Naphthotetrathiophene Based Helicene-like Molecules: Synthesis and Photophysical Properties

Supporting information for: Naphthotetrathiophene Based Helicene-like Molecules: Synthesis and Photophysical Properties Xueqian Zhao 1, Lipeng Zhang 1, Jinsheng Song 1, *, Yuhe Kan 2, and Hua Wang 1, * 1 National & Local Joint Engineering Research Center for Applied Technology of Hybrid Nanomaterials, Henan University, Kaifeng, 475004, P.R. China. 2 Jiangsu Province Key Laboratory for Chemistry of Low Dimensional Materials, School of Chemistry and Chemical Engineering, Huaiyin Normal University, Huaian, 223300, China * Corresponding Author, E-mail: songjs@henu.edu.cn, hwang@henu.edu.cn Table of contents 1. Experimental section... 2 General procedures and materials.... 2 2.Structural Characterization... 5 Figure S1. 1 H NMR (400 MHz, CDCl 3 ) of compound 6... 5 Figure S2 13 C NMR (100 MHz, CDCl 3 ) of compound 6... 5 Figure S3 HRMS of compound 6... 6 Figure S4 IR spectrum of compound 6... 6 Figure S5 1 H NMR (400 MHz, CDCl 3 ) of compound 7... 7 Figure S6 13 C NMR (100 MHz, CDCl 3 ) of compound 7... 7 Figure S7 HRMS of compound compound 7... 8 Figure S8 IR spectrum of compound 7... 8 Figure S9 1 H NMR (400 MHz, CDCl 3 ) of NTT-COT... 9 Figure S10 13 C NMR (100 MHz, CDCl 3 ) of NTT-COT... 9 Figure S11 LRMS of NTT-COT... 10 Figure S12 HRMS of NTT-COT... 10 S1

Figure S13 IR spectrum of NTT-COT... 11 Figure S14 1 H NMR (400 MHz, CDCl 3 ) of NTT-T... 11 Figure S15 13 C NMR (100 MHz, CDCl 3 ) of NTT-T... 12 Figure S16 HRMS of NTT-T... 12 Figure S17 IR of NTT-T... 13 3. DFT quantum calculation... 13 Figure S18 Quantum calculation prediction for UV/vis spectra of NTT based molecules in chloroform performed by TD-DFT/PCM approach at the 6-31G (d, p) level.... 14 Table S1. Selected calculated absorption wavelength (nm), oscillator strength (f) and transition contributions of NTT based molecules in chloroform solvent at TD-B3LYP/6-31G (d,p) level of theory.... 14 Cartesian coordinate of ground state for NTT-T and NTT-COT optimized by B3LYP/6-31G(d,p)... 15 4. Cyclic voltammetry... 22 5. UV-vis absorption and photoluminescence properties... 23 6. X-ray crystallographic data... 24 Figure S21. ORTEP drawing of 6 with 30% thermal ellipsoids; hydrogen atoms were omitted for clarity.... 24 Table S2. Crystal data and structure refinement for 6.... 24 1. Experimental section General procedures and materials. Ether and tetrahydrofuran (THF) for use were freshly distilled from sodium/benzophenone prior to use. Concentration of n-buli (hexane) was determined by titration with N-pivaloyl-o-toluidine S1. Column chromatography was carried out on silica gel (300-400 mesh). Analytical thin-layer chromatography was performed on glass plates of Silica Gel GF-254 with detection by UV. Standard techniques for synthesis under inert atmosphere, using gasbag and Schlenk glassware equipped with an 8-mm PTFE vacuum stop-cock, were employed. All starting materials and reagents were commercially available. (11-bromonaphtho[1,2-b:4,3-b :5,6-b :8,7-b ]- tetrathiophene-2,5,8-triyl)tris(trimethylsilane) (5) was prepared according to the literature method S2. 1 H and 13 C NMR spectra were recorded on a 400M NMR S2

spectrometer. NMR spectra were obtained using chloroform-d (CDCl 3 ) as solvent. The chemical shift references were as follows: ( 1 H) CDCl 3, 7.26 ppm (CHCl 3 ); ( 13 C) CDCl 3, 77.00 ppm (CDCl 3 ). IR spectra were obtained using an FT-IR instrument, equipped with an ATR sampling accessory. HRMS spectra were recorded on a mass spectrometer equipped with TOF (EI+) and MALDI/DHB. Melting point determination was taken on a Melt-Temp apparatus and was uncorrected. UV-vis spectra were obtained with a double-beam spectrophotometer at room temperature. The X-ray crystallographic analyses was performed using crystal of 6 (triclinic crystal system) with the size 0.29 x 0.10 x 0.08 mm. The intensity data were collected with the ω scan mode (207K) on a diffractometer with CCD detector using Mo Kα radiation (λ=0.71073 Å). The data were corrected for Lorentz and polarisation effects and absorption corrections were performed using SADABS program S3. The crystal structures were solved using the SHELXTL program and refined using full matrix least squares S4. The positions of hydrogen atoms were calculated theoretically and included in the final cycles of refinement in a riding model along with attached carbons. Further details are in the deposited CIFs. Single crystals of compound 6 suitable for X-ray analysis were obtained by slow evaporation from CHCl 3 -CH 3 OH (4:1 v/v), respectively. The geometry optimization of NTT-T and NTT-COT were performed using Gaussian 09 program [1] at the B3LYP/6-31G(d,p) level of theory. The predicted absorption spectra were computed in the Linear-Response (LR) formalisms within the TD-DFT/PCM approaches based on hybrid B3LYP and hybrid Coulomb-attenuating CAM-B3LYP/6-31G(d,p) levels. Reference: [S1] Suffert, J. J. Org. Chem. 1989, 54, 509. [S2] (a) Erik Fischer.; Jan Larsen.; Hans G. Madsen.; Niels Harrit.; et al.; J. Org. Chem. 1996, 61, 6997-7705. (b) Jinsheng Song, Tianjing Wu, Xueqian Zhao Hua Wang.; et al.; Tetrahedron, 2015, 71,1838-1843. S3

[S3] Sheldrick, G. M. SADABS. University of Gottingen, Germany, 1996. [S4] Sheldrick, G. M. SHELXTL, version 5.1; Bruker Analytical X-ray Systems, Inc.: Madison, WI, 1997. [S5] Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Scalmani, G.; Barone, V.; Mennucci, B.; Petersson, G. A.; Nakatsuji, H.; Caricato, M.; Li, X.; Hratchian, H. P.; Izmaylov, A. F.; Bloino, J.; Zheng, G.; Sonnenberg, J. L.; Hada, M.; Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.; Ishida, M.; Nakajima, T.; Honda, Y.; Kitao, O.; Nakai, H.; Vreven, T.; Montgomery, J. A. J.; Peralta, J. E.; Ogliaro, F.; Bearpark, M.; Heyd, J. J.; Brothers, E.; Kudin, K. N.; Staroverov, V. N.; Kobayashi, R.; Normand, J.; Raghavachari, K.; Rendell, A.; Burant, J. C.; Iyengar, S. S.; Tomasi, J.; Cossi, M.; Rega, N.; Millam, J. M.; Klene, M.; Knox, J. E.; Cross, J. B.; Bakken, V.; Adamo, C.; Jaramillo, J.; Gomperts, R.; Stratmann, R. E.; Yazyev, O.; Austin, A. J.; Cammi, R.; Pomelli, C.; Ochterski, J. W.; Martin, R. L.; Morokuma, K.; Zakrzewski, V. G.; Voth, G. A.; Salvador, P.; Dannenberg, J. J.; Dapprich, S.; Daniels, A. D.; Farkas, O.; Foresman, J. B.; Ortiz, J. V.; Cioslowski, J.; Fox, G. D. J. Gaussian 09W, Revision D.01; Gaussian, Inc., Wallingford, CT, 2013. S4

2.Structural Characterization Figure S1. 1 H NMR (400 MHz, CDCl 3 ) of compound 6 Figure S2 13 C NMR (100 MHz, CDCl 3 ) of compound 6 S5

Figure S3 HRMS of compound 6 Figure S4 IR spectrum of compound 6 S6

Figure S5 1 H NMR (400 MHz, CDCl 3 ) of compound 7 Figure S6 13 C NMR (100 MHz, CDCl 3 ) of compound 7 S7

Figure S7 HRMS of compound compound 7 Figure S8 IR spectrum of compound 7 S8

Figure S9 1 H NMR (400 MHz, CDCl 3 ) of NTT-COT Figure S10 13 C NMR (100 MHz, CDCl 3 ) of NTT-COT S9

Figure S11 LRMS of NTT-COT Figure S12 HRMS of NTT-COT S10

Figure S13 IR spectrum of NTT-COT Figure S14 1 H NMR (400 MHz, CDCl 3 ) of NTT-T S11

Figure S15 13 C NMR (100 MHz, CDCl 3 ) of NTT-T Figure S16 HRMS of NTT-T S12

1.0 0.8 3. DFT quantum calculation 0.6 Normalized 0.4 0.2 Figure S17 IR of NTT-T NTT-COT-TD NTT-COT-CAM NTT-COT-EXP 2.5 2.0 1.5 1.0 0.5 Oscillator Strength 0.0 0.0 250 300 350 400 450 500 Wavelength (nm) S13

1.5 Normalized 1.0 0.8 0.6 0.4 0.2 NTT-T-TD NTT-T-CAM NTT-T-EXP 1.0 0.5 Oscillator Strength 0.0 0.0 250 300 350 400 450 Wavelength (nm) Figure S18 Quantum calculation prediction for UV/vis spectra of NTT based molecules in chloroform performed by TD-DFT/PCM approach at the 6-31G (d, p) level. Table S1. Selected calculated absorption wavelength (nm), oscillator strength (f) and transition contributions of NTT based molecules in chloroform solvent at TD- B3LYP/6-31G (d,p) level of theory. Compound Band State λ calc /nm Oscillator strength (f) Major transition contributions NTT-T I 1 389 0.4251 HOMO LUMO (85%) 3 370 0.2845 H-1 LUMO (37%), HOMO L+1 (21%) II 7 342 0.7924 H-2 LUMO (39%), H-1 L+3 (37%) 10 333 0.2686 HOMO L+2 (67%) 11 330 0.9293 H-3 L+1 (63%) 13 317 0.2580 H-2 L+2 (82%) NTT-COT I 1 420 0.3566 HOMO LUMO (96%) 2 404 1.3484 H-1 LUMO (63%) 5 392 0.4984 H-4 LUMO (25%), H-1 L+1 S14

(62%) II 34 325 2.1007 H-1 L+5 (34%) 35 324 0.4046 H-6 L+3 (37%), H-1 L+4 (20%) 43 318 0.3639 H-7 L+3 (52%), H-2 L+5 (42%) 44 316 0.4088 H-5 L+4 (48%) Cartesian coordinate of ground state for NTT-T and NTT-COT optimized by B3LYP/6-31G(d,p) NTT-T E = -7414.987917454619 a.u. NImag=0 C, -6.782567090395, 0.983765599476, 0.054407402248 C, -6.716419034669, -0.389953595100-0.321406619621 Si, 8.926872627013, 4.374329474199, -1.279032587056 C, 8.463517936813, 5.034807150615, -2.988323113578 C, -5.469166727062, -0.947914391201, -0.632876510789 C, -4.248905623634, -0.200594097923, -0.594190298904 C, 10.636181235521, 3.569309757481, -1.327824999585 C, 8.903235760996, 5.783090599404, -0.018851129960 C, -4.310236404234, 1.181230132565, -0.187253254249 C, -5.598104732610, 1.732062552869, 0.118455354032 H, -8.940715956764, 1.318360817948, 0.418157169757 H, 0.337372637014, -0.251673599704, -1.450555549623 C, -2.973643911320, -0.720033088513, -0.975034259536 C, -1.773788798090, -0.002738451940, -0.829927290771 H, -8.820797036577, -1.071737792802, -0.210675487561 H, 8.936558740296, 1.323101182453, -0.428151219748 C, -1.814416476633, 1.313365696932, -0.273231260575 C, -3.079253185472, 1.905811896416, -0.105652654515 H, 8.817051996268, -1.069686056189, 0.191261496209 H, -0.339505373730, -0.251710153681, 1.448279775238 S, -5.969036975822, 3.369222124520, 0.644874514805 C, -7.691210306596, 3.043241324275, 0.756873673032 H, -8.473058685106, 4.218947539582, 3.735793222227 H, -9.175385428783, 5.790321224417, 3.319610762573 C, -7.942136368292, 1.740663344781, 0.414617508430 C, -0.729333114076, 2.245947949941, -0.038417831706 H, -7.468045200888, 5.467602055772, 2.991858985996 H, -10.679645949716, 2.734951840233, 2.042982069005 C, -1.218629141959, 3.539926973768, 0.055626407551 S, -2.947152467426, 3.661425239330, 0.119857804977 H, -11.397006354448, 4.294682715404, 1.626210190564 H, -10.932795508378, 3.171888938516, 0.344483330353 S, -2.662400681584, -2.240905409352, -1.799173097342 C, -0.952585893870, -1.887264683639, -1.991670746313 H, -9.622113158148, 6.563948940199, 0.305368320851 H, -9.176691967411, 5.426545468484, -0.976810284219 S15

C, -0.656119790644, -0.678197377686, -1.422635676414 C, -7.788581037121, -1.332861936187, -0.415731103741 C, -7.405079617137, -2.596185547350, -0.783154668425 S, -5.666016377354, -2.649308053262, -1.028207778135 C, 0.724601983714, 2.246051430553, 0.031345555894 C, 1.213420667260, 3.540244247279, -0.062530443945 S, -0.002757724502, 4.792602813708, -0.003299625262 C, 1.810120414639, 1.313642075625, 0.265382220508 C, 3.074672404950, 1.906815703323, 0.097259319135 S, 2.941793478842, 3.662372969324, -0.127609522469 C, 1.770793136267, -0.002063574515, 0.823840307753 C, 2.971582506638, -0.718017129574, 0.968908366115 C, 4.245895303601, -0.198983598296, 0.584006457375 C, 4.306180837424, 1.183014592333, 0.177615832152 C, 5.466234873432, -0.946316582832, 0.619828010558 C, 6.712957421695, -0.387807664407, 0.307293306283 C, 6.778487398394, 0.986739924873, -0.065633285857 C, 5.593736533173, 1.734789535527, -0.127814226221 C, 7.937793833952, 1.744955723702, -0.423864062219 C, 7.686431571449, 3.048360055805, -0.762640821320 S, 5.964116103666, 3.373335212897, -0.650199509043 S, 5.663566762951, -2.648466539725, 1.011501255501 C, 7.402174592793, -2.595094987124, 0.763229790307 C, 7.785190175145, -1.331038195591, 0.397799801952 C, 0.654799144150, -0.676643591573, 1.421440788894 C, 0.954522968357, -1.881857873307, 1.997145243707 S, 2.663558987081, -2.236137347710, 1.799329564471 Si, -8.931876050820, 4.366834503983, 1.278778920650 C, -8.467950378369, 5.020843819339, 2.990419523335 H, -7.918124209771, 6.241411861446, -0.041748539088 H, -10.620235272889, -2.820386887947, -1.345665898320 H, -10.400792082444, -3.238519704437, 0.361964833068 H, -10.952514928137, -4.462486345093, -0.785588650933 H, -8.568850086132, -6.370871106585, 0.065247366944 H, -6.909364309383, -5.761702154601, 0.013562901899 H, -8.038556537725, -5.138945401975, 1.221652183413 H, -8.649027530330, -3.968799172646, -3.512632132975 H, -8.954962466662, -5.624053044850, -2.962106661934 H, -7.299908708126, -5.004880362106, -3.035008966730 H, 2.310113157349, -1.973609794510, -2.039486488143 H, 1.839016286490, -1.251010460928, -3.586757424603 H, 2.617477131549, -2.836921666104, -3.549512278785 H, -0.577910102629, -2.431174666468, -5.211410299440 H, 0.178083423752, -4.032352735822, -5.215135866026 H, -1.468319675323, -3.830881256729, -4.601797161365 H, -0.603472094310, -5.162106400058, -1.854165916740 H, 0.801126527946, -4.520551636390, -0.987223423541 H, 1.020699493819, -5.378394254737, -2.519890433206 H, 1.376131791443, -3.420810794300, 4.879115843104 H, -0.299908603377, -3.694866182822, 5.375587339855 H, 0.320215143707, -2.044073523540, 5.215894986665 H, -0.452946773857, -4.787350306170, 1.214317395151 H, 0.900536432417, -5.166632982246, 2.289172227161 H, -0.759385889104, -5.448227924167, 2.827288862137 H, -2.656108991640, -2.964260598550, 3.369870456610 H, -2.282754921122, -2.266632398500, 1.788899274514 H, -2.023349741237, -1.319419029568, 3.261801672440 H, 10.397669195827, -3.233695470630, -0.385314992438 S16

C, -10.640884827499, 3.561039293882, 1.325463678405 C, -8.909313890878, 5.780516787100, 0.024123159905 Si, -8.496441810632, -4.117922062263, -1.018454639261 C, -10.280683663884, -3.605805344892, -0.662530810058 C, -7.952064209743, -5.472642733657, 0.182492176688 C, -8.334574321986, -4.735818851034, -2.797473560691 Si, 0.219405159005, -3.044251618895, -2.918284583760 C, 1.899668995239, -2.192030445173, -3.030477240939 C, -0.478632739596, -3.363947687876, -4.646845787734 C, 0.371260032005, -4.678906478208, -1.981337264042 Si, -0.201642967977, -3.017916933179, 2.969145153271 C, 0.351703141628, -3.047087707319, 4.778151824429 C, -0.118713928028, -4.766649188528, 2.256298265341 C, -1.950367546552, -2.323059653374, 2.830040721418 Si, 8.493394913868, -4.117944949179, 0.992156001098 C, 10.277638830911, -3.604725246501, 0.637843040359 C, 7.948578360451, -5.467706779950, -0.214179960717 H, 10.949342510530, -4.461976906155, 0.757589798020 H, 10.617430315962, -2.821894339301, 1.323819445316 H, 6.905859145121, -5.757279873248, -0.046268257159 H, 8.034986284661, -5.129867636149, -1.252010849350 H, 8.565243796098, -6.366495286995, -0.100639522423 H, 8.951582241149, -5.632281380648, 2.929449863873 H, 7.296926635575, -5.012464773860, 3.005363573515 H, 8.646786940940, -3.979135676519, 3.486898693157 H, 7.463458345411, 5.481223078161, -2.988470235437 H, 8.469241570856, 4.235840237356, -3.736827160487 H, 9.170827201796, 5.805822625242, -3.314163703019 H, 11.392174172399, 4.304279223104, -1.625637864202 H, 10.927779331399, 3.176864120133, -0.348063444105 H, 10.675588800666, 2.745729148754, -2.048183071722 H, 9.170283578008, 5.425280311517, 0.980808461757 H, 7.911872827258, 6.243408076783, 0.048412346104 H, 9.615918873860, 6.567839186745, -0.296691977773 C, 8.331681733308, -4.743003522294, 2.768664055858 NTT-COT E = -14033.64940296565 a.u. NImag=0 C, -3.895510594917, 4.787373738138, -4.357630661677 C, -5.042837764625, 5.141739780648, -3.590446546752 C, -5.252240801040, 4.518747687024, -2.351906359367 C, -4.363707664412, 3.530749537406, -1.816244281310 C, -3.214750496483, 3.156288481001, -2.601969396472 C, -3.015730462746, 3.815319582614, -3.859784584687 C, -4.533614694288, 2.898575440622, -0.544577079545 C, -3.667346558117, 1.911072293987, -0.042951003262 C, -2.560949396499, 1.492212223911, -0.848015135361 C,5.252250802490, -4.518731695287, -2.351911360092 C,4.363712665137, -3.530740541393, -1.816246276309 C,3.214758487059, -3.156277479406, -2.601973397052 C,3.015744459484, -3.815301580004, -3.859792585847 C,4.533614694288, -2.898572440187, -0.544576079400 C,3.667342557537, -1.911074294277, -0.042949003290 C,2.560947396209, -1.492213224056, -0.848014135216 C,2.348408360165, -2.144342335604, -2.075676316940 S,1.700407259793, -3.578807541873, -5.004179763179 S17

C, -2.348405359730, 2.144347325745, -2.075674316650 S, -1.700390257328, 3.578828555502, -5.004169761729 C, -2.335827356282, 4.772465735512, -6.124755954012 C, -3.494239535207, 5.308977841568, -5.627958849207 C, -1.571990239830, 0.470367076165, -0.575090085318 C, -0.592691086840, 0.424309062185, -1.540003237289 S, -0.884594136982, 1.553202240822, -2.844641436107 S, -5.789774848907, 3.243266498446, 0.633085096586 C, -5.147271783733, 2.090910319211, 1.788167274209 C, -4.032012617729, 1.483952222147, 1.276215199757 C, -6.063611957105, 6.088101962683, -3.920962597108 C, -7.050725068357, 6.212360930078, -2.978813459740 S, -6.732352032459, 5.135182782398, -1.628892246074 C, -1.571992240120, -0.470370076070, 0.575087084883 C, -0.592695092711, -0.424313062236, 1.540003237289 C, -2.560953397079, -1.492214224201, 0.848010134636 C, -2.348414361035, -2.144349326035, 2.075670316070 S, -0.884604138432, -1.553205235965, 2.844640435962 C, -3.667347558262, -1.911073294132, 0.042944003305 C, -4.533618694868, -2.898574440477, 0.544567083386 C, -4.363716665717, -3.530748537261, 1.816234279860 C, -3.214762487639, -3.156287480856, 2.601962400749 C, -5.252251802635, -4.518743686444, 2.351894357627 C, -5.042855772527, -5.141733785069, 3.590436555885 C, -3.895530597817, -4.787368737413, 4.357623660662 C, -3.015747459919, -3.815316582179, 3.859778583817 C, -3.494264538832, -5.308971808947, 5.627953874941 C, -2.335853360052, -4.772460724204, 6.124753943138 S, -1.700411260373, -3.578825544483, 5.004168761584 C,2.335851359762, -4.772436736599, -6.124771935165 C,3.494263538687, -5.308947837218, -5.627974830360 C,1.571986239250, -0.470370076070, -0.575087084883 C,0.592690086695, -0.424309062185, -1.540002237144 S,0.884598137562, -1.553196239952, -2.844644436542 S,5.789771885514, -3.243266498446, 0.633088097021 C,5.147261782283, -2.090916320081, 1.788173275079 C,4.032003616424, -1.483958223017, 1.276221195335 C,6.063631960005, -6.088072963770, -3.920974598848 C,7.050742054947, -6.212336958348, -2.978821455609 S,6.732361028472, -5.135167780223, -1.628894246364 C,1.571985239105, 0.470364075730, 0.575092085608 C,0.592686086115, 0.424304062518, 1.540005237579 C,2.560945385336, 1.492207223186, 0.848020136086 C,2.348403359440, 2.144338335024, 2.075682317810 S,0.884591136547, 1.553192239372, 2.844647426394 C,3.667341562684, 1.911068293407, 0.042957003285 C,4.533612688707, 2.898567439462, 0.544587080995 C,4.363707664412, 3.530736540813, 1.816256277759 C,3.214751496628, 3.156274478971, 2.601980398067 C,5.252243801475, 4.518729694997, 2.351922361687 C,5.042844765640, 5.141715782459, 3.590466544360 C,3.895517595932, 4.787349724075, 4.357648664287 C,3.015733457889, 3.815299579714, 3.859798597301 C,3.494247536367, 5.308948842654, 5.627980862981 C,2.335834357297, 4.772437736744, 6.124774951475 S,1.700393257763, 3.578806541728, 5.004183763759 S,6.732357059643, 5.135164779788, 1.628910253975 C,7.050734064371, 6.212334947475, 2.978836447200 S18

S, -6.732362033909, -5.135178781818, 1.628875243609 C, -7.050741049510, -6.212354950375, 2.978796457275 C, -6.063630954569, -6.088094924625, 3.920949600514 C, -4.032009617294, -1.483953222292, -1.276225195915 C, -5.147267783153, -2.090910319211, -1.788180276094 S, -5.789775854344, -3.243265498301, -0.633099098616 Si, -1.466626223458, 5.188520785161, -7.747605149363 C,0.284271041541, 5.798614860687, -7.381799151998 C, -2.469020380838, 6.544892949957, -8.600855308246 C, -1.392504218021, 3.643949557564, -8.835253365254 Si, -8.558510280193, 7.346535150548, -3.021313462643 C, -8.551987270997, 8.246786250593, -4.683389715488 C, -8.448879306574, 8.590240277220, -1.601921240590 C, -10.127977556361, 6.307930976260, -2.843851437976 Si, -5.956130924814, 1.787127266287, 3.467350536322 C, -4.811364734862, 0.667941102376, 4.467881682862 C, -6.192372952864, 3.444572535564, 4.347670662125 C, -7.635322151044, 0.956098154399, 3.213484487540 Si, -5.956121928801, -1.787128266432, -3.467366522766 C, -7.635312149594, -0.956095143380, -3.213506496022 C, -6.192364962287, -3.444574525270, -4.347685664300 C, -4.811349737978, -0.667946103101, -4.467895679600 Si, -8.558527266782, -7.346528165409, 3.021292459598 C, -8.552006268461, -8.246783287200, 4.683366717444 C, -8.448896293164, -8.590229270333, 1.601896242257 C, -10.127993590432, -6.307921980246, 2.843832435221 Si, -1.466658222806, -5.188514794874, 7.747607160237 C,0.284238041518, -5.798614860687, 7.381807142574 C, -2.469058381056, -6.544883054342, 8.600857266202 C,6.063620953119, 6.088072963770, 3.920986600588 C,4.032006616859, 1.483953222292, -1.276211199177 C,5.147265782863, 2.090911319356, -1.788161278631 S,5.789771885514, 3.243262497866, -0.633076100572 Si, 1.466656222516, -5.188486785522, -7.747626157700 C, -0.284239041663, -5.798591841477, -7.381827145474 C,2.469058381056, -6.544848975327, -8.600882296286 C,1.392528216209, -3.643908556911, -8.835264372141 Si, 8.558532293966, -7.346506151635, -3.021323458801 C,8.552007273897, -8.246759262553, -4.683398716793 C,8.448908305487, -8.590208314914, -1.601928241605 C, 10.127996553825, -6.307894939289, -2.843866434859 Si, 5.956115949098, -1.787139278610, 3.467361527333 C,4.811343737108, -0.667961099984, 4.467893679310 C,6.192359935104, -3.444588522008, 4.347674662705 C,7.635306169891, -0.956105144830, 3.213504495732 Si, 5.956122934238, 1.787133267157, -3.467347535887 C,6.192365967724, 3.444581520993, -4.347661660820 C,7.635314160467, 0.956101154834, -3.213486487830 C,4.811353738558, 0.667953098824, -4.467880682717 Si, 8.558522292516, 7.346505146198, 3.021340461266 C,8.552001294195, 8.246750266540, 4.683420719983 C,8.448896293164, 8.590215300054, 1.601952239794 C, 10.127986552375, 6.307895944726, 2.843875436164 Si, 1.466635219471, 5.188487785667, 7.747627163137 C, -0.284260041533, 5.798589883521, 7.381823123727 C,2.469033377431, 6.544852044555, 8.600884307160 C,1.392507218456, 3.643911557346, 8.835267388451 H,4.059631621921, -6.069838944548, -6.154206943381 S19

C, -1.392535217224, -3.643942556549, 8.835252359817 H, -4.059602617715, 6.069873923164, -6.154187945918 H, -3.469202534982, 0.748696117083, 1.832811281071 H, -6.058154922561, 6.659502052710, -4.842443738037 H, -4.059631621921, -6.069865932587, 6.154182971652 H, -6.058177941771, -6.659494062133, 4.842431741589 H, -3.469197523674, -0.748698117373, -1.832819282231 H,0.268218040638, 6.691372017119, -6.748307044023 H,0.812206123679, 6.052326934764, -8.307997294257 H,0.873277136460, 5.035439776724, -6.862211071009 H, -2.526226383535, 7.450329140357, -7.987869242012 H, -2.001180304899, 6.820392045141, -9.552508463714 H, -3.491168529127, 6.218592944704, -8.819254379061 H, -0.889932138397, 3.857160585213, -9.785537486261 H, -2.396318364339, 3.270471500817, -9.062306389128 H, -0.842214135604, 2.835137433882, -8.342932253292 H, -8.609219272173, 7.546227170598, -5.522872820227 H, -7.650669190866, 8.855257376538, -4.811546734793 H, -9.414681444572, 8.918394360800, -4.754750722753 H, -9.318572378444, 9.257053406539, -1.596075239600 H, -8.410381291285, 8.085341257062, -0.630934096904 H, -7.550428150025, 9.209972400860, -1.687754261346 H, -10.214636575177, 5.579245860893, -3.656361558109 H, -11.021584677291, 6.941969036403, -2.863694436498 H, -10.136079577550, 5.752864841625, -1.899803295133 H, -5.243131797881, 0.471621075958, 5.455703822835 H, -3.830176583137, 1.128570175194, 4.621559703779 H, -4.655285715055, -0.299670042865, 3.980266612969 H, -5.233586800294, 3.948714599417, 4.506517686410 H,3.469190522659, -0.748706118533, 1.832818282086 H,6.058180958081, -6.659468026612, -4.842458740212 H,4.059613619311, 6.069839949984, 6.154213928521 H,6.058166934884, 6.659469032049, 4.842469741807 H,3.469194523239, 0.748701117808, -1.832809280781 H, -0.268183040326, -6.691353019656, -6.748340064683 H, -0.812171123896, -6.052301957598, -8.308028251126 H, -0.873251137982, -5.035423763821, -6.862236048175 H,2.526268384333, -7.450288129120, -7.987901204318 H,2.001222300406, -6.820345054201, -9.552537462627 H,3.491205529200, -6.218540926580, -8.819277345354 H,0.889959137020, -3.857115583980, -9.785550504021 H,2.396341362382, -3.270423499148, -9.062312368831 H,0.842232122339, -2.835103434244, -8.342939291350 H,8.609235306244, -7.546200182559, -5.522882821677 H,7.650691151722, -8.855234357328, -4.811551735518 H,9.414705469219, -8.918364356450, -4.754760724203 H,9.318607409978, -9.257014406176, -1.596078240035 H,8.410403252141, -8.085307230965, -0.630942098064 H,7.550462176122, -9.209948376213, -1.687762257214 H, 10.214652556330, -5.579213845669, -3.656379560719 H, 11.021604680191, -6.941931041476, -2.863707438383 H, 10.136097569576, -5.752826846698, -1.899820287014 H,5.243107799693, -0.471644076118, 5.455718851469 H,3.830156580237, -1.128593178529, 4.621567704939 H,4.655263717157, 0.299652042901, 3.980282604705 H,5.233575798699, -3.948733602172, 4.506515686120 H,6.830214051142, -4.121083626445, 3.768721578177 H,6.663910046276, -3.302453502633, 5.326731844107 S20

H, -6.830222041718, 4.121072624850, 3.768718577742 H, -6.663927032866, 3.302435500023, 5.326725811486 H, -8.302107286887, 1.576859242033, 2.605684400680 H, -8.130476266326, 0.776939121795, 4.174659637259 H, -7.525376158209, -0.008050000631, 2.706888417112 H, -8.302100248829, -1.576854241308, -2.605707398723 H, -8.130463248565, -0.776936121360, -4.174683640739 H, -7.525366156759, 0.008054000629, -2.706911415155 H, -5.233579799279, -3.948718599997, -4.506527682568 H, -6.830217067452, -4.121071624705, -3.768733579917 H, -6.663915020542, -3.302437500313, -5.326741845557 H, -5.243113800563, -0.471626076154, -5.455719856905 H, -3.830161580962, -1.128577176209, -4.621569705229 H, -4.655269707443, 0.299666042814, -3.980281604560 H, -7.650688188329, -8.855256371102, 4.811522736605 H, -9.414701447472, -8.918391344490, 4.754725724419 H, -8.609239275073, -7.546226165162, 5.522851864808 H, -8.410393303609, -8.085327233865, 0.630911098861 H, -7.550448152925, -9.209965415720, 1.687731258011 H, -9.318592381344, -9.257039383342, 1.596045240542 H, -11.021600711362, -6.941960040389, 2.863671438455 H, -10.136093547829, -5.752852882219, 1.899786287376 H, -10.214653561766, -5.579239828272, 3.656344560936 H,0.873248137547, -5.035443772013, 6.862219061586 H,0.268184040471, -6.691374027993, 6.748316040036 H,0.812170123751, -6.052326934764, 8.308007295707 H, -2.001222300406, -6.820382043691, 9.552512485461 H, -3.491206524053, -6.218578974424, 8.819252368187 H, -2.526265383898, -7.450320144344, 7.987872205404 H,8.130457268863, -0.776949117953, 4.174681640449 H,7.525359171619, 0.008046000633, 2.706911415155 H,8.302095274563, -1.576861242323, 2.605702397998 H,6.663918036852, 3.302447501763, -5.326717820910 H,5.233580799424, 3.948725601012, -4.506504695109 H,6.830217067452, 4.121078625720, -3.768708576292 H,8.130466264876, 0.776945117373, -4.174662637694 H,8.302100248829, 1.576859242033, -2.605683400535 H,7.525367162196, -0.008049000592, -2.706893417837 H,4.655274702877, -0.299660043002, -3.980269613404 H,5.243119801433, 0.471635075872, -5.455703822835 H,3.830166581687, 1.128583177079, -4.621556703344 H,7.650685172019, 8.855225361315, 4.811577739288 H,9.414698484080, 8.918355360437, 4.754784722391 H,8.609230279060, 7.546188170235, 5.522900866622 H,8.410395261565, 8.085318237852, 0.630963095817 H,7.550447147488, 9.209950387087, 1.687787260839 H,9.318592381344, 9.257024407626, 1.596107244240 H, 11.021595684178, 6.941932046913, 2.863719440123 H, 10.136086562690, 5.752832879319, 1.899826293176 H, 10.214644565753, 5.579209823922, 3.656384561444 H, -0.873270135445, 5.035419763241, 6.862231073909 H, -0.268204040725, 6.691351061700, 6.748336042936 H, -0.812195122084, 6.052299946724, 8.308023276859 H,2.001194301637, 6.820349075948, 9.552538468064 H,3.491180536159, 6.218546959201, 8.819281367101 H,2.526243391292, 7.450291145431, 7.987902262672 H,2.396320364629, 3.270428499873, 9.062318401452 H,0.842213135459, 2.835104434389, 8.342942254742 S21

H, -2.396348363397, -3.270459499077, 9.062301361944 H,0.889935138832, 3.857118584415, 9.785552461977 H, -0.842240134083, -2.835132438449, 8.342931247856 H, -0.889966138035, -3.857152584053, 9.785538491697 C,3.895529597672, -4.787349724075, -4.357641673856 C,5.042854777674, -5.141715782459, -3.590455542765 4. Cyclic voltammetry 0.1 0.0 Current (ma) -0.1-0.2-0.3-0.4 NTT-T NTT-COT 0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 Voltage vs Ag/Ag + (V) Figure S19. Cyclic voltammograms of NTT-T and NTT-COT. S22

5 (NTT-monomer) 7 (NTT-dimer) 0.8 DTT-T DTT-COT 0.6 5. UV-vis absorption and photoluminescence properties 0.4 Absorbance 0.2 0.0 (a) 250 300 350 400 450 500 Wavelength(nm) PL intensity (a.u.) 2500 2000 1500 1000 500 0 NTT-T NTT-COT (b) 350 400 450 500 550 Wavelength(nm) Figure S20. (a) UV/vis spectra of compound 5, 7, NTT-T and NTT-COT in dichloromethane at room temperature ([C] = 5 10 6 M); (b) photoluminescence spectra of compound NTT-T and NTT-COT in dichloromethane ([C] = 5 10 6 M), λ ex = 300 nm, slit: 5/5. S23

6. X-ray crystallographic data Figure S21. ORTEP drawing of 6 with 30% thermal ellipsoids; hydrogen atoms were omitted for clarity. Table S2. Crystal data and structure refinement for 6. Identification code 6 Empirical formula C27 H31 Br S4 Si3 Formula weight 647.94 Temperature 293(2) K Wavelength 0.71073 A Crystal system, space group Monoclinic, P2(1)/c Unit cell dimensions a = 12.218(15) A alpha = 90 deg. b = 19.59(2) A beta = 108.61(3) deg. c = 14.050(17) A gamma = 90 deg. Volume 3187(7) A^3 S24

Z, Calculated density 4, 1.350 Mg/m^3 Absorption coefficient 1.680 mm^-1 F(000) 1336 Crystal size 0.36 x 0.21 x 0.13 mm Theta range for data collection 1.76 to 25.00 deg. Limiting indices -14<=h<=14, -23<=k<=23, -16<=l<=12 Reflections collected / unique 15371 / 5597 [R(int) = 0.1225] Completeness to theta = 25.00 99.3 % Absorption correction Semi-empirical from equivalents Max. and min. transmission 0.8112 and 0.5830 Refinement method Full-matrix least-squares on F^2 Data / restraints / parameters 5597 / 0 / 316 Goodness-of-fit on F^2 1.005 Final R indices [I>2sigma(I)] R1 = 0.0633, wr2 = 0.1500 R indices (all data) R1 = 0.1623, wr2 = 0.1774 Largest diff. peak and hole 0.632 and -0.580 e.a^-3 S25