s 1 · 2019. 5. 21. · 2. dft calculation data table s 1.c oordinates of the opti mized gas -phase...
TRANSCRIPT
Supporting Information for
Charge-Separated Mixed Valency in an Unsymmetrical Acceptor–Donor–DonorCharge-Separated Mixed Valency in an Unsymmetrical Acceptor–Donor–DonorTriad Based on Diarylboryl and Triarylamine Units
Keishiro Tahara, *a Haruya Koyama,b Mamoru Fujitsuka,c Ken Tokunaga,d Xu Lei,c Tetsuro Majima,*c Jun-ichi Kikuchi,b Yoshiki Ozawa,a and Masaaki Abe*a
a Department of Material Science and Research Center for New Functional Materials, Graduate School of Material Science, University of Hyogo, 3-2-1, Kouto, Kamigori, Ako 678-1297, JapanAko 678-1297, Japanb Graduate School of Materials Science, Nara Institute of Science and Technology, 8916-5, Takayama, Ikoma 630-0192, Japanc Institute of Scientific and Industrial Research (SANKEN), Osaka University, 8-1, Mihogaoka, Ibaraki, Osaka, 5670-047, Japand Division of Liberal Arts, Centre for Promotion of Higher Education, Kogakuin University, 2665-1, Nakano, Hachioji, Tokyo 1920-015, Japan
Contents1. Characterization of new compounds2. DFT calculation data3. UV-vis-NIR spectral data4. Photophysical properties
S1
1. Characterization of new compounds
Figure S1. 1H-NMR spectrum of 3 in DMSO-d6 (600 MHz).
S2
6
S2
Figure S2. 13C-NMR spectrum of 3 in DMSO-d6 (150 MHz).
S3
6
S3
Figure S3. HR-EI-MS of 3. Inset: experimental (bottom) and theoretical (top) isotopic distributions for [M]+.
S4S4
Figure S4. 1H-NMR spectrum of 2 in DMSO-d6 (600 MHz).
S5
6
S5
Figure S5. 13C-NMR spectrum of 2 in DMSO-d6 (150 MHz).
S6
6
S6
Figure S6. HR-ESI-MS of 2. Inset: experimental (bottom) and theoretical (top) isotopic distributions for [M]+.
S7S7
Figure S7. 1H-NMR spectrum of NB′in DMSO-d6 (600 MHz).
S8
6
S8
Figure S8. 13C-NMR spectrum of NB′ in DMSO-d6 (150 MHz).
S9
6
S9
Figure S9. HR-ESI-MS of NB′. Inset: experimental (bottom) and theoretical (top) isotopic distributions for [M]+.
S10S10
2. DFT calculation dataTable S1. Coordinates of the optimized gas-phase geometries of NAr3 derivatives.
22CenterNumber
AtomicNumber
Coordinates (Å) UnitX Y Z
1 6 8.727557 -4.02647 -2.38703 TPA22 6 9.162497 -3.85991 -1.06766 TPA23 6 7.883775 -3.06205 -2.95803 TPA24 6 8.744446 -2.74905 -0.33151 TPA25 1 9.812119 -4.58881 -0.59644 TPA26 1 7.560569 -3.19815 -3.98547 TPA27 6 7.491584 -1.94916 -2.22784 TPA28 6 7.911119 -1.77777 -0.89643 TPA29 1 9.077006 -2.63302 0.69537 TPA29 1 9.077006 -2.63302 0.69537 TPA210 1 6.850998 -1.20167 -2.68545 TPA211 7 7.513243 -0.63317 -0.14659 TPA212 6 6.164959 -0.21254 -0.13925 TPA213 6 8.49528 0.076969 0.603546 TPA214 6 5.114169 -1.144 -0.22219 TPA215 6 5.832825 1.151465 -0.04874 TPA216 6 8.257523 0.438012 1.941775 TPA217 6 9.726148 0.415099 0.031306 TPA218 1 5.342391 -2.20349 -0.27371 TPA219 6 3.789859 -0.72227 -0.22064 TPA220 6 4.504302 1.558989 -0.03477 TPA221 1 6.624364 1.892248 -0.00343 TPA221 1 6.624364 1.892248 -0.00343 TPA222 1 7.310362 0.177531 2.403787 TPA223 6 9.216544 1.124986 2.672314 TPA224 6 10.70532 1.086318 0.7672 TPA225 1 9.925172 0.143498 -1.00079 TPA226 1 3.003583 -1.47162 -0.25341 TPA227 6 3.445639 0.637676 -0.12331 TPA228 1 4.285037 2.622601 0.004678 TPA229 1 9.036544 1.40646 3.705259 TPA230 6 10.45213 1.45187 2.093883 TPA231 1 11.64893 1.327291 0.29098 TPA232 6 2.033344 1.080144 -0.11374 TPA133 6 1.618043 2.190304 0.643476 TPA133 6 1.618043 2.190304 0.643476 TPA134 6 1.049318 0.410216 -0.86328 TPA135 6 0.291727 2.607861 0.659436 TPA136 1 2.340551 2.714364 1.262883 TPA137 1 1.335412 -0.42831 -1.49206 TPA138 6 -0.27737 0.826786 -0.86354 TPA139 6 -0.67853 1.930781 -0.09485 TPA140 1 -0.00253 3.457387 1.267634 TPA141 1 -1.00966 0.303608 -1.47048 TPA142 7 -2.03093 2.373891 -0.09806 TPA143 6 -3.1001 1.462918 -0.01329 TPA144 6 -2.28793 3.777178 -0.18832 TPA1
S11
44 6 -2.28793 3.777178 -0.18832 TPA145 6 -2.96552 0.247212 0.688764 TPA146 6 -4.3402 1.749328 -0.62002 TPA147 6 -3.13081 4.411945 0.739535 TPA148 6 -1.68977 4.548295 -1.18868 TPA1
49 1 -2.0235 0.010476 1.171999 TPA150 6 -4.03434 -0.63244 0.779431 TPA151 6 -5.39017 0.846585 -0.5315 TPA152 1 -4.46435 2.676331 -1.16984 TPA152 1 -4.46435 2.676331 -1.16984 TPA153 1 -3.59602 3.825117 1.525532 TPA154 6 -3.37432 5.775257 0.65627 TPA155 6 -1.91299 5.924715 -1.26729 TPA156 1 -1.03602 4.068816 -1.91086 TPA157 1 -3.90397 -1.55087 1.345547 TPA158 6 -5.28617 -0.37544 0.172928 TPA159 1 -6.32648 1.088461 -1.02744 TPA160 1 -4.02518 6.272321 1.36873 TPA161 6 -2.76385 6.545562 -0.34545 TPA162 1 -1.42989 6.493175 -2.05371 TPA163 5 -6.4796 -1.37649 0.277964 BMes264 6 -6.44874 -2.49923 1.40388 BMes64 6 -6.44874 -2.49923 1.40388 BMes265 6 -7.69228 -1.24418 -0.74253 BMes266 6 -6.36667 -2.17825 2.782165 BMes267 6 -6.46505 -3.87954 1.050928 BMes268 6 -7.5082 -1.34026 -2.14517 BMes269 6 -9.01044 -0.98195 -0.26997 BMes270 6 -6.3005 -3.19692 3.744967 BMes271 6 -6.41628 -0.75538 3.308072 BMes272 6 -6.38191 -4.86215 2.037445 BMes273 6 -6.53465 -4.33158 -0.39366 BMes274 6 -8.59624 -1.1789 -3.01601 BMes275 6 -6.17673 -1.68626 -2.78604 BMes276 6 -10.0634 -0.81371 -1.16969 BMes277 6 -9.31376 -0.83546 1.20759 BMes278 6 -6.30132 -4.54455 3.398461 BMes279 1 -6.24679 -2.91943 4.797034 BMes280 1 -6.28015 -0.0065 2.526875 BMes281 1 -5.64048 -0.591 4.065517 BMes282 1 -7.38161 -0.55773 3.793097 BMes283 1 -6.37915 -5.90896 1.736826 BMes284 1 -6.52819 -5.4245 -0.45866 BMes285 1 -5.68212 -3.965 -0.97814 BMes286 1 -7.44142 -3.96932 -0.88882 BMes287 6 -9.88176 -0.91283 -2.55384 BMes287 6 -9.88176 -0.91283 -2.55384 BMes288 1 -8.42492 -1.26546 -4.08833 BMes289 1 -5.33454 -1.58691 -2.1001 BMes290 1 -5.9803 -1.04149 -3.65097 BMes291 1 -6.18365 -2.72056 -3.15555 BMes292 1 -11.0569 -0.59628 -0.78036 BMes293 1 -10.3797 -0.64289 1.367189 BMes294 1 -8.76097 -0.00157 1.657313 BMes295 1 -9.04583 -1.73633 1.768759 BMes296 6 -6.21876 -5.63118 4.444565 BMes297 6 -11.0448 -0.74694 -3.50339 BMes298 1 -6.15624 -5.211 5.453563 BMes299 1 -5.33795 -6.26782 4.292227 BMes2
S12
99 1 -5.33795 -6.26782 4.292227 BMes2100 1 -7.09693 -6.28858 4.410094 BMes2101 1 -11.7506 -1.58411 -3.42175 BMes2102 1 -10.7079 -0.69957 -4.54407 BMes2
103 1 -11.61 0.168563 -3.29029 BMes2104 8 11.33046 2.117339 2.903087 TPA2105 8 -3.06009 7.878248 -0.33169 TPA1106 8 9.065054 -5.07645 -3.19496 TPA2106 8 9.065054 -5.07645 -3.19496 TPA2107 6 9.914213 -6.07986 -2.66456 TPA2108 1 9.459553 -6.57893 -1.79812 TPA2109 1 10.05576 -6.80793 -3.46555 TPA2110 1 10.89023 -5.67025 -2.37088 TPA2111 6 12.59373 2.473014 2.367617 TPA2112 1 12.49377 3.153085 1.510842 TPA2113 1 13.12773 2.983501 3.171349 TPA2114 1 13.16607 1.588035 2.057917 TPA2115 6 -2.47199 8.706083 -1.32187 TPA1116 1 -2.77604 8.405252 -2.33338 TPA1117 1 -2.83523 9.715876 -1.12235 TPA1118 1 -1.37565 8.69627 -1.25805 TPA1118 1 -1.37565 8.69627 -1.25805 TPA1Lowest frequency = 5.17 cm−1
Total energy = −2565.23710456 hartree (1 hartree = 627.5095 kcal/mol)
2•+
CenterNumber
AtomicNumber
Coordinates (Å) UnitX Y Z
1 6 8.621357 -4.36294 -1.81612 TPA22 6 9.095328 -3.9913 -0.54755 TPA23 6 7.763663 -3.49344 -2.51627 TPA23 6 7.763663 -3.49344 -2.51627 TPA24 6 8.710861 -2.7738 0.006758 TPA25 1 9.751018 -4.64445 0.015719 TPA26 1 7.421312 -3.7885 -3.50262 TPA27 6 7.388357 -2.2821 -1.96239 TPA28 6 7.854324 -1.9086 -0.68717 TPA29 1 9.070128 -2.4952 0.992107 TPA210 1 6.744352 -1.60836 -2.51852 TPA211 7 7.483388 -0.65626 -0.11628 TPA212 6 6.157285 -0.22792 -0.13379 TPA213 6 8.501637 0.144679 0.47844 TPA214 6 5.09091 -1.15902 -0.14078 TPA215 6 5.837845 1.151315 -0.14285 TPA215 6 5.837845 1.151315 -0.14285 TPA216 6 8.30758 0.728212 1.745192 TPA217 6 9.72234 0.338366 -0.1819 TPA218 1 5.307723 -2.22028 -0.09689 TPA219 6 3.779892 -0.72666 -0.15464 TPA220 6 4.521827 1.567985 -0.15418 TPA221 1 6.635862 1.884359 -0.1762 TPA222 1 7.375542 0.564088 2.276543 TPA223 6 9.306424 1.491878 2.323402 TPA224 6 10.73199 1.101966 0.39691 TPA225 1 9.878467 -0.10423 -1.16042 TPA226 1 2.99209 -1.47118 -0.10608 TPA227 6 3.443387 0.649419 -0.15971 TPA2
S13
27 6 3.443387 0.649419 -0.15971 TPA228 1 4.319922 2.632506 -0.21151 TPA229 1 9.174253 1.937194 3.303931 TPA230 6 10.53056 1.68866 1.656714 TPA2
31 1 11.66206 1.241903 -0.14097 TPA232 6 2.054833 1.098141 -0.16442 TPA133 6 1.683438 2.369272 0.3373 TPA134 6 1.010775 0.282421 -0.66498 TPA134 6 1.010775 0.282421 -0.66498 TPA135 6 0.370519 2.796378 0.348282 TPA136 1 2.436755 3.013475 0.778985 TPA137 1 1.246847 -0.67815 -1.11126 TPA138 6 -0.30614 0.696871 -0.6639 TPA139 6 -0.66289 1.966729 -0.14942 TPA140 1 0.121082 3.760421 0.776484 TPA141 1 -1.07197 0.057653 -1.08797 TPA142 7 -1.98964 2.392301 -0.13824 TPA143 6 -3.06536 1.46046 -0.05177 TPA144 6 -2.30527 3.783546 -0.20536 TPA145 6 -3.00764 0.384656 0.850186 TPA146 6 -4.20711 1.633146 -0.85066 TPA146 6 -4.20711 1.633146 -0.85066 TPA147 6 -3.22319 4.343053 0.702197 TPA148 6 -1.72477 4.60142 -1.18267 TPA149 1 -2.13843 0.263475 1.489236 TPA150 6 -4.07811 -0.49754 0.941662 TPA151 6 -5.25854 0.728985 -0.75558 TPA152 1 -4.25349 2.462456 -1.5492 TPA153 1 -3.67512 3.715945 1.463901 TPA154 6 -3.54267 5.687562 0.632144 TPA155 6 -2.0386 5.956962 -1.25511 TPA156 1 -1.03281 4.171795 -1.90038 TPA157 1 -4.02946 -1.30921 1.661786 TPA158 6 -5.23379 -0.36014 0.142561 TPA159 1 -6.12446 0.861091 -1.39771 TPA160 1 -4.24323 6.134316 1.329823 TPA161 6 -2.95359 6.510583 -0.3462 TPA162 1 -1.58231 6.564765 -2.02739 TPA163 5 -6.44734 -1.3724 0.25356 BMes264 6 -6.60603 -2.20702 1.585951 BMes265 6 -7.43785 -1.49228 -0.97179 BMes266 6 -6.7032 -1.58745 2.858441 BMes267 6 -6.60423 -3.63276 1.542447 BMes268 6 -6.98996 -1.81466 -2.27913 BMes269 6 -8.82673 -1.21965 -0.79692 BMes269 6 -8.82673 -1.21965 -0.79692 BMes270 6 -6.77748 -2.36656 4.021363 BMes271 6 -6.82936 -0.08649 3.03954 BMes272 6 -6.6626 -4.36969 2.724949 BMes273 6 -6.50322 -4.39776 0.237646 BMes274 6 -7.89323 -1.84369 -3.35015 BMes275 6 -5.56452 -2.23508 -2.58227 BMes276 6 -9.68887 -1.24416 -1.89317 BMes277 6 -9.41195 -0.85647 0.553524 BMes278 6 -6.75223 -3.75812 3.981566 BMes279 1 -6.86551 -1.86478 4.983799 BMes280 1 -6.56155 0.478406 2.1449 BMes281 1 -6.19557 0.266278 3.861742 BMes2
S14
81 1 -6.19557 0.266278 3.861742 BMes282 1 -7.86227 0.181989 3.297632 BMes283 1 -6.64055 -5.45656 2.667197 BMes284 1 -6.51088 -5.47646 0.422104 BMes2
85 1 -5.57808 -4.16801 -0.3054 BMes286 1 -7.33531 -4.16571 -0.43443 BMes287 6 -9.24614 -1.55771 -3.18384 BMes288 1 -7.52399 -2.10459 -4.3408 BMes288 1 -7.52399 -2.10459 -4.3408 BMes289 1 -4.85981 -1.95907 -1.79571 BMes290 1 -5.21329 -1.78952 -3.5203 BMes291 1 -5.50448 -3.32469 -2.70578 BMes292 1 -10.7408 -1.01111 -1.73809 BMes293 1 -10.4891 -0.68157 0.472158 BMes294 1 -8.96537 0.05744 0.964399 BMes295 1 -9.25489 -1.64973 1.29102 BMes296 6 -6.82636 -4.58693 5.241435 BMes297 6 -10.2106 -1.59791 -4.34475 BMes298 1 -6.8898 -3.95609 6.133432 BMes299 1 -5.94506 -5.23175 5.347769 BMes2100 1 -7.70384 -5.24534 5.23358 BMes100 1 -7.70384 -5.24534 5.23358 BMes2101 1 -10.909 -2.43952 -4.25153 BMes2102 1 -9.68561 -1.7075 -5.29886 BMes2103 1 -10.8158 -0.68499 -4.39405 BMes2104 8 11.43842 2.447077 2.310282 TPA2105 8 -3.33507 7.807971 -0.32577 TPA1106 8 8.928011 -5.51701 -2.44897 TPA2107 6 9.803477 -6.44404 -1.81039 TPA2108 1 9.378512 -6.80636 -0.86657 TPA2109 1 9.907407 -7.27733 -2.50572 TPA2110 1 10.78774 -5.99741 -1.62478 TPA2111 6 12.70831 2.67941 1.704412 TPA2112 1 12.60248 3.213632 0.752521 TPA2113 1 13.26174 3.299688 2.409838 TPA2114 1 13.24849 1.738949 1.541921 TPA2115 6 -2.78916 8.702729 -1.29119 TPA1116 1 -3.05019 8.395194 -2.31115 TPA1117 1 -3.2369 9.674018 -1.0791 TPA1118 1 -1.69875 8.774415 -1.19568 TPA1Lowest frequency = 4.86 cm−1
Total energy = − 2565.03997666 hartree (1 hartree = 627.5095 kcal/mol)
1Center
NumberAtomicNumber
Coordinates (Å) UnitX Y Z
1 6 -7.12594 -3.50013 1.13948 TPA22 6 -7.494 -2.78309 -0.00414 TPA23 6 -6.03036 -3.06396 1.899378 TPA24 6 -6.76473 -1.6537 -0.38231 TPA25 1 -8.33248 -3.09666 -0.61556 TPA26 1 -5.75982 -3.62422 2.789111 TPA27 6 -5.32464 -1.92758 1.529659 TPA28 6 -5.67808 -1.20501 0.375946 TPA29 1 -7.05006 -1.10884 -1.2769 TPA2
S15
9 1 -7.05006 -1.10884 -1.2769 TPA210 1 -4.48788 -1.59104 2.133901 TPA211 7 -4.96235 -0.033 -0.00335 TPA212 6 -3.54894 -0.02818 -0.02385 TPA2
13 6 -5.69639 1.134232 -0.36187 TPA214 6 -2.82486 -1.18729 -0.35577 TPA215 6 -2.82405 1.136216 0.287008 TPA216 6 -5.37996 1.859642 -1.52456 TPA216 6 -5.37996 1.859642 -1.52456 TPA217 6 -6.76435 1.575623 0.426596 TPA218 1 -3.35915 -2.09453 -0.61832 TPA219 6 -1.4348 -1.1774 -0.36705 TPA220 6 -1.43431 1.136551 0.257542 TPA221 1 -3.35716 2.039542 0.565003 TPA222 1 -4.55843 1.528849 -2.1524 TPA223 6 -6.10283 2.991781 -1.87364 TPA224 6 -7.51096 2.700604 0.069667 TPA225 1 -7.02133 1.028585 1.328439 TPA226 1 -0.9083 -2.08266 -0.65737 TPA227 6 -0.69896 -0.01772 -0.06543 TPA228 1 -0.90631 2.045724 0.532528 TPA228 1 -0.90631 2.045724 0.532528 TPA229 1 -5.86088 3.55406 -2.7703 TPA230 6 -7.17943 3.420703 -1.08313 TPA231 1 -8.33398 3.008277 0.704696 TPA232 6 0.780652 -0.01182 -0.08535 TPA133 6 1.505789 1.116687 -0.5084 TPA134 6 1.526486 -1.13285 0.319401 TPA135 6 2.895321 1.127856 -0.53265 TPA136 1 0.969644 1.991935 -0.86553 TPA137 1 1.007679 -2.01423 0.686946 TPA138 6 2.916917 -1.12923 0.313871 TPA139 6 3.630405 0.003586 -0.11582 TPA140 1 3.421453 2.00792 -0.888 TPA141 1 3.459332 -2.00399 0.657528 TPA142 7 5.044611 0.014134 -0.13049 TPA143 6 5.774241 -1.17854 -0.40194 TPA144 6 5.761485 1.207489 0.171613 TPA145 6 5.430417 -2.00196 -1.4894 TPA146 6 6.862531 -1.55035 0.394596 TPA147 6 6.849919 1.607353 -0.62398 TPA148 6 5.411441 2.004185 1.267367 TPA149 1 4.593409 -1.72607 -2.12327 TPA150 6 6.145321 -3.16072 -1.75643 TPA151 6 7.601441 -2.70304 0.117937 TPA151 6 7.601441 -2.70304 0.117937 TPA152 1 7.142052 -0.92723 1.238459 TPA153 1 7.134887 1.001871 -1.4788 TPA154 6 7.563085 2.759688 -0.32553 TPA155 6 6.109462 3.178112 1.560015 TPA156 1 4.577965 1.708448 1.896992 TPA157 1 5.881705 -3.79877 -2.59433 TPA158 6 7.241695 -3.5207 -0.95841 TPA159 1 8.441126 -2.95423 0.756125 TPA160 1 8.404195 3.070308 -0.93769 TPA161 6 7.19641 3.560329 0.766349 TPA162 1 5.803978 3.771364 2.414483 TPA163 8 -7.83438 4.538035 -1.52244 TPA2
S16
63 8 -7.83438 4.538035 -1.52244 TPA264 8 7.955546 4.680134 0.966812 TPA165 8 -7.76126 -4.62111 1.597795 TPA266 6 -8.87641 -5.1015 0.866798 TPA2
67 1 -8.59845 -5.38497 -0.1574 TPA268 1 -9.22789 -5.98593 1.401656 TPA269 1 -9.68439 -4.35836 0.825878 TPA270 6 -8.93174 5.010426 -0.76006 TPA270 6 -8.93174 5.010426 -0.76006 TPA271 1 -8.62707 5.295133 0.256185 TPA272 1 -9.30406 5.8928 -1.2841 TPA273 1 -9.73323 4.261839 -0.69703 TPA274 6 7.623526 5.524293 2.055735 TPA175 1 7.710081 4.999364 3.016769 TPA176 1 8.341952 6.34587 2.028982 TPA177 1 6.606965 5.92921 1.959238 TPA178 8 7.885539 -4.67357 -1.31451 OCH379 6 8.998851 -5.08184 -0.53847 OCH380 1 8.716689 -5.27435 0.50554 OCH381 1 9.356816 -6.00878 -0.99067 OCH382 1 9.803618 -4.33446 -0.55995 OCH82 1 9.803618 -4.33446 -0.55995 OCH3
Lowest frequency = 9.17 cm−1
Total energy = −1956.29057656 hartree (1 hartree = 627.5095 kcal/mol)
1•+
CenterNumber
AtomicNumber
Coordinates (Å) UnitX Y Z
1 6 -7.135762 -3.475401 1.108814 TPA22 6 -7.484786 -2.753199 -0.043318 TPA23 6 -6.046037 -3.046916 1.889473 TPA23 6 -6.046037 -3.046916 1.889473 TPA24 6 -6.75057 -1.626812 -0.404648 TPA25 1 -8.315084 -3.063857 -0.666106 TPA26 1 -5.800492 -3.606444 2.786093 TPA27 6 -5.322991 -1.922829 1.528323 TPA28 6 -5.664204 -1.19994 0.369653 TPA29 1 -7.018269 -1.077169 -1.301317 TPA210 1 -4.498188 -1.587286 2.149043 TPA211 7 -4.936943 -0.029552 -0.000067 TPA212 6 -3.544402 -0.026238 -0.01445 TPA213 6 -5.676803 1.137239 -0.355953 TPA214 6 -2.814123 -1.219582 -0.231875 TPA215 6 -2.816112 1.171009 0.187584 TPA215 6 -2.816112 1.171009 0.187584 TPA216 6 -5.360835 1.86162 -1.520863 TPA217 6 -6.750316 1.559241 0.43867 TPA218 1 -3.346437 -2.143821 -0.425433 TPA219 6 -1.433524 -1.208029 -0.24332 TPA220 6 -1.435646 1.167052 0.168496 TPA221 1 -3.349158 2.092313 0.392761 TPA222 1 -4.546521 1.529745 -2.157199 TPA223 6 -6.095436 2.982561 -1.868192 TPA224 6 -7.496169 2.682401 0.091286 TPA225 1 -6.998714 1.008403 1.340153 TPA226 1 -0.913833 -2.134829 -0.463496 TPA227 6 -0.690885 -0.018378 -0.04578 TPA2
S17
27 6 -0.690885 -0.018378 -0.04578 TPA228 1 -0.916328 2.096731 0.377126 TPA229 1 -5.869439 3.543045 -2.76934 TPA230 6 -7.172028 3.406279 -1.067015 TPA2
31 1 -8.316023 2.989203 0.72968 TPA232 6 0.768382 -0.013702 -0.061685 TPA133 6 1.504565 1.152641 -0.384006 TPA134 6 1.519433 -1.174628 0.245027 TPA134 6 1.519433 -1.174628 0.245027 TPA135 6 2.884969 1.165575 -0.400209 TPA136 1 0.978456 2.054396 -0.679863 TPA137 1 1.005977 -2.081003 0.54896 TPA138 6 2.900192 -1.17679 0.235758 TPA139 6 3.621478 -0.002527 -0.088022 TPA140 1 3.412267 2.067728 -0.688751 TPA141 1 3.43945 -2.075347 0.513227 TPA142 7 5.014827 0.003878 -0.099503 TPA143 6 5.750389 -1.184962 -0.38017 TPA144 6 5.742474 1.19924 0.1756 TPA145 6 5.40309 -2.002835 -1.472333 TPA146 6 6.849941 -1.537989 0.412941 TPA146 6 6.849941 -1.537989 0.412941 TPA147 6 6.822029 1.575256 -0.645572 TPA148 6 5.412527 1.999565 1.277302 TPA149 1 4.569016 -1.725538 -2.109121 TPA150 6 6.131779 -3.146561 -1.74917 TPA151 6 7.590232 -2.683961 0.135437 TPA152 1 7.123236 -0.914636 1.258193 TPA153 1 7.083274 0.962886 -1.502494 TPA154 6 7.54125 2.725102 -0.371396 TPA155 6 6.129424 3.161135 1.554868 TPA156 1 4.597665 1.704584 1.930985 TPA157 1 5.881441 -3.779419 -2.594178 TPA158 6 7.234176 -3.501132 -0.94909 TPA159 1 8.431108 -2.935147 0.770856 TPA160 1 8.369498 3.031222 -1.001861 TPA161 6 7.202952 3.533 0.730705 TPA162 1 5.857443 3.755617 2.418866 TPA163 8 -7.826726 4.508318 -1.498627 TPA264 8 7.968875 4.633329 0.907945 TPA165 8 -7.77736 -4.580097 1.553005 TPA266 6 -8.903396 -5.062619 0.823996 TPA267 1 -8.622447 -5.354356 -0.195261 TPA268 1 -9.253439 -5.939531 1.369263 TPA269 1 -9.702748 -4.312668 0.785558 TPA269 1 -9.702748 -4.312668 0.785558 TPA270 6 -8.941105 4.985301 -0.748438 TPA271 1 -8.642421 5.278311 0.265414 TPA272 1 -9.305637 5.86056 -1.286827 TPA273 1 -9.735952 4.231501 -0.695018 TPA274 6 7.687675 5.499668 2.00415 TPA175 1 7.799683 4.977791 2.962309 TPA176 1 8.421674 6.303381 1.940299 TPA177 1 6.677413 5.920298 1.929517 TPA178 8 7.879555 -4.633735 -1.308388 OCH379 6 9.017328 -5.047028 -0.555211 OCH380 1 8.749607 -5.255317 0.487773 OCH381 1 9.367661 -5.963764 -1.030194 OCH3
S18
81 1 9.367661 -5.963764 -1.030194 OCH382 1 9.811376 -4.291336 -0.588321 OCH3
Lowest frequency = 10.19 cm−1
Total energy = − 1956.09860060 hartree (1 hartree = 627.5095 kcal/mol)
2*
Center Atomic Coordinates (Å) UnitCenterNumber
AtomicNumber
Coordinates (Å) UnitX Y Z
1 6 8.403161 -4.813713 -0.377361 TPA2 6 8.947266 -4.093653 0.695826 TPA3 6 7.549558 -4.162926 -1.284616 TPA4 6 8.631062 -2.745668 0.858136 TPA5 1 9.60554 -4.571056 1.411848 TPA6 1 7.147135 -4.731192 -2.116664 TPA7 6 7.246428 -2.820482 -1.122603 TPA8 6 7.779454 -2.097214 -0.041505 TPA9 1 9.04692 -2.193149 1.694753 TPA10 1 6.598339 -2.321219 -1.836084 TPA11 7 7.478957 -0.708542 0.123023 TPA11 7 7.478957 -0.708542 0.123023 TPA12 6 6.167494 -0.252339 0.084897 TPA13 6 8.568062 0.194334 0.327803 TPA14 6 5.085701 -1.107124 0.414143 TPA15 6 5.866495 1.082565 -0.285619 TPA16 6 8.540664 1.12076 1.384914 TPA17 6 9.690066 0.146026 -0.50553 TPA18 1 5.286991 -2.122711 0.734445 TPA19 6 3.786352 -0.649194 0.371837 TPA20 6 4.562226 1.527365 -0.32103 TPA21 1 6.670083 1.749115 -0.57663 TPA22 1 7.682907 1.152502 2.049406 TPA22 1 7.682907 1.152502 2.049406 TPA23 6 9.605118 1.984808 1.587245 TPA24 6 10.768161 1.005944 -0.301617 TPA25 1 9.719285 -0.567885 -1.322541 TPA26 1 2.996028 -1.324255 0.679934 TPA27 6 3.464996 0.685013 0.003509 TPA28 1 4.376191 2.540862 -0.658951 TPA29 1 9.59772 2.700543 2.402706 TPA30 6 10.730198 1.936438 0.746545 TPA31 1 11.621812 0.948142 -0.96638 TPA32 6 2.095588 1.15956 -0.038814 DPA33 6 1.779127 2.544119 0.01814 DPA34 6 0.992531 0.265636 -0.123956 DPA34 6 0.992531 0.265636 -0.123956 DPA35 6 0.484571 3.003891 -0.020603 DPA36 1 2.574252 3.270857 0.149933 DPA37 1 1.171439 -0.801895 -0.197141 DPA38 6 -0.308685 0.701812 -0.163636 DPA39 6 -0.616669 2.097379 -0.128732 DPA40 1 0.291819 4.065149 0.068931 DPA41 1 -1.120726 -0.00777 -0.240576 DPA42 7 -1.908136 2.52118 -0.160498 DPA43 6 -3.013974 1.572788 -0.090414 BMes244 6 -2.249905 3.906784 -0.320718 DPA45 6 -3.518592 1.159797 1.155218 BMes246 6 -3.588487 1.068905 -1.26939 BMes
S19
46 6 -3.588487 1.068905 -1.26939 BMes247 6 -3.139014 4.519796 0.5764 DPA48 6 -1.771881 4.640767 -1.409591 DPA49 1 -3.05989 1.525694 2.072078 BMes2
50 6 -4.572015 0.260893 1.210609 BMes251 6 -4.642072 0.172518 -1.19625 BMes252 1 -3.21262 1.399786 -2.235594 BMes253 1 -3.546431 3.945992 1.400941 DPA53 1 -3.546431 3.945992 1.400941 DPA54 6 -3.509849 5.842818 0.399819 DPA55 6 -2.14315 5.974795 -1.595337 DPA56 1 -1.116931 4.164186 -2.132775 DPA57 1 -4.92516 -0.064498 2.185772 BMes258 6 -5.197755 -0.286284 0.043989 BMes259 1 -5.084664 -0.184354 -2.122616 BMes260 1 -4.194068 6.327262 1.088827 DPA61 6 -3.013915 6.584491 -0.685879 DPA62 1 -1.763242 6.513349 -2.455742 DPA63 5 -6.369434 -1.288591 0.118298 BMes264 6 -7.170137 -1.472014 1.492301 BMes265 6 -6.773623 -2.135786 -1.178683 BMes65 6 -6.773623 -2.135786 -1.178683 BMes266 6 -7.788842 -0.376028 2.158759 BMes267 6 -7.312011 -2.748893 2.110814 BMes268 6 -5.837884 -2.959542 -1.866238 BMes269 6 -8.100046 -2.11461 -1.702313 BMes270 6 -8.491312 -0.563886 3.357908 BMes271 6 -7.741359 1.035306 1.606949 BMes272 6 -8.01545 -2.898179 3.309252 BMes273 6 -6.674647 -3.988161 1.516634 BMes274 6 -6.21876 -3.69876 -2.995625 BMes275 6 -4.398481 -3.098341 -1.410798 BMes276 6 -8.443186 -2.860568 -2.833111 BMes277 6 -9.179975 -1.254563 -1.078911 BMes278 6 -8.620022 -1.816033 3.955424 BMes279 1 -8.960648 0.298308 3.831913 BMes280 1 -7.813949 1.047814 0.515462 BMes281 1 -6.798778 1.540573 1.853924 BMes282 1 -8.558985 1.640155 2.016804 BMes283 1 -8.090408 -3.88997 3.755383 BMes284 1 -6.860556 -4.864564 2.148339 BMes285 1 -5.587995 -3.870837 1.420262 BMes286 1 -7.053824 -4.20501 0.51306 BMes287 6 -7.51659 -3.666693 -3.501081 BMes288 1 -5.475814 -4.326777 -3.487618 BMes288 1 -5.475814 -4.326777 -3.487618 BMes289 1 -4.317934 -3.113694 -0.319663 BMes290 1 -3.779779 -2.257459 -1.750275 BMes291 1 -3.953498 -4.019564 -1.805739 BMes292 1 -9.465412 -2.807218 -3.207883 BMes293 1 -10.119205 -1.340296 -1.637507 BMes294 1 -8.891794 -0.196094 -1.071314 BMes295 1 -9.375851 -1.530839 -0.038145 BMes296 6 -9.403614 -2.006163 5.234045 BMes297 6 -7.917589 -4.48397 -4.707847 BMes298 1 -9.582481 -1.050229 5.739141 BMes299 1 -8.876748 -2.663216 5.937485 BMes2100 1 -10.385066 -2.463982 5.046051 BMes2
S20
100 1 -10.385066 -2.463982 5.046051 BMes2101 1 -8.579264 -5.317498 -4.433793 BMes2102 1 -7.042078 -4.912816 -5.208236 BMes2103 1 -8.460185 -3.878423 -5.445217 BMes2
104 8 11.7186 2.821284 1.034112 TPA105 8 -3.444008 7.874476 -0.765736 DPA106 8 8.63881 -6.125962 -0.629207 TPA107 6 9.486241 -6.849007 0.255741 TPA107 6 9.486241 -6.849007 0.255741 TPA108 1 9.079035 -6.866483 1.274421 TPA109 1 9.524739 -7.866104 -0.136168 TPA110 1 10.499109 -6.427165 0.274132 TPA111 6 12.887696 2.823927 0.223652 TPA112 1 12.650451 3.062999 -0.82067 TPA113 1 13.531988 3.601707 0.635514 TPA114 1 13.407925 1.85878 0.268104 TPA115 6 -3.016833 8.660176 -1.867718 DPA116 1 -3.3413 8.224982 -2.821902 DPA117 1 -3.486247 9.636777 -1.738119 DPA118 1 -1.925303 8.781106 -1.878033 DPATotal energy, E(TD-HF/TD-KS) = −2565.15481100 hartree (1 hartree = 627.5095 kcal/mol)
Table S2. Selected torsion angles and bond lengths in DFT-optimized structures.a
2 2•+ 2* 1 1•+
φ (°) 34.74 24.64 20.10 35.67 25.05d (Å) 1.480 1.459 1.450 1.480 1.459
a φ1 is torsion angles of two phenyl rings of biphenyl moieties, while d is C-C bond lengths between two phenyl rings.
Table S3. DFT-calculated NPA charges of fragments for NAr 3 derivatives.a
Compound TPA1 TPA2 Xb
2 −0.248 0.013 0.2352•+ 0.152
(0.444)0.535(0.533)
0.313(0.023)
2* −0.176 0.420 −0.2431 0.203 0.000 −0.2031•+ 0.671
(0.488)0.495(0.493)
−0.165(0.019)
0.671(0.488)
0.495(0.493)
−0.165(0.019)
aNPA spin densities are also shown in parentheses. a X = OCH3 (1), BMes2 (2).
S21
3. UV-vis-NIR spectral data
Figure S10. UV-vis-NIR spectra of (a) 2 and (b) 1 in CH2Cl2 in the absence (black line)and presence of 1.0 equiv of magic blue (red line).
S22
Table S4. IVCT parameters for NAr3+ derivatives.
2•+ 1•+
∆υ1/2 (cm−1) 2960 3040∆υ1/2 (cm ) 2960 3040υmax (cm−1) 6610 6260εmax (cm−1M−1) 3.04 × 104 2.96 × 104
rDA (Å) c 9.95 9.95rDA (Å) c 9.95 9.95µeg (D) 11.7 12.1HAB (cm−1) 1600 a
(1610)b1560 a
(1590)b(1610)b (1590)b
α d 0.242 0.248∆G0 (cm−1) 1060 0λ (cm−1) 5550 6260a Determined by the equation: HAB = 0.0206(υmaxεmax∆υ1/2)1/2/rDA. b Determined by the equation: HAB = µeg υmax/(e rDA), where µeg and e are the transition moment connectingequation: HAB = µeg υmax/(e rDA), where µeg and e are the transition moment connectingbetween the ground and excited atetes and the elementary charge, respectively. c The N···N distance in the DFT-optimized structure. d Delocalization parameter α = H /υ .HAB/υmax.
4. Photophysical properties4. Photophysical properties
Figure S11. Fluorescence emission spectra of NB in several solvents.
S23