.04) 284 (12690, 4.10) 304 (4530, 3.66) 340 (1395, 3.14) 478 499 (0.10) [20,040] 3.71, 4.64 538 [18,590] 246(0.29) 260(0.02) 268(0.02) 277(0.79) (H L+1) 295(0.20) 337(0.02) 417(0.02) (H L) 398 (630,2.80) i Pr 2 NBF 248 (30000, 4.48) 260 (37615, 4.58) 270 (10469, 380 439 (0.07) [22,780] 4.17, 4.89 463 [21,600] 253(0.66) (H L+1) 258(0.05) 285(0.19) 298(0.02) S28
4.02) 361(0.01) (H L) 296 (10730, 4.03) 354 (520, 2.72) t BuOBF 248 (4.21) 404 443 (0.02) 4.05/4.94 485 252(0.85) (H L+1) 284 (4.21) 22,570 [20,620] 270(0.06) 314 (4.00) 378(0.01) (H L) 364(3.32) Table S3. Crystallographic Data Compound Mes F BF ipr 2 NBF TipBF(OMe) 2 Empirical formula C 21 H 10 B F 9 C 18 H 22 BN C 29 H 35 BO 2 Formula weight 444.10 263.18 426.38 Temperature (K) 173(2) 173(2) 173(2) Wavelength (Å) 0.71073 0.71073 0.71073 Crystal system Monoclinic orthorhombic monoclinic Space group Cc Pbcn P 21/c a (Å) 13.8383(7) 21.983(3) 15.9247(4) b (Å) 33.6770(17) 15.019(2) 10.6597(3) c (Å) 8.1729(4) 9.2362(14) 16.2801(5) α ( ) 90 90 90 β ( ) 94.676(3) 90 113.8860(10) γ ( ) 90 90 90 Volume (Å 3 ) 3796.2(3) 3049.3(8) 2526.89(12) Z 8 8 4 F(000) 1776 1080 920 Color yellow colorless yellow Crystal size (mm 3 ) 0.16x0.10x0.06 0.16x0.11x0.09 0.39x0.33x0.32 θ range for data collection ( o ) 1.209-26.459 1.642-26.258 1.398-30.578 Data/restraints/parameters 7764/2/559 3077/0/196 7754/0/297 Goodness-of-fit F 2 (all data) 1.050 1.721 1.077 Final R indices [I>2σ(I)] 0.040 0.0847 0.0522 wr2 indices (all data) 0.1109 0.2164 0.1594 S29