difluoroboranyls derived from amides carrying donor group Supporting Information

The influence of the π-conjugated spacer on photophysical properties of difluoroboranyls derived from amides carrying donor group Supporting Information Anna Maria Grabarz a Adèle D. Laurent b, Beata Jędrzejewska c, Anna Zakrzewska c, Denis Jacquemin b,* and Borys Ośmiałowski c,* a Faculty of Chemistry, Wrocław University of Technology, Wyb. Wyspiańskiego 27, PL-50370 Wrocław, Poland. b Laboratoire CEISAM, UMR CNRS 6230, Université de Nantes, 2 Rue de la Houssinière, BP92208, 44322 Cedex 3 Nantes, France. E-mail: Denis.Jacquemin@univ-nantes.fr c Faculty of Chemical Technology and Engineering, UTP University of Science and Technology, Seminaryjna 3, PL-85326 Bydgoszcz, Poland. E-mail: borys.osmialowski@utp.edu.pl Table of Contents 1. Linear relations for properties of studied compounds S2 2. NMR spectra S3 3. Cartesian coordinates for optimized structures S21 4. Additional fluorescence spectra (fluorescence decomposition, variable temperature spectra) S39 1

1. Relationships between Stokes shifts and number of π electrons. Fig. S1. Correlation between the number of conjugated electrons in the space and the Stokes shift (experimental values). We give the correlation equation, together with the determination coefficient (R 2 ) Fig. S2. Correlation between the number of conjugated electrons in the space and the Stokes shift (theoretical values) We give the correlation equation, together with the determination coefficient (R 2 ) 2

2. NMR spectra Spectra were recorded on a 400 MHz spectrometer. Spectra of A2 1 H 13 C 3

Spectra of A3 1 H 13 C 4

Spectra of A4 1 H 13 C 5

Spectra of A5 1 H 13 C 6

Spectra of A6 1 H 13 C 7

Spectra of A7 1 H 13 C 8

Spectra of B1 1 H 11 B 9

13 C 19 F 10

Spectra of B2 1 H 11 B 11

13 C 19 F 12

Spectra of B3 1 H 11 B 13

13 C 19 F 14

Spectra of B4 1 H NMR 11 B NMR 13 C NMR 15

19 F NMR Spectra of B5 1 H 16

11 B 13 C 19 F 17

Spectra of B6 1 H 11 B 18

13 C 19 F 19

Spectra of B7 1 H 11 B 20

13 C 19 F 21

3. Cartesian coordinates for optimized structures All calculation were performed with M06-2X, GS indicates the ground state structure and ES the excited state structure. 3.1 B1 GS Energy = -774.818961 C 0.81584-0.95394 0.07261 N 1.28856 0.31461-0.04453 C 2.60846 0.57385-0.19623 C 3.54299-0.42753-0.21127 C 3.09196-1.75419-0.06245 C 1.75135-2.01676 0.07627 B 0.26949 1.51147 0.10409 F 0.66911 2.54042-0.71185 N -0.50375-1.22229 0.18060 C -1.36640-0.24730-0.06180 N -2.68143-0.51085-0.07751 C -3.19504-1.86022 0.08479 O -1.03658 0.99663-0.33825 F 0.22023 1.88129 1.43215 C -3.68034 0.52301-0.29126 H 2.85919 1.62307-0.30052 H 4.59269-0.19314-0.33155 H 3.80519-2.57229-0.06402 H 1.36408-3.02286 0.17894 H -4.45315 0.43324 0.47813 H -3.22129 1.50591-0.23129 H -4.14923 0.39882-1.27347 H -3.78485-1.92495 1.00499 H -3.84221-2.10457-0.76379 H -2.36590-2.56076 0.13163 ES Energy = -774.809926 C 0.83448-0.97162 0.06626 N 1.26177 0.36216-0.13197 C 2.58994 0.57226-0.31181 C 3.53164-0.45544-0.23833 C 3.14167-1.78040 0.02602 C 1.74933-2.01421 0.15122 B 0.28007 1.53424 0.11690 F 0.60997 2.59156-0.69781 N -0.48822-1.22148 0.11118 C -1.36886-0.22227-0.06729 22

N -2.67614-0.53908-0.06942 C -3.15685-1.90785 0.02050 O -1.08045 1.03920-0.25196 F 0.27282 1.89375 1.45315 C -3.70036 0.47797-0.23373 H 2.87682 1.59898-0.51004 H 4.57437-0.19949-0.39252 H 3.85981-2.58463 0.10465 H 1.34336-3.01066 0.28412 H -4.49595 0.29378 0.49380 H -3.27599 1.46542-0.07639 H -4.12843 0.41804-1.24147 H -3.77923-2.01444 0.91460 H -3.76871-2.12922-0.86011 H -2.31562-2.59223 0.07090 3.2 B2(E) GS Energy = -852.178287 C -3.47246 0.09486-0.18641 N -2.13955-0.09081-0.05091 C -1.27963 0.95475 0.06557 C -1.81847 2.26377 0.08336 C -3.17318 2.45357-0.03976 C -4.03151 1.34635-0.18652 B -1.57083-1.56154 0.07668 F -2.26751-2.37458-0.78791 N 0.05861 0.77904 0.15056 C 0.56659-0.42177-0.07478 C 1.98086-0.62936-0.12764 H 2.31922-1.64565-0.28153 O -0.15881-1.50286-0.30012 F -1.71365-1.96509 1.39045 C 2.84109 0.42718 0.00612 H -1.12333 3.08803 0.18453 H -3.58201 3.45895-0.02981 H -5.10180 1.46598-0.29429 H -4.05278-0.81454-0.29147 N 4.17560 0.36160-0.00139 C 5.00329 1.55166 0.09036 C 4.83875-0.91944-0.16899 H 5.91632-0.77721-0.08639 H 4.51165-1.62023 0.60603 H 4.60936-1.35024-1.15021 H 5.59407 1.68179-0.82238 H 4.36594 2.42618 0.22495 H 5.68534 1.47628 0.94287 23

ES H 2.41842 1.42009 0.13670 Energy = -852.173518 C -3.47183 0.09491-0.17330 N -2.14718-0.11876-0.08261 C -1.27460 0.96913 0.01326 C -1.81108 2.27498 0.07519 C -3.17345 2.48241-0.00252 C -4.02623 1.35877-0.14585 B -1.55975-1.57059 0.09428 F -2.33485-2.44549-0.63905 N 0.05058 0.77578 0.01506 C 0.54965-0.45944-0.17853 C 1.95989-0.61808-0.17609 H 2.33721-1.62425-0.31926 O -0.19080-1.54819-0.41950 F -1.57341-1.88824 1.44615 C 2.82873 0.46294-0.00565 H -1.10624 3.09430 0.16445 H -3.58308 3.48514 0.03979 H -5.10029 1.47186-0.22888 H -4.07689-0.80098-0.26699 N 4.16524 0.36744 0.01190 C 5.00193 1.54440 0.15549 C 4.82884-0.91402-0.14789 H 5.90507-0.76852-0.05911 H 4.49803-1.61548 0.62600 H 4.60653-1.34504-1.13133 H 5.63202 1.67358-0.73189 H 4.37317 2.42634 0.27740 H 5.65045 1.44182 1.03220 H 2.41190 1.45615 0.12328 3.3 B2(Z) GS Energy = -852.179120 C 4.40004-0.30280-0.27441 C 3.40284 0.63777-0.23444 N 2.10827 0.29486-0.04988 C 1.72274-1.00144 0.07963 C 2.72237-2.00171 0.05696 C 4.04076-1.65484-0.11659 B 1.01487 1.42704 0.11626 F 1.00813 1.82709 1.43879 N 0.42153-1.35717 0.21460 C -0.51474-0.44726 0.01298 24

ES O -0.26468 0.82608-0.25684 F 1.32586 2.46355-0.73340 C -1.88636-0.84693 0.04181 C -2.88326 0.07937-0.10659 N -4.19679-0.17232-0.11969 C -4.67659-1.53209 0.04776 C -5.18051 0.89426-0.18575 H -2.07973-1.89989 0.19667 H 2.40176-3.03006 0.16870 H 4.80501-2.42517-0.13764 H 5.42899-0.00056-0.42082 H 3.58437 1.70060-0.34455 H -5.75953-1.54629-0.07660 H -4.22440-2.18754-0.70343 H -4.42590-1.91537 1.04374 H -5.75974 0.94577 0.74243 H -4.67192 1.84708-0.33602 H -5.86772 0.72469-1.02017 H -2.60882 1.12352-0.23074 Energy = -852.174927 C 4.40147-0.33803-0.26519 C 3.40978 0.62051-0.25509 N 2.10691 0.31964-0.09338 C 1.71995-1.02120 0.04209 C 2.71479-2.02326 0.06761 C 4.04900-1.70148-0.08286 B 1.03310 1.44015 0.13359 F 1.00018 1.76817 1.48323 N 0.42176-1.34839 0.11038 C -0.51234-0.39835-0.04566 O -0.25906 0.89204-0.29171 F 1.36407 2.53417-0.64080 C -1.87162-0.80122 0.02028 C -2.91029 0.12099-0.11849 N -4.21215-0.18424-0.07057 C -4.65333-1.55158 0.14146 C -5.23277 0.83223-0.25132 H -2.05833-1.85582 0.18034 H 2.37797-3.04707 0.18864 H 4.81007-2.47293-0.06697 H 5.43223-0.03557-0.40539 H 3.62592 1.67729-0.37424 H -5.74224-1.57198 0.16897 H -4.30294-2.19881-0.67095 H -4.26369-1.93582 1.09072 H -5.88507 0.87026 0.62761 H -4.75953 1.80405-0.38933 25

H -5.84395 0.60131-1.13090 H -2.66519 1.16630-0.27668 3.4 B3(E) GS Energy = -929.543527 C -4.72686 1.72611-0.17778 C -4.34391 0.40935-0.16178 N -3.04707 0.04634-0.04283 C -2.05242 0.96717 0.04071 C -2.40544 2.33655 0.04023 C -3.72430 2.70800-0.06622 B -2.68445-1.48820 0.10329 F -2.87504-1.84890 1.42274 N -0.74653 0.61147 0.10681 C -0.41367-0.64884-0.09324 O -1.27962-1.62865-0.27836 F -3.49204-2.20773-0.74706 C 0.96745-1.04953-0.16017 C 1.99079-0.15950-0.05586 C 3.37534-0.47943-0.09969 C 4.31038 0.51501 0.01915 H 1.15061-2.11010-0.29915 H -1.60218 3.05908 0.11431 H -3.99208 3.75973-0.07007 H -5.77277 1.98845-0.27142 H -5.04491-0.41355-0.24030 H 1.72197 0.88871 0.07568 H 3.67220-1.51637-0.22337 N 5.64384 0.37157-0.03050 H 3.97058 1.53917 0.16249 C 6.54259 1.47913 0.23884 C 6.22278-0.94820-0.19752 H 7.27888 1.57318-0.56504 H 5.96975 2.40545 0.29953 H 7.07397 1.33153 1.18583 H 7.30328-0.85179-0.30662 H 6.00684-1.58647 0.66789 H 5.81864-1.42776-1.09479 ES Energy = -929.538435 C -4.79723 1.64669-0.12738 C -4.37063 0.33898-0.13000 N -3.06899 0.00440-0.05822 C -2.08747 0.97563-0.00319 C -2.49274 2.33729 0.03242 26

C -3.82311 2.66940-0.03149 B -2.63247-1.50723 0.11363 F -2.67840-1.81188 1.46763 N -0.78879 0.65678 0.00198 C -0.41807-0.62015-0.18926 O -1.28080-1.62530-0.41143 F -3.50610-2.29417-0.60973 C 0.95934-0.93361-0.21884 C 1.98608 0.00918-0.06606 C 3.34270-0.34391-0.10164 C 4.36258 0.60022 0.05151 H 1.21377-1.97875-0.37513 H -1.71101 3.08572 0.09312 H -4.12654 3.71114-0.01241 H -5.85417 1.87256-0.19041 H -5.05588-0.50009-0.18646 H 1.70457 1.04825 0.08543 H 3.60034-1.38933-0.25185 N 5.67307 0.33320 0.03286 H 4.10078 1.64467 0.20123 C 6.66391 1.37919 0.21433 C 6.15520-1.02384-0.15744 H 7.32226 1.43170-0.65940 H 6.16319 2.33882 0.34221 H 7.27387 1.17269 1.10056 H 7.24457-1.01720-0.14205 H 5.78968-1.67718 0.64308 H 5.81349-1.42108-1.11993 3.5 B3(Z) GS Energy = -929.544692 C 5.05311-1.50045-0.22073 C 5.32431-0.12642-0.35495 C 4.27288 0.75078-0.26726 N 3.00770 0.32488-0.05833 C 2.70716-0.99475 0.05015 C 3.76246-1.93129-0.02204 B 1.85240 1.38725 0.15983 F 2.07491 2.45019-0.68455 N 1.43121-1.43288 0.20727 C 0.43975-0.57730 0.05643 C -0.91106-1.06647 0.10581 C -1.98839-0.24284-0.00360 C -3.35046-0.65156 0.02836 C -4.34705 0.28110-0.08912 N -5.66891 0.05111-0.05070 C -6.16198-1.30423 0.10444 27

ES F 1.86767 1.76907 1.48696 O 0.59982 0.71466-0.17917 C -6.63613 1.10172-0.31077 H -1.02314-2.13713 0.23826 H 3.50725-2.97938 0.07253 H 5.86195-2.22162-0.27967 H 6.32858 0.24201-0.52020 H 4.38672 1.82486-0.35685 H -1.79232 0.82227-0.12642 H -3.57984-1.70646 0.14366 H -4.07357 1.32636-0.22162 H -7.37469 1.14522 0.49544 H -6.12244 2.06223-0.36754 H -7.15978 0.92662-1.25734 H -7.24781-1.27973 0.19957 H -5.89353-1.92309-0.76039 H -5.73870-1.76053 1.00515 Energy = -929.540303 C 5.02228-1.61679-0.15316 C 5.34088-0.24430-0.31092 C 4.31763 0.67180-0.26148 N 3.03158 0.31186-0.08292 C 2.67788-1.02163 0.03523 C 3.71460-1.99408 0.01963 B 1.91757 1.40508 0.14587 F 2.20882 2.49917-0.64561 N 1.39931-1.39945 0.14230 C 0.42831-0.48593 0.00301 C -0.91613-0.91842 0.07583 C -2.01564-0.06344-0.06061 C -3.34136-0.51714 0.00952 C -4.43118 0.34911-0.12891 N -5.71649-0.01136-0.06818 C -6.09420-1.39654 0.15497 F 1.91240 1.74564 1.49244 O 0.64619 0.81316-0.25182 C -6.78570 0.95759-0.23516 H -1.06907-1.98028 0.24349 H 3.42087-3.03172 0.12996 H 5.80821-2.36478-0.17292 H 6.36024 0.08873-0.45990 H 4.48365 1.73939-0.36000 H -1.82242 0.99373-0.22581 H -3.51759-1.57660 0.17787 H -4.24915 1.40732-0.29888 H -7.42428 0.96997 0.65430 H -6.36026 1.94986-0.38385 28

H -7.39942 0.69607-1.10401 H -7.18112-1.46675 0.18011 H -5.71267-2.03321-0.65136 H -5.69027-1.75436 1.10863 3.6 B4 GS Energy = -1005.765497 C 1.67606 1.24458 0.10559 C 1.00491 0.01963-0.01926 C 1.77029-1.14690-0.15157 C 3.15101-1.10064-0.15959 C 3.83576 0.13316-0.03277 C 3.05465 1.30905 0.10104 C -0.45541-0.03897-0.01085 O -0.97459-1.22960-0.22851 B -2.36561-1.52468 0.12815 F -2.46166-1.90993 1.44808 N 5.19970 0.18879-0.03910 C 5.97437-1.03023-0.17425 N -3.17111-0.16955-0.04807 C -4.51024-0.21362-0.21912 C -5.26746 0.93063-0.27044 C -4.61139 2.16641-0.14031 C -3.24455 2.20667 0.01992 C -2.50606 1.00687 0.05635 N -1.14858 1.05600 0.17327 F -2.89600-2.45862-0.72753 C 5.87501 1.46539 0.09695 H -2.69660 3.13625 0.11022 H -5.18067 3.08964-0.17184 H -6.33953 0.86735-0.40558 H -4.93015-1.20859-0.30926 H 1.26623-2.10267-0.24618 H 3.70544-2.02507-0.26170 H 3.53485 2.27453 0.19966 H 1.09212 2.15315 0.20642 H 5.75661-1.54051-1.12023 H 5.77157-1.72751 0.64762 H 7.03460-0.78115-0.15694 H 5.62517 1.95253 1.04729 H 5.61073 2.14800-0.71972 H 6.95163 1.30227 0.06982 ES Energy = -1005.759853 C 1.65873 1.24750 0.09472 29

C 0.98255 0.00003-0.07859 C 1.77918-1.17447-0.22651 C 3.14681-1.11222-0.20290 C 3.82348 0.13793-0.02897 C 3.02465 1.31664 0.11886 C -0.44494-0.07556-0.10697 O -0.99058-1.27885-0.33205 B -2.34814-1.52151 0.15139 F -2.34510-1.80985 1.50949 N 5.17705 0.20172-0.00595 C 5.97479-1.00647-0.14806 N -3.16457-0.19131-0.07137 C -4.50503-0.21296-0.19133 C -5.26531 0.93403-0.22016 C -4.60793 2.18597-0.10226 C -3.23996 2.22084 0.00967 C -2.48255 1.01801 0.00214 N -1.14894 1.05697 0.04302 F -2.94503-2.52941-0.57834 C 5.85097 1.47936 0.16427 H -2.68879 3.15130 0.08679 H -5.18103 3.10698-0.10454 H -6.34093 0.86609-0.32390 H -4.94254-1.20344-0.26027 H 1.27772-2.12616-0.35673 H 3.71793-2.02510-0.31821 H 3.50110 2.27973 0.25325 H 1.06057 2.14357 0.20855 H 5.78186-1.49117-1.11173 H 5.75027-1.71888 0.65354 H 7.02907-0.74347-0.09510 H 5.58120 1.93923 1.12173 H 5.58562 2.17097-0.64315 H 6.92681 1.31849 0.14545 3.7 B5(E) GS Energy = -1083.129422 C -6.07157 1.40330-0.23753 C -5.53482 0.14040-0.19914 N -4.20707-0.06193-0.05242 C -3.33636 0.97330 0.03910 C -3.84514 2.28824 0.01533 C -5.19858 2.49853-0.12001 B -3.66834-1.54493 0.11178 F -3.84615-1.92028 1.42633 N -1.99213 0.77461 0.13086 C -1.51580-0.43264-0.04703 30

ES O -2.24371-1.51438-0.23161 F -4.35855-2.35448-0.75724 C -0.08087-0.67067-0.08687 C 0.81570 0.33010 0.02363 C 2.26263 0.21804 0.00720 H 0.20867-1.70875-0.21102 H -3.13512 3.10188 0.09518 H -5.59034 3.51025-0.14141 H -7.13945 1.53691-0.35319 H -6.13117-0.76082-0.28119 H 0.41549 1.33657 0.13962 C 3.04382 1.37779 0.12930 C 4.42621 1.33883 0.11922 C 5.10982 0.10808-0.01714 C 4.32479-1.06675-0.13921 C 2.94631-1.00366-0.12636 H 2.54603 2.33869 0.23559 H 4.97914 2.26468 0.21796 N 6.47528 0.05022-0.03098 H 4.80322-2.03266-0.24394 H 2.38617-1.92934-0.22176 C 7.14693-1.22885-0.15702 C 7.25084 1.26749 0.10548 H 8.31099 1.02007 0.06776 H 7.03424 1.97317-0.70577 H 7.04820 1.76890 1.06003 H 8.22407-1.06694-0.14487 H 6.89160-1.90126 0.67124 H 6.88619-1.72820-1.09807 Energy = -1083.121494 C -6.08473 1.35511-0.21313 C -5.52500 0.10015-0.17673 N -4.19684-0.09267-0.06499 C -3.32260 0.96957-0.00759 C -3.86833 2.28375-0.01361 C -5.22302 2.47214-0.11750 B -3.61363-1.55014 0.14134 F -3.67335-1.84289 1.49635 N -1.99929 0.79199 0.03894 C -1.49016-0.44138-0.12463 O -2.24023-1.53178-0.33827 F -4.37590-2.43013-0.59935 C -0.09144-0.61835-0.13644 C 0.82390 0.43028 0.01210 C 2.22968 0.28761 0.00110 H 0.24537-1.64054-0.27685 H -3.17049 3.11055 0.04806 31

H -5.63261 3.47719-0.13045 H -7.15710 1.47013-0.30614 H -6.11554-0.80791-0.23217 H 0.41714 1.42858 0.14589 C 3.06381 1.43973 0.15994 C 4.42878 1.36192 0.15697 C 5.08812 0.10231-0.00839 C 4.26977-1.05795-0.16839 C 2.90385-0.96619-0.16344 H 2.58632 2.40725 0.28713 H 5.01013 2.26689 0.28214 N 6.43822 0.01529-0.01240 H 4.72927-2.03018-0.29615 H 2.32353-1.87382-0.28743 C 7.09152-1.27436-0.17787 C 7.25349 1.20956 0.15137 H 8.30402 0.92829 0.11897 H 7.05968 1.92931-0.65159 H 7.05084 1.69348 1.11321 H 8.16993-1.13146-0.15285 H 6.81098-1.96144 0.62820 H 6.82115-1.72989-1.13695 3.8 B5(Z) GS Energy = -1083.130644 N -4.19065 0.20291 0.05141 C -5.50566 0.44351 0.24120 C -6.42146-0.57763 0.31358 C -5.95591-1.89674 0.18517 C -4.61192-2.13758 0.00570 C -3.70722-1.05917-0.05218 H -5.77445 1.48975 0.32846 H -7.47051-0.35690 0.46320 H -6.65368-2.72640 0.23257 H -4.20693-3.13778-0.08454 N -2.37214-1.30882-0.18831 C -1.52576-0.32087-0.03106 O -1.86045 0.93478 0.18856 B -3.19861 1.42678-0.14767 C -0.10575-0.62325-0.06031 C 0.83464 0.33602 0.05743 C 2.27557 0.15704 0.04744 C 3.10965 1.28058 0.15735 C 4.48876 1.17695 0.15044 C 5.11465-0.08566 0.03083 C 4.27605-1.22412-0.07730 C 2.90173-1.09652-0.06863 32

ES H 2.65732 2.26502 0.25018 H 5.08381 2.07739 0.23881 N 6.47630-0.20666 0.02015 H 4.70904-2.21259-0.16880 H 2.29929-1.99638-0.15315 H 0.13280-1.67336-0.18623 H 0.48601 1.36146 0.17070 F -3.26316 1.81537-1.46865 F -3.57469 2.43112 0.71014 C 7.08826-1.51662-0.08910 C 7.30698 0.97626 0.13190 H 8.17178-1.40478-0.07448 H 6.79941-2.16657 0.74604 H 6.80764-2.01485-1.02515 H 7.11823 1.67704-0.69051 H 7.13265 1.50291 1.07842 H 8.35459 0.68034 0.09351 Energy = -1083.123237 N -4.18419 0.19433 0.06344 C -5.50829 0.39493 0.21430 C -6.40704-0.64230 0.27353 C -5.91050-1.96295 0.15820 C -4.56392-2.17622 0.01484 C -3.65838-1.07807-0.01299 H -5.80756 1.43535 0.28154 H -7.46332-0.44064 0.39782 H -6.59438-2.80528 0.18718 H -4.13927-3.17025-0.06337 N -2.34273-1.29443-0.09707 C -1.49508-0.26142 0.03987 O -1.88677 0.99897 0.26490 B -3.21230 1.41728-0.17285 C -0.11011-0.52335-0.00309 C 0.86412 0.47063 0.12380 C 2.26024 0.24951 0.08769 C 3.16168 1.35330 0.22197 C 4.51922 1.19703 0.19194 C 5.10147-0.10025 0.02299 C 4.21476-1.21333-0.11067 C 2.85716-1.04265-0.08042 H 2.74288 2.34711 0.35215 H 5.15428 2.06732 0.30056 N 6.44314-0.26515-0.00908 H 4.61560-2.21065-0.24213 H 2.22235-1.91519-0.18809 H 0.15468-1.56543-0.14263 H 0.51973 1.49272 0.25532 33

F -3.22170 1.71817-1.52744 F -3.65849 2.48241 0.58304 C 7.01748-1.59416-0.15743 C 7.33061 0.88258 0.11053 H 8.10249-1.51528-0.14135 H 6.70235-2.24875 0.66255 H 6.71296-2.04888-1.10665 H 7.14008 1.60758-0.68794 H 7.19934 1.38121 1.07728 H 8.36113 0.54273 0.03129 3.9 B6(E) GS Energy = -1160.497929 C -6.00927 2.67719-0.10742 C -6.98921 1.67597-0.21839 C -6.58260 0.36504-0.18597 N -5.28104 0.02927-0.05077 C -4.30989 0.97138 0.03447 C -4.68279 2.33086 0.01600 B -4.89386-1.50147 0.10806 F -5.66856-2.23486-0.75713 N -2.99153 0.63768 0.11480 C -2.64190-0.61149-0.06602 C -1.23730-0.98729-0.11534 C -0.23900-0.08448-0.01494 C 1.16171-0.41473-0.05189 C 2.11849 0.53484 0.05002 C 3.56011 0.34971 0.02672 F -5.10002-1.85885 1.42329 O -3.47549-1.61472-0.24477 H -1.03563-2.04692-0.23863 H -3.89338 3.06831 0.09054 H -6.29684 3.72336-0.12456 H -8.03914 1.91675-0.32450 H -7.26784-0.47099-0.26362 H -0.50710 0.96466 0.10278 H 1.42345-1.46463-0.16751 H 1.78646 1.56796 0.16251 C 4.40202 1.46769 0.13209 C 5.78110 1.35743 0.11399 C 6.40037 0.09312-0.01424 C 5.55508-1.03975-0.11699 C 4.18067-0.90574-0.09717 H 3.95670 2.45485 0.23177 H 6.38077 2.25507 0.20088 N 7.76278-0.03424-0.03879 H 5.98188-2.03056-0.21329 34

ES H 3.57506-1.80375-0.17880 C 8.36651-1.34883-0.13127 C 8.59914 1.14216 0.09097 H 9.45079-1.24293-0.12764 H 8.08075-1.98559 0.71548 H 8.07611-1.85940-1.05753 H 9.64526 0.84271 0.03938 H 8.40857 1.85861-0.71730 H 8.43371 1.65330 1.04800 Energy = -1160.488521 C -6.09263 2.60566-0.11172 C -7.04367 1.56381-0.19800 C -6.58685 0.26960-0.16283 N -5.27562-0.02753-0.05882 C -4.31927 0.95580-0.00915 C -4.75718 2.30948-0.01684 B -4.81420-1.52784 0.14131 F -5.64212-2.33989-0.60666 N -3.01225 0.67368 0.03338 C -2.60518-0.59286-0.13543 C -1.22728-0.88832-0.16709 C -0.22022 0.07320-0.03982 C 1.13988-0.23858-0.07104 C 2.15588 0.71777 0.05371 C 3.54451 0.46739 0.03125 F -4.90288-1.82235 1.49400 O -3.44145-1.61918-0.33254 H -0.96099-1.93302-0.30434 H -3.99499 3.07762 0.03802 H -6.41905 3.64083-0.12518 H -8.10365 1.76596-0.28319 H -7.24670-0.58956-0.21264 H -0.52249 1.10989 0.09012 H 1.40783-1.28573-0.20063 H 1.84817 1.75482 0.18016 C 4.46436 1.55243 0.16825 C 5.82038 1.37106 0.15388 C 6.37900 0.06467-0.00090 C 5.47230-1.03094-0.13902 C 4.11780-0.83402-0.12343 H 4.06485 2.55575 0.28817 H 6.46964 2.23069 0.26318 N 7.71703-0.12790-0.01582 H 5.85440-2.03693-0.25948 H 3.46962-1.69690-0.23202 C 8.26560-1.46813-0.16194 C 8.62446 1.00196 0.12099 35

H 9.35192-1.41003-0.14186 H 7.93606-2.11763 0.65638 H 7.95766-1.91687-1.11270 H 9.64976 0.64060 0.07244 H 8.47205 1.72650-0.68619 H 8.47800 1.50915 1.08092 3.10 B6(Z) GS Energy = -1160.499149 C 7.19035-1.69432-0.24311 C 7.54209-0.33879-0.35085 C 6.54470 0.60051-0.25040 N 5.25680 0.24697-0.05262 C 4.88247-1.05296 0.03225 C 5.87321-2.05035-0.05493 B 4.16771 1.37977 0.17873 F 4.44933 2.42767-0.66282 N 3.57407-1.41635 0.17646 C 2.64725-0.50018 0.04481 C 1.25655-0.91590 0.08104 C 0.23391-0.03989-0.01684 C -1.15762-0.41002 0.01213 C -2.14071 0.51245-0.08549 C -3.57674 0.28608-0.06729 F 4.21331 1.74758 1.50636 O 2.87229 0.78306-0.15510 H 1.08850-1.98198 0.19333 H 5.55437-3.08245 0.02021 H 7.95455-2.46146-0.31338 H 8.56715-0.02782-0.50641 H 6.72421 1.66694-0.32080 H 0.46717 1.01851-0.12344 H -1.38938-1.46797 0.11829 H -1.83805 1.55533-0.19012 C -4.44965 1.37919-0.18062 C -5.82516 1.22982-0.16725 C -6.40867-0.05112-0.03740 C -5.53205-1.15855 0.07778 C -4.16184-0.98565 0.06205 H -4.03217 2.37828-0.28162 H -6.44975 2.10996-0.25770 N -7.76719-0.21766-0.02339 H -5.93101-2.16013 0.18182 H -3.53122-1.86525 0.15431 C -8.33338-1.54266 0.13319 C -8.63607 0.93881-0.11175 H -9.42020-1.46888 0.11775 36

ES H -8.02496-2.20923-0.68141 H -8.03343-2.00151 1.08384 H -9.67351 0.60850-0.07445 H -8.46678 1.63504 0.71940 H -8.48386 1.48401-1.05138 Energy = -1160.490004 C 7.12762-1.81078-0.21328 C 7.52886-0.45940-0.32601 C 6.56038 0.50946-0.24211 N 5.25670 0.21079-0.06631 C 4.82341-1.09045 0.01205 C 5.80301-2.12115-0.04532 B 4.20633 1.36494 0.18358 F 4.55655 2.44916-0.59533 N 3.52724-1.40305 0.12544 C 2.60601-0.43657 0.00528 C 1.24344-0.79101 0.05854 C 0.20066 0.13166-0.05214 C -1.14843-0.22710-0.00765 C -2.19642 0.69658-0.11067 C -3.57562 0.40212-0.07377 F 4.23171 1.68322 1.53343 O 2.90389 0.84903-0.21431 H 1.02910-1.84721 0.18980 H 5.45182-3.14332 0.03182 H 7.86820-2.60276-0.26463 H 8.56575-0.18331-0.46869 H 6.78050 1.56930-0.30876 H 0.45992 1.18089-0.17625 H -1.37933-1.28395 0.11507 H -1.92359 1.74401-0.23048 C -4.52991 1.45989-0.19100 C -5.87902 1.23656-0.16509 C -6.39575-0.08818-0.01740 C -5.45429-1.15662 0.10411 C -4.10692-0.91783 0.07663 H -4.16233 2.47600-0.30481 H -6.55558 2.07670-0.25839 N -7.72670-0.32160 0.00583 H -5.80387-2.17495 0.21992 H -3.43105-1.76076 0.17223 C -8.23364-1.67796 0.15468 C -8.66968 0.78020-0.12216 H -9.32132-1.65195 0.14650 H -7.89363-2.31566-0.66861 H -7.90229-2.11866 1.10122 H -9.68286 0.38528-0.08215 37

H -8.54383 1.50069 0.69320 H -8.53570 1.30165-1.07612 38

Fluorescence 1.0 0.8 0.6 0.4 0.2 D1 in CHCl 3 EXP 1 2 Fluorescence 1.0 0.8 0.6 0.4 0.2 D2 in CHCl 3 EXP 1 2 Fluorescence 1.0 0.8 0.6 0.4 0.2 D3 in CHCl 3 EXP 1 2 0.0 20000 22000 24000 26000 28000 30000 32000 ν (cm -1 ) 0.0 16000 18000 20000 22000 24000 26000 28000 ν (cm -1 ) 0.0 16000 18000 20000 22000 ν (cm -1 ) 1.0 0.8 D4 in CHCl 3 EXP 1 2 1.0 0.8 D5 in CHCl 3 EXP 1 2 1.0 0.8 D6 in CHCl 3 EXP 1 2 Fluorescence 0.6 0.4 Fluorescence 0.6 0.4 Fluorescence 0.6 0.4 0.2 0.2 0.2 0.0 16000 18000 20000 22000 24000 26000 ν (cm -1 ) Fig. S3. Decomposed fluorescence spectra of B1-B6 in CHCl 3. 0.0 14000 16000 18000 20000 22000 ν (cm -1 ) 0.0 12000 14000 16000 18000 20000 ν (cm -1 ) 39

Absorbance 4000 3000 2000 1000 B1 in CHCl 3 Em = 415 nm Em = 384 nm Absorbance 1.8 1.6 1.4 1.2 1.0 0.8 0.6 0.4 B1 in CHCl 3 Em = 415 nm Absorbance Fluorescence 9000 8000 7000 6000 5000 4000 3000 2000 B1 in CHCl 3 Ex = 350 nm Ex = 312 nm Ex = 276 nm Ex = 255 nm 0.2 1000 0 250 300 350 400 0.0 240 280 320 360 400 0 300 350 400 450 500 550 Absorbance 400 300 200 100 B2 in CHCl 3 Em = 470 nm Em = 425 nm Em = 410 nm Absorbance 1.0 0.8 0.6 0.4 0.2 B2 in CHCl 3 Em = 470 nm Absorbance Fluorescence 4200 3500 2800 2100 1400 700 B2 in CHCl 3 Ex = 404 nm Ex = 400 nm Ex = 364 nm Ex = 311 nm 0 250 300 350 400 450 0.0 300 350 400 450 500 0 350 420 490 560 40

200 1.2 200 Absorbance 150 100 50 B3 in CHCl 3 Em = 530 nm Em = 493 nm Em = 485 nm Absorbance 1.0 0.8 0.6 0.4 0.2 B3 in CHCl 3 Em = 530 nm Absorbance Fluorescence 150 100 50 B3 in CHCl 3 Ex = 470 nm Ex = 455 nm Ex = 433 nm Ex = 400 nm Ex = 340 nm 0 300 350 400 450 500 0.0 350 400 450 500 0 420 490 560 630 Absorbance 600 500 400 300 200 B4 in CHCl 3 Em = 500 nm Em = 462 nm Em = 450 nm Absorbance 1.0 0.8 0.6 0.4 B4 in CHCl 3 Em = 462 nm Absorbance Fluorescence 8000 7000 6000 5000 4000 3000 B4 in CHCl 3 Ex = 430 nm Ex = 404 nm Ex = 380 nm Ex = 365 nm 100 0.2 2000 1000 0 300 350 400 450 0.0 300 350 400 450 500 0 420 490 560 630 41

Absorbance 800 600 400 200 B5 in CHCl 3 Em = 570 nm Em = 533 nm Em = 510 nm Absorbance 1.0 0.8 0.6 0.4 0.2 B5 in CHCl 3 Em = 533 nm Absorbance Fluorescence 700 600 500 400 300 200 100 B5 in CHCl 3 Ex = 443 nm Ex = 410 nm Ex = 385 nm Ex = 310 nm Ex = 480 nm 0 300 350 400 450 500 550 0.0 300 350 400 450 500 550 0 490 560 630 700 400 350 350 300 B6 in CHCl 3 Em = 570 nm Em = 607 nm Em = 650 nm 1.0 0.8 B6 in CHCl 3 Em = 570 nm Absorbance 300 250 B6 in CHCl 3 Ex = 404 nm Ex = 461 nm Ex = 515nm Absorbance 250 200 150 100 50 Absorbance 0.6 0.4 0.2 Fluorescence 200 150 100 50 0 350 400 450 500 550 600 0.0 300 350 400 450 500 550 600 0 490 560 630 700 770 Fig. S4. Electronic absorption excitation (left and middle panels) and fluorescence spectra of B1-B6 in CHCl 3. 42

1.0 0.8 B1 in CHCl 3 ; λ ex =312 nm 40 o C 0 o C -20 o C 1.0 0.8 B2 in CHCl 3 ; λ ex =364 nm 40 o C 0 o C -20 o C 1.0 0.8 B3 in CHCl 3 ; λ ex =430 nm 40 o C 0 o C -20 o C Fluorescence 0.6 0.4 Fluorescence 0.6 0.4 Fluorescence 0.6 0.4 0.2 0.2 0.2 0.0 350 400 450 500 550 0.0 400 450 500 550 600 0.0 450 500 550 600 650 1.0 0.8 B4 in CHCl 3 ; λ ex =380 nm 40 o C 0 o C -20 o C 1.0 0.8 B5 in CHCl 3 ; λ ex =445 nm 40 o C 0 o C -20 o C 1.0 0.8 B6 in CHCl 3 ; λ ex =461 nm 40 o C 0 o C -20 o C Fluorescence 0.6 0.4 Fluorescence 0.6 0.4 Fluorescence 0.6 0.4 0.2 0.2 0.2 0.0 400 450 500 550 600 0.0 450 500 550 600 650 700 0.0 500 550 600 650 700 750 800 Fig. S5. Fluorescence spectra of B1-B6 in CHCl 3 in different temperatures. 43

Table S1. Fluorescence wavelengths maximum of B1-B6 in CHCl 3 measured at different temperatures. B1 B2 B3 B4 B5 B6 Temperature λ max (nm) 40 o C 383.8 424 492.6 458.4 529.2 604 0 o C 384.8 426.6 497.6 465.6 538.4 614.6-20 o C 385.2 428.2 500.4 470.6 543 618.2 44