SUPPORTING INFORMATION. Visible Light Excitation of a Molecular Motor with an Extended Aromatic Core

SUPPORTING INFORMATION Visible Light Excitation of a Molecular Motor with an Extended Aromatic Core Thomas van Leeuwen, Jasper Pol, Diederik Roke, Sander J. Wezenberg, Ben L. Feringa* Stratingh Institute for Chemistry, University of Groningen, Nijenborgh 4, 9747 AG Groningen, The Netherlands. Email: b.l.feringa@rug.nl Table of Contents General Remarks... S2 NMR spectra... S4 HRMS spectra... S8 Eyring Plot... S10 Computational Details... S11 References... S21 S1

General Remarks Compounds 4 and 6 were synthesized following procedures that are described in the literature. 1,2 All other reagents were obtained from commercial sources and used as received without further purification. Dry solvents were obtained from a MBraun solvent purification system. Column chromatography was performed on a Reveleris X2 Flash Chromatography system, TLC: silica gel 60, Merck, 0.25 mm. High Resolution Mass spectra (HRMS) were recorded on an LTQ Orbitrap XL. NMR spectra were obtained using a Varian Mercury Plus ( 1 H, 400 MHz, 13 C, 100 MHz), or a Varian Innova ( 1 H: 600 MHz) instrument in CDCl 3, or CD 2 Cl 2. Chemical shifts are reported in δ units (ppm) relative to the residual solvent signal of CDCl 3 ( 1 H-NMR, δ 7.26 ppm; 13 C-NMR, δ 77.0 ppm) or CD 2 Cl 2 ( 1 H-NMR, δ 5.32 ppm; 13 C- NMR, δ 54.0 ppm). For 1 H NMR spectroscopy, the splitting pattern of peaks is designated as follows: s (singlet), d (doublet), t (triplet), (multiplet), br (broad), p (quintet) or dd (doublet of doublets). UV-vis absorption spectra were measured on a Hewlett-Packard 8453 spectrometer diode array spectrometer in a 1 cm quartz cuvette. Dichloromethane used for spectroscopic studies was of spectroscopic grade (UVASOL, Merck). Irradiation experiments were performed using Thorlab LEDs. Density functional theory (DFT) calculations were carried out with the Gaussian 09 program (rev. D.01) program package. 3 All of the calculations were performed on systems in the gas phase using the Becke s three parameter hybrid functional 4 with the LYP correlation functional 5,6 (DFT B3LYP/6-31G(d,p)). Each geometry optimization was followed by a vibrational analysis to determine that a minimum or saddle point on the potential energy surface was found. (7H-dibenzo[c,g]fluoren-7-ylidene)hydrazine (5) Hydrazine monohydrate (2 ml) was added to a solution of ketone 4 (0.30 g, 1.07 mmol) in EtOH (50 ml) and the solution was heated at reflux for 3 h. The reaction mixture was poured onto water and extracted with CH 2 Cl 2 (2 x 50 ml). The organic layer was dried over Na 2 SO 4 and concentrated in vacuo. The crude compound was purified by column chromatography (SiO 2, pentane: ethyl acetate = 5: 1). Hydrazone 5 was obtained as an orange crystalline solid (0.20 g, 0.68 mmol, 64 %). 1 H-NMR (400 MHz, CDCl 3 ): δ(ppm) 8.69 8.60 (m, 1H), 8.51 (d, J = 8.1 Hz, 1H), 8.09 (d, J = 8.4 Hz, 1H), 8.04 7.81 (m, 5H), 7.64 7.43 (m, 4H). 13 C- NMR: δ(ppm) 145.1, 140.2, 137.3, 135.7, 135.1, 134.9, 129.0, 128.7, 128.5, 128.4, 128.3, 128.2, 127.9, 127.7, 126.8, 126.4, 125.5, 125.3, 125.1, 121.8, 118.6. HRMS (ESI) m/z: [M + H] + Calcd for C 21 H 15 N 2 + 295.1230; Found 295.1233. S2

7-(2-methyl-2,3-dihydro-1H-cyclopenta[a]naphthalen-1-ylidene)-7H-dibenzo[c,g]fluorene (2) Activated MnO 2 (0.20 g, 2.30 mmol) was added to a stirred solution of 5 (0.20 g, 0.68 mmol) in dry THF (5 ml). The mixture was stirred for 15 min and filtered over a plug of celite. The obtained diazo solution was added dropwise to solution of 6 (0.17 g, 0.80 mmol) in toluene (5 ml). The reaction mixture was stirred at room temperature for 16 h and subsequently concentrated in vacuo. After evaporation of the solvent the crude product was purified by column chromatography (SiO 2, pentane: CH 2 Cl 2 = 5: 1), followed by recrystallization (ethanol: heptane = 1:1), to give alkene 2 as an orange solid (53 mg, 0.12 mmol, 18%). 1 H- NMR (400 MHz, CDCl 3 ): δ(ppm) 8.68 (d, J = 7.4 Hz, 1H), 8.64 (d, J = 8.4 Hz, 1H), 8.01 7.95 (m, 7H), 7.92 (d, J = 8.5 Hz, 1H), 7.78 (d, J = 8.2 Hz, 1H), 7.63 (d, J = 8.2 Hz, 1H), 7.60 7.40 (m, 12H), 7.34 7.28 (m, 3H), 7.05 (d, J = 8.6 Hz, 1H), 4.52 (p, J = 6.5 Hz, 1H), 3.65 (dd, J = 14.9, 5.6 Hz, 1H), 2.86 (d, J = 14.9 Hz, 1H), 1.46 (d, J = 6.7 Hz, 4H). 13 C-NMR (100 MHz, CDCl 3 ): δ(ppm) 154.5, 148.3, 139.2, 137.5, 136.9, 136.5, 136.4, 133.9, 133.8, 132.7, 132.1, 131.4, 130.4, 128.7, 128.6, 128.4, 128.3, 128.3, 127.4, 127.3, 127.1, 126.9, 126.2, 125.5, 125.2, 125.0, 124.8, 124.6, 124.0, 123.5, 121.7, 46.1, 42.3, 19.6. HRMS(APCI) m/z: [M + H] + Calcd for C 35 H 25 445.1951; Found 445.1945 S3

NMR spectra Figure S1: 1 H-NMR of 5 Figure S2: 13 C-NMR of 5 S4

Figure S3: 1 H-NMR of 2 Figure S4: 13 C-NMR of 2 S5

H c H b H b H a H c H b H b H a Figure S5: 1 H-NMR of 2 in CD 2 Cl 2 upon irradiation. Initial state (bottom spectrum), PSS (top spectrum). NMR irradiation experiments were performed at 40 C with a Thorlab model M420F2 high-power LED coupled to a 600 mm optical fiber, which guided the light into the NMR tube inside the spectrometer. 7 S6

Figure S6: Plot of concentration of metastable 1 and 2 versus irradiation time, as determined by UV/Vis spectroscopy (Toluene, -5 C, Abs 420 >2) using the same light-source (Thorlab model M420F2 high-power LED) and setup (= equal photon flux for both experiments). It can be concluded that the photochemical efficiency for the conversion of the stable to the metastable form is lower for 2 than for 1. However, since the PSS ratio for 2 remains in favour of the metastable isomer, the photoconversion efficiency of the backward isomerization process is also significantly lower and the switching function is thus retained. S7

HRMS spectra Relative Abundance 100 90 80 70 60 50 40 30 20 10 0 100 90 80 70 60 50 40 30 20 10 295.12338 307.07999 279.10449 80.94768 132.95821 164.98445 219.18735 335.15462 413.26570 472.55510 528.50986 295.12298 NL: 5.34E6 JP_03#6-22 RT: 0.13-0.58 AV: 17 T: FTMS + p ESI Full ms [50.00-550.00] NL: 7.91E5 C 21 H 15 N 2: C 21 H 15 N 2 pa Chrg 1 0 100 150 200 250 300 350 400 450 500 550 m/z Figure S7: HRMS of 5 (top: measured, bottom: calcd.) Relative Abundance 100 90 80 70 60 50 40 30 20 265.10086 NL: 4.43E6 JP_009#6-14 RT: 0.12-0.34 AV: 9 T: FTMS + p APCI corona Full ms [250.00-850.00] 10 0 100 90 80 415.14762 281.09604 403.14820 445.19454 529.19417 564.63599 607.39053 663.45236 719.68341 785.14900 831.33056 445.19508 NL: 6.84E5 C 35 H 25: C 35 H 25 pa Chrg 1 70 60 50 40 30 20 10 0 300 350 400 450 500 550 600 650 700 750 800 850 m/z Figure S8: HRMS of 2 (top: measured, bottom: calcd.) S8

Relative Abundance 100 90 80 70 60 50 40 30 20 10 0 100 90 80 429.16343 432.14650 435.13788 437.11748 443.14267 441.12706 445.19454 445.19508 447.13759 455.14298 449.11704 451.13287 457.15824 459.13759 471.13751 474.15660 461.15324 477.14804 463.13251 469.12170 465.14841 479.12820 485.11693 NL: 1.47E5 JP_009#6-14 RT: 0.12-0.34 AV: 9 T: FTMS + p APCI corona Full ms [250.00-850.00] NL: 6.84E5 C 35 H 25: C 35 H 25 pa Chrg 1 70 60 50 40 30 20 10 0 450.21185 430 435 440 445 450 455 460 465 470 475 480 485 m/z Figure S9: HRMS of 2 (top: measured, bottom: calcd.) S9

Eyring Plot Figure S10: Eyring Plot of the THI of 2. A solution of 2 in CH 2 Cl 2 (~1 x 10-5 M) in a 1cm cuvette was irradiated to PSS at 420 nm. The rate of the thermal relaxation was followed by monitoring the absorbance at 475 nm at 6 different temperatures (10, 15, 20, 25, 30, 35 C). The Eyring equation gave the thermodynamic parameters of the process. S10

Computational Details Figure S11: DFT optimized structures of TS1 (top left), TS2 (top right), TS3 (bottom left) and TS4 (bottom right) S11

SCF energy in Hartree, number of imaginary frequencies and Cartesian coordinates in Ångströms. (P,M)-2 0-1348.24807303 C -1.637242000-1.317061000-0.532154000 C -0.376234000-0.782022000-0.366445000 C -1.924230000-2.652909000-1.244648000 C -3.399472000-2.497038000-1.717958000 C -3.954167000-1.396757000-0.862467000 C -2.934728000-0.730238000-0.178325000 C 0.875148000-1.521611000-0.135744000 C 1.936238000-0.603032000 0.008205000 C 1.425236000 0.726391000-0.371712000 C 0.020062000 0.635148000-0.452132000 C 1.064281000-2.895127000 0.147667000 C 2.300148000-3.348853000 0.539451000 C 3.366405000-2.444549000 0.795980000 C 3.171408000-1.032485000 0.593649000 C 4.595886000-2.909071000 1.332524000 C 5.575976000-2.030783000 1.734801000 C 5.345436000-0.639719000 1.641101000 C 4.177526000-0.156893000 1.091451000 C 2.082010000 1.929370000-0.790601000 C 1.264891000 3.084807000-1.053921000 C -0.151796000 2.971327000-1.019464000 C -0.763389000 1.763723000-0.788725000 C 3.473264000 2.035653000-1.072687000 C 4.038930000 3.227734000-1.470988000 C 3.244855000 4.386997000-1.620104000 C 1.884395000 4.305909000-1.428644000 C -5.308321000-1.047222000-0.713985000 C -5.650701000-0.044111000 0.164400000 C -4.667848000 0.592222000 0.971380000 C -3.281702000 0.235030000 0.835857000 C -5.049651000 1.547444000 1.950735000 C -4.121033000 2.099895000 2.802506000 C -2.769071000 1.700656000 2.715371000 C -2.360466000 0.796362000 1.757514000 C -1.010491000-2.993849000-2.430243000 H -1.894498000-3.472547000-0.511044000 H -3.417361000-2.214921000-2.779901000 H -3.975259000-3.425104000-1.631152000 H 0.241134000-3.594806000 0.063423000 H 2.461002000-4.407425000 0.724931000 H 4.736248000-3.980815000 1.448492000 H 6.506972000-2.400894000 2.153876000 H 6.088799000 0.056633000 2.018365000 H 4.006324000 0.911099000 1.069786000 H -0.748582000 3.851442000-1.243399000 H -1.840414000 1.681695000-0.860433000 S12

H 4.094538000 1.152288000-1.008958000 H 5.102739000 3.271293000-1.686157000 H 3.702906000 5.325662000-1.917602000 H 1.252963000 5.175514000-1.592546000 H -6.071534000-1.566884000-1.286476000 H -6.690129000 0.249099000 0.286139000 H -6.099227000 1.819114000 2.027607000 H -4.426221000 2.823671000 3.552251000 H -2.042043000 2.106214000 3.412665000 H -1.321575000 0.499230000 1.713766000 H -1.375920000-3.898581000-2.928579000 H 0.025853000-3.165750000-2.141235000 H -1.021634000-2.179206000-3.161585000 (M,M)-2 0-1348.24597800 C -5.243675000 2.036822000 0.695337000 C -5.267525000 0.657588000 0.640344000 C -6.384955000 2.952920000 0.208673000 C -5.646559000 4.279057000-0.141663000 C -4.358810000 4.204695000 0.622911000 C -4.140679000 2.913638000 1.109454000 C -6.446199000-0.212563000 0.741657000 C -6.072678000-1.554001000 0.523148000 C -4.602423000-1.590230000 0.392947000 C -4.141389000-0.258021000 0.394572000 C -7.754368000 0.110052000 1.174374000 C -8.711876000-0.871341000 1.248325000 C -8.432069000-2.196956000 0.815471000 C -7.098486000-2.551310000 0.402516000 C -9.465985000-3.166202000 0.741594000 C -9.237415000-4.416221000 0.212626000 C -7.956821000-4.733756000-0.291183000 C -6.920641000-3.828887000-0.197924000 C -3.645408000-2.659246000 0.338391000 C -2.290097000-2.328242000-0.017978000 C -1.922404000-0.969592000-0.221723000 C -2.811586000 0.047553000 0.021729000 C -3.909357000-4.004968000 0.717264000 C -2.934904000-4.978399000 0.651511000 C -1.633779000-4.664968000 0.200471000 C -1.321793000-3.361475000-0.112977000 C -3.462001000 5.259815000 0.868642000 C -2.353029000 5.028968000 1.650740000 C -2.141182000 3.766728000 2.270526000 C -3.057601000 2.684074000 2.034576000 C -1.055575000 3.579826000 3.167079000 C -0.896272000 2.396417000 3.850608000 C -1.834711000 1.356121000 3.672912000 C -2.883020000 1.494427000 2.787350000 C -7.195417000 2.461661000-0.998787000 H -7.066246000 3.164829000 1.046409000 S13

H -5.459263000 4.318281000-1.223815000 H -6.232128000 5.170888000 0.107558000 H -7.997269000 1.124620000 1.470224000 H -9.714494000-0.636467000 1.595025000 H -10.458595000-2.888548000 1.087192000 H -10.042381000-5.142578000 0.151160000 H -7.788652000-5.693340000-0.771584000 H -5.963932000-4.077670000-0.636672000 H -0.902774000-0.745430000-0.523012000 H -2.498400000 1.079301000-0.082147000 H -4.882160000-4.260900000 1.114624000 H -3.167780000-5.991880000 0.965455000 H -0.878107000-5.442166000 0.134742000 H -0.311485000-3.094669000-0.412876000 H -3.647752000 6.243253000 0.446093000 H -1.641049000 5.826950000 1.844394000 H -0.362159000 4.402806000 3.319397000 H -0.066813000 2.267850000 4.539500000 H -1.733393000 0.436715000 4.241790000 H -3.594222000 0.687754000 2.674433000 H -7.860688000 3.262213000-1.341045000 H -7.808524000 1.587271000-0.785035000 H -6.524678000 2.206058000-1.825525000 (P,P)-2 0-1348.25093996 C 1.479343000-1.470792000-0.109544000 C 0.252801000-0.855837000-0.077551000 C 1.691631000-2.977107000-0.299955000 C 2.874435000-2.992154000-1.314084000 C 3.640932000-1.748440000-0.939937000 C 2.831515000-0.883840000-0.202314000 C -1.052900000-1.494295000 0.193449000 C -2.083302000-0.545450000 0.035844000 C -1.453731000 0.765692000-0.211831000 C -0.073966000 0.551645000-0.387892000 C -1.354138000-2.805888000 0.629400000 C -2.662598000-3.190420000 0.802128000 C -3.732750000-2.321175000 0.465305000 C -3.450588000-0.979115000 0.028525000 C -5.077266000-2.776600000 0.502891000 C -6.110762000-1.984758000 0.058794000 C -5.828634000-0.704991000-0.470079000 C -4.539271000-0.218667000-0.484386000 C -1.967114000 2.104912000-0.243485000 C -1.112199000 3.137103000-0.767907000 C 0.215163000 2.818337000-1.162256000 C 0.741678000 1.569806000-0.934158000 C -3.215492000 2.506485000 0.309024000 C -3.636976000 3.818048000 0.258380000 C -2.835059000 4.808681000-0.351547000 C -1.594183000 4.470516000-0.841198000 S14

C 4.986883000-1.446450000-1.217243000 C 5.537338000-0.295411000-0.696570000 C 4.788029000 0.557269000 0.160019000 C 3.410405000 0.259751000 0.441991000 C 5.394293000 1.681432000 0.782903000 C 4.695515000 2.457172000 1.678948000 C 3.356592000 2.132245000 1.997360000 C 2.729482000 1.064545000 1.392691000 C 2.088263000-3.710597000 0.996589000 H 0.806280000-3.444920000-0.734754000 H 3.482287000-3.900900000-1.244666000 H 2.491948000-2.931603000-2.341803000 H -0.567533000-3.512729000 0.852086000 H -2.894992000-4.191886000 1.154107000 H -5.270950000-3.783103000 0.865115000 H -7.132929000-2.350844000 0.081840000 H -6.632782000-0.103454000-0.883980000 H -4.345055000 0.743690000-0.937637000 H 0.831259000 3.598597000-1.600657000 H 1.771933000 1.366479000-1.192749000 H -3.825933000 1.775804000 0.823073000 H -4.587615000 4.093693000 0.705765000 H -3.184517000 5.835672000-0.402597000 H -0.945275000 5.230747000-1.268636000 H 5.584729000-2.119739000-1.825181000 H 6.575020000-0.043445000-0.899071000 H 6.432251000 1.906111000 0.551446000 H 5.173100000 3.308602000 2.154531000 H 2.817470000 2.729072000 2.726992000 H 1.705059000 0.823166000 1.647890000 H 2.233143000-4.778665000 0.801786000 H 1.327724000-3.607014000 1.775326000 H 3.024190000-3.308392000 1.396677000 (M,P)-2 0-1348.25185525 C 1.556801000-1.330160000-0.431135000 C 0.299779000-0.788877000-0.334818000 C 1.865027000-2.726272000-0.984111000 C 3.130067000-2.441875000-1.848112000 C 3.792290000-1.314525000-1.096669000 C 2.875491000-0.693672000-0.247699000 C -0.979849000-1.524558000-0.222426000 C -2.025697000-0.596368000-0.043423000 C -1.485165000 0.747719000-0.317074000 C -0.082129000 0.639679000-0.376714000 C -1.242008000-2.913260000-0.151068000 C -2.512848000-3.360264000 0.124812000 C -3.550851000-2.455876000 0.470491000 C -3.296784000-1.040151000 0.444775000 C -4.814630000-2.930262000 0.911723000 C -5.772267000-2.065814000 1.389665000 S15

C -5.486643000-0.683551000 1.469875000 C -4.285394000-0.187130000 1.012616000 C -2.122523000 1.980990000-0.674134000 C -1.287461000 3.137633000-0.864573000 C 0.125161000 3.000762000-0.822786000 C 0.717851000 1.774006000-0.644771000 C -3.509076000 2.123428000-0.965582000 C -4.052759000 3.343458000-1.304220000 C -3.241218000 4.498097000-1.380595000 C -1.884986000 4.387066000-1.178778000 C 5.138255000-0.908842000-1.156073000 C 5.576376000 0.089258000-0.312929000 C 4.708253000 0.675112000 0.649014000 C 3.330074000 0.271950000 0.711035000 C 5.192842000 1.628693000 1.584479000 C 4.373925000 2.137592000 2.565935000 C 3.031382000 1.703011000 2.658228000 C 2.521829000 0.796889000 1.753695000 C 2.186887000-3.762825000 0.110774000 H 1.046464000-3.087342000-1.610276000 H 3.777740000-3.319119000-1.953702000 H 2.836222000-2.127939000-2.858712000 H -0.459744000-3.639322000-0.320034000 H -2.722832000-4.426283000 0.144250000 H -4.999448000-4.001347000 0.893475000 H -6.729615000-2.443773000 1.736079000 H -6.214554000-0.007432000 1.908945000 H -4.071839000 0.867863000 1.123830000 H 0.737886000 3.880566000-0.999920000 H 1.792639000 1.685507000-0.716821000 H -4.144740000 1.248530000-0.957698000 H -5.113106000 3.413920000-1.529095000 H -3.682974000 5.457934000-1.631583000 H -1.239044000 5.254571000-1.287817000 H 5.823373000-1.385719000-1.851449000 H 6.612155000 0.417155000-0.343119000 H 6.233252000 1.936602000 1.520242000 H 4.758475000 2.860497000 3.279189000 H 2.395923000 2.085804000 3.451287000 H 1.492630000 0.469962000 1.836769000 H 2.410918000-4.735788000-0.339915000 H 1.355291000-3.892998000 0.808007000 H 3.059578000-3.449753000 0.692240000 TS1 1-1348.23342369 C -1.533730000-1.420760000-0.418273000 C -0.299608000-0.808725000-0.295114000 C -1.760917000-2.832197000-0.997242000 C -3.210875000-2.745116000-1.560442000 C -3.837537000-1.619911000-0.792454000 C -2.861722000-0.860338000-0.142181000 S16

C 0.970036000-1.446363000 0.026563000 C 2.032410000-0.507363000 0.020137000 C 1.422821000 0.820300000-0.396566000 C 0.028463000 0.595477000-0.525641000 C 1.102273000-2.765536000 0.514461000 C 2.320391000-3.224221000 0.922952000 C 3.453057000-2.374264000 0.877962000 C 3.338491000-0.997956000 0.435994000 C 4.700632000-2.904792000 1.299062000 C 5.847026000-2.148814000 1.303190000 C 5.763412000-0.812102000 0.871685000 C 4.561897000-0.274124000 0.462454000 C 1.899878000 2.159086000-0.713024000 C 0.938326000 3.147848000-1.159635000 C -0.429906000 2.816675000-1.318750000 C -0.873918000 1.562069000-1.020707000 C 3.236295000 2.638406000-0.638866000 C 3.606907000 3.930046000-0.947444000 C 2.653249000 4.873425000-1.372247000 C 1.343933000 4.471731000-1.472870000 C -5.208761000-1.327510000-0.685350000 C -5.611276000-0.283678000 0.117285000 C -4.671850000 0.459240000 0.884231000 C -3.268254000 0.163917000 0.788621000 C -5.112893000 1.466476000 1.783369000 C -4.222589000 2.132974000 2.593456000 C -2.850370000 1.802523000 2.543655000 C -2.385607000 0.847619000 1.663513000 C -0.782637000-3.297872000-2.082787000 H -1.777728000-3.566885000-0.177968000 H -3.171747000-2.512651000-2.633938000 H -3.762981000-3.685959000-1.461073000 H 0.229982000-3.402926000 0.588334000 H 2.439064000-4.237001000 1.297434000 H 4.724210000-3.942361000 1.622096000 H 6.793686000-2.570246000 1.627146000 H 6.652821000-0.188780000 0.854494000 H 4.588465000 0.742822000 0.134336000 H -1.113103000 3.575511000-1.689538000 H -1.913221000 1.300912000-1.169416000 H 4.021735000 1.988028000-0.318408000 H 4.651513000 4.214063000-0.857613000 H 2.946700000 5.890183000-1.614879000 H 0.577609000 5.169212000-1.801052000 H -5.937752000-1.922144000-1.228620000 H -6.665392000-0.034889000 0.207591000 H -6.175829000 1.688078000 1.832209000 H -4.572471000 2.896568000 3.281630000 H -2.151843000 2.302966000 3.207601000 H -1.331444000 0.606241000 1.647020000 H -1.137619000-4.239623000-2.515781000 H 0.228400000-3.461245000-1.710694000 H -0.727394000-2.557144000-2.887022000 S17

TS2 1-1348.21154991 C -1.651827000-0.988469000-0.901969000 C -0.363998000-0.501328000-1.051276000 C -1.958651000-2.438802000-1.302565000 C -2.971442000-2.946240000-0.268381000 C -3.511231000-1.688229000 0.336117000 C -2.863387000-0.534413000-0.125888000 C 0.836359000-1.401194000-0.967185000 C 1.820260000-0.716294000-0.220734000 C 1.515761000 0.726383000-0.298341000 C 0.224024000 0.845141000-0.851368000 C 1.115147000-2.709266000-1.432713000 C 2.246606000-3.371662000-1.007911000 C 3.086791000-2.813974000-0.011844000 C 2.855249000-1.462696000 0.424786000 C 4.131341000-3.569046000 0.585291000 C 4.867412000-3.061881000 1.630875000 C 4.569386000-1.774941000 2.137076000 C 3.594946000-0.998267000 1.549499000 C 2.365723000 1.877281000-0.192223000 C 1.825033000 3.152510000-0.591299000 C 0.561062000 3.207824000-1.229329000 C -0.191668000 2.071247000-1.406369000 C 3.740879000 1.851385000 0.179252000 C 4.488273000 3.004754000 0.271946000 C 3.915905000 4.263667000-0.020038000 C 2.615655000 4.325919000-0.460777000 C -4.518664000-1.673226000 1.320953000 C -4.922922000-0.480663000 1.860213000 C -4.402226000 0.740039000 1.356906000 C -3.402939000 0.735657000 0.316900000 C -4.915732000 1.972312000 1.839912000 C -4.531769000 3.173764000 1.291027000 C -3.633882000 3.172077000 0.205017000 C -3.099368000 1.988891000-0.260120000 C -2.503287000-2.488239000-2.743150000 H -1.068384000-3.055295000-1.251975000 H -3.766482000-3.557003000-0.713851000 H -2.484991000-3.569841000 0.493446000 H 0.496831000-3.170301000-2.192542000 H 2.484545000-4.352832000-1.409321000 H 4.316337000-4.575568000 0.218711000 H 5.651261000-3.656990000 2.089789000 H 5.102722000-1.401375000 3.006367000 H 3.347975000-0.035491000 1.980264000 H 0.230899000 4.153821000-1.649724000 H -1.052971000 2.105401000-2.058990000 H 4.223347000 0.904701000 0.370661000 H 5.533576000 2.942027000 0.560524000 H 4.510773000 5.167617000 0.071536000 H 2.173659000 5.277932000-0.743446000 S18

H -4.945457000-2.613464000 1.659132000 H -5.673200000-0.446952000 2.645506000 H -5.646646000 1.942389000 2.643768000 H -4.938861000 4.107941000 1.665919000 H -3.366758000 4.106355000-0.280148000 H -2.456262000 2.011602000-1.116882000 H -2.722067000-3.521553000-3.034529000 H -1.778910000-2.076600000-3.452777000 H -3.427817000-1.907741000-2.833417000 TS3 1-1348.21969579 C -1.555837000-1.186084000-0.722103000 C -0.275529000-0.654452000-0.603560000 C -1.756830000-2.642204000-1.153522000 C -2.730165000-3.199227000-0.103955000 C -3.449467000-1.956474000 0.350159000 C -2.894085000-0.782644000-0.187288000 C 0.904074000-1.468776000-0.184622000 C 2.028300000-0.629984000-0.026988000 C 1.587563000 0.752714000-0.225837000 C 0.250682000 0.718786000-0.679732000 C 0.990525000-2.811147000 0.276272000 C 2.193443000-3.338587000 0.677288000 C 3.394890000-2.584464000 0.589583000 C 3.327552000-1.201676000 0.205879000 C 4.656364000-3.183096000 0.843660000 C 5.827168000-2.480157000 0.662105000 C 5.772536000-1.148630000 0.193207000 C 4.559281000-0.528446000-0.025973000 C 2.227690000 2.019407000-0.000115000 C 1.619052000 3.191000000-0.570797000 C 0.404604000 3.058919000-1.297784000 C -0.273459000 1.865012000-1.323322000 C 3.359159000 2.212631000 0.840794000 C 3.906927000 3.463916000 1.035460000 C 3.358486000 4.597349000 0.393913000 C 2.230566000 4.458283000-0.384680000 C -4.513376000-1.935196000 1.273636000 C -5.062725000-0.733393000 1.648581000 C -4.658825000 0.471790000 1.011565000 C -3.610437000 0.452197000 0.023830000 C -5.346924000 1.685276000 1.279145000 C -5.096344000 2.824185000 0.546638000 C -4.171357000 2.770836000-0.517801000 C -3.458640000 1.615779000-0.767392000 C -2.364271000-2.655090000-2.575445000 H -0.825228000-3.194969000-1.212979000 H -3.423976000-3.946383000-0.505460000 H -2.197187000-3.672321000 0.731354000 H 0.112820000-3.436418000 0.354834000 H 2.243520000-4.364635000 1.031189000 S19

H 4.681024000-4.222706000 1.160112000 H 6.786954000-2.952865000 0.847798000 H 6.693629000-0.610538000-0.011046000 H 4.548267000 0.476544000-0.426018000 H -0.000518000 3.928185000-1.808134000 H -1.180747000 1.792828000-1.897738000 H 3.771461000 1.368098000 1.377149000 H 4.758787000 3.579235000 1.699223000 H 3.807694000 5.575101000 0.540184000 H 1.771182000 5.327376000-0.848475000 H -4.868294000-2.868074000 1.702026000 H -5.854508000-0.692354000 2.391291000 H -6.108334000 1.685674000 2.054395000 H -5.638840000 3.741638000 0.752782000 H -4.032687000 3.636214000-1.158808000 H -2.826440000 1.565845000-1.637890000 H -2.492459000-3.689804000-2.909566000 H -1.706261000-2.146389000-3.286199000 H -3.340597000-2.161871000-2.599539000 TS4 1-1348.23677230 C 1.439611000-1.504891000-0.288820000 C 0.210184000-0.889551000-0.285062000 C 1.699584000-2.981219000-0.614526000 C 3.008312000-2.893539000-1.452780000 C 3.696424000-1.689843000-0.863935000 C 2.783192000-0.903157000-0.160610000 C -1.111268000-1.497323000-0.080888000 C -2.107090000-0.492449000 0.036295000 C -1.431254000 0.829539000-0.271203000 C -0.068708000 0.533371000-0.499269000 C -1.403819000-2.873035000 0.041598000 C -2.693715000-3.289717000 0.218532000 C -3.736260000-2.347845000 0.374441000 C -3.457927000-0.927429000 0.341815000 C -5.053527000-2.827934000 0.602783000 C -6.101663000-1.975182000 0.844672000 C -5.840393000-0.591641000 0.889789000 C -4.574295000-0.102790000 0.651901000 C -1.851465000 2.204780000-0.495105000 C -0.910600000 3.115124000-1.115325000 C 0.406504000 2.698814000-1.428308000 C 0.829421000 1.443463000-1.098450000 C -3.095831000 2.796095000-0.143236000 C -3.426079000 4.104645000-0.425722000 C -2.521193000 4.949806000-1.095203000 C -1.282260000 4.452067000-1.416411000 C 5.061666000-1.357411000-0.938893000 C 5.521111000-0.253241000-0.255667000 C 4.652720000 0.519915000 0.563560000 C 3.256098000 0.189670000 0.643596000 S20

C 5.156183000 1.597612000 1.340483000 C 4.336177000 2.300875000 2.192409000 C 2.973913000 1.942962000 2.310406000 C 2.447335000 0.917502000 1.554797000 C 1.920229000-3.854322000 0.637177000 H 0.893006000-3.396375000-1.221450000 H 3.615338000-3.803045000-1.386931000 H 2.769305000-2.736537000-2.513242000 H -0.621513000-3.611539000-0.030856000 H -2.931342000-4.348758000 0.265528000 H -5.207730000-3.903853000 0.596196000 H -7.102939000-2.356363000 1.020474000 H -6.640227000 0.105252000 1.123102000 H -4.443881000 0.954506000 0.747313000 H 1.074413000 3.398524000-1.922524000 H 1.835398000 1.127097000-1.338705000 H -3.814669000 2.238134000 0.420371000 H -4.395199000 4.483176000-0.113654000 H -2.788764000 5.975892000-1.328372000 H -0.543179000 5.084680000-1.901101000 H 5.742720000-1.971072000-1.521885000 H 6.571401000 0.022606000-0.301229000 H 6.211312000 1.846038000 1.260536000 H 4.734580000 3.118710000 2.785345000 H 2.335020000 2.479968000 3.005134000 H 1.402995000 0.653065000 1.660381000 H 2.115386000-4.892850000 0.348657000 H 1.053354000-3.842867000 1.302970000 H 2.780826000-3.493510000 1.208896000 References (1) Tian, Y.; Uchida, K.; Kurata, H.; Hirao, Y.; Nishiuchi, T.; Kubo, T. J. Am. Chem. Soc. 2014, 136, 12784. (2) Pijper, D.; Feringa, B. L. Angew. Chem. Int. Ed. 2007, 46, 3693. (3) 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, N. J.; 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, Ö.; Foresman, J. B.; Ortiz, J. V.; Cioslowski, J.; Fox, D. J. Gaussian 09, Revision D.01, 2013.. (4) Becke, A. D. J. Chem. Phys. 1993, 98, 5648 S21

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