Hash Mark-shaped Azaacene Tetramers with Axial Chirality

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1 Supporting Information for Hash Mark-shaped Azaacene Tetramers with Axial Chirality Yuki Inoue, Daisuke Sakamaki,*, Yusuke Tsutsui, Masayuki Gon, Yoshiki Chujo, and Shu Seki*, Department of Molecular Engineering, Graduate School of Engineering, Kyoto University, Nishikyo-ku, Kyoto , Japan Department of Polymer Chemistry, Graduate School of Engineering, Kyoto University, Nishikyo-ku, Kyoto , Japan S1

2 Contents: p.s3 S4 p.s5 S10 p.s11 p.s1 S1 p.s S39 p.s40 S47 p.s48 S5 p.s53 General information Synthetic details Mass spectra X-ray crystallography Electronic properties NMR spectra High resolution mass spectra References S

3 General Information All the purchased reagents were of standard quality and used without further purification. Dry dichloromethane and dry dimethylformamide were purchased from Kanto Chemical Co., Inc. Column chromatography was performed with silica gel (Fuji Silysia, PSQ 60N, spherical neutral). 1 H and 13 C NMR spectra were recorded by a JEOL JNM-AL400 FT-NMR spectrometer. 6,13-dihydro-6,13-diazapentacene (DHDAP) and 13H-dibenzo[b,i]phenoxazine 6 were synthesized by the solvent-free condensation of,3-diaminonaphthalene and,3-dihydroxynaphthalene (for DHDAP), and condensation of 3-amino--naphthol and,3-dihydroxynaphthalene (for 6), according to the literature. S1 Low and high resolution matrix-assisted-laser-desorption/ionization (MALDI) mass spectra (MS) were obtained on a Bruker autoflex III mass spectrometer with dithranol as a matrix. Low and high resolution atmospheric pressure chemical ionization MS were obtained on a Thermo Fisher Exactive mass spectrometer. UV-Vis-NIR absorption spectra were obtained with a Perkin-Elmer Lambda 19 spectrometer. Fluorescence spectra were recorded on an absolute PL quantum yield measurement system (HAMAMATSU Quantaurus-QY). The redox properties were evaluated by cyclic voltammetry (CV) and differential pulse voltammetry (DPV) in CH Cl solution at 98 K with 0.1 M tetra-n-butylammonium tetrafluoroborate (TBABF 4 ) as supporting electrolyte (scan rate 100 mv s 1 ) using an ALS/chi Electrochemical Analyzer model 61A. A three-electrode assembly was used, which was equipped with platinum disk ( mm ), a platinum wire, and Ag/0.01 M AgNO 3 (acetonitrile) as the working electrode, the counter electrode, and the reference electrode, respectively. The redox potential were referenced against a ferrocene/ferrocenium (Fc 0/+ ) redox potential measured in the same electrolytic solution. S3

4 Spectroelectrochemical measurements were carried out with a custom-made optically transparent thin-layer electrochemical (OTTLE) cell (light pass length = 1 mm) equipped with a platinum mesh, a platinum coil, and a silver wire as the working electrode, the counter electrode, and the pseudo-reference electrode, respectively. The potential was applied with an ALS/chi Electrochemical Analyzer model 61A. Circular dichroism (CD) spectra were recorded on a JASCO J-80 spectropolarimeter with CH Cl as a solvent at room temperature. Circularly polarized luminescence (CPL) spectra were recorded on a JASCO CPL-00S with CH Cl as a solvent at room temperature. S4

5 Synthetic Details 6-n-propyl-6,13-dihydro-6,13-diazapentacene (5): A mixture of 6,13-dihydro-6,13-diazapentacene (.8 g, mmol) and sodium hydride (60% in oil, 0.53 g,. mmol) in DMF (100 ml) was stirred under an N atmosphere at rt for 1 h. To the reaction solution, 1-bromopropane (0.9 ml, 10 mmol) was added and stirred for 1 h. The reaction was quenched by adding water and the precipitate was collected by filtration. The crude product was chromatographed on silica gel (toluene/hexane = 1: as eluent) to afford 5 (0.93 g, 9%) as a yellow powder. 1 HNMR (400 MHz, acetone-d 6, Figure S) δ = 1.17 (t, J = 7.3 Hz, 3H), (m, H), 3.79 (t, J = 8.9, H), 6.63 (s, H), 6.83 (s, H), (m, 4H), (m, H), (m, H), 8.16 (s, 1H); 13C NMR (100 MHz, acetone-d 6, Figure S7) δ = 11.50, 18.53, 47.6, , 107.4, 14.7, 14.98, 16.08, 17.56, 13.03, 13.6, 134.6, ; HRMS (APCI, in dichloromethane solution, Figure S3): m/z calcd for C 3 H 1 N : [M+H] + ; found ; elemental analysis calcd (%) for C 3 H 0 N : C 85.15, H 6.1, N 8.63; found C 84.57, H 6.4, N 8.44; mp: S5

6 n-pr N N n-pr 6,13-di-n-propyl-6,13-dihydro-6,13-diazapentacene (5 ): A mixture of 6,13-dihydro-6,13-diazapentacene (0.90 g, 1.0 mmol) and sodium hydride (60% in oil, 0.09 g,.3 mmol) in DMF (0 ml) was stirred under an N atmosphere at rt for 1 h. To the reaction solution, 1-bromopropane (0.19 ml,.1 mmol) was added and stirred for 17 h. The reaction was quenched by adding water and the precipitate was collected by filtration. The crude product was chromatographed on silica gel (toluene/hexane = 1: as eluent) to afford 5 (0.315 g, 84%) as a yellow powder. 1 HNMR (400 MHz, CD Cl, Figure S3) δ = 1.16 (t, J = 7.3 Hz, 6H), (m, 4H), (m, 4H), (m, 4H), 6.65 (s, 4H), (m, 4H), (m, 4H); 13 C NMR (100 MHz, CD Cl, Figure S8) δ = 11.40, 17.76, 48.17, , 14.34, 16.6, , ; HRMS (APCI, in dichloromethane solution, Figure S34): m/z calcd for C 6 H 7 N : [M+H] + ; found ; elemental analysis calcd (%) for C 6 H 6 N : C 85.1, H 7.15, N 7.64; found C 85.01, H 7.14, N 7.60; mp: S6

7 3: To a solution of 5 (0.165 g, 0.51 mmol) in CH Cl (80 ml), was added dropwise a solution of DDQ (0.059 g, 0.6 mmol) in CH Cl (0 ml) for 1 h under an N atmosphere at rt. After the addition of DDQ, the reaction mixture was kept stirring for 0.5 h. The reaction solution was washed with aqueous NaHCO 3. The organic layer was dried over Na SO 4, and the solvent was removed under reduced pressure. The crude product was chromatographed on silica gel (hexane : CH Cl = 3:1 as eluent) to afford 3 (0.15 g, 77%) as yellow powder. 1 HNMR (400 MHz, CD Cl, Figure S4); δ = (m, 6H), (m, 4H), 3.83 (t, J = 8.9 Hz, H), 3.90 (t, J = 8.9 Hz, H), 6.6 (s, H), 6.5 (s, 1H), 6.55 (s, 1H), 6.74 (s, 1H), 6.84 (s, H), 6.88 (s, 1H), (m, 10H), 7.3 (d, J = 7.81 Hz, 1H), 7.46 (d, J = 8.9 Hz, H), 7.50 (d, J = 8.9 Hz, H), 7.64 (d, J = 8.9 Hz, 1H); 13 C NMR (100 MHz, CDCl 3, Figure S8) δ =11.5 (two peaks are overlapped), 18.8 (two peaks are overlapped), 48.1, 48.49, 107.0, , , , , 11.98, 11.67, 14.45, 14.54, 14.70, 14.73, 14.88, 15.36, 15.77, 16.36, 16.41, 16.77, 17.70, , , , , S7

8 13.14, 13.18, 13.63, , , , 134.7; HRMS (APCI, in dichloromethane solution, Figure S36): m/z calcd for C 46 H 39 N 4 : [M+H] + ; found ; elemental analysis calcd (%) for C 46 H 38 N 4 : C 85.4, H 5.9, N 8.66; found C 85.5, H 5.83, N 8.5; mp: (from 6): To a solution of 6 (0.90 g, 1.0 mmol) in CH Cl (300 ml), a solution of DDQ (0.8 g, 1.00 mmol) in CH Cl (100 ml) was added dropwise over.5 h and stirred for another 1 h at rt. The reaction was monitored by TLC and MALDI-MS, and the generation of 4 was observed. To the reaction solution, DDQ (0.113 g, 0.50 mmol) was added. After the addition of DDQ, the reaction mixture was kept stirring for 15 h. The reaction mixture was quenched by adding hydrazinium hydroxide, and extracted with CH Cl. The organic layer was dried over Na SO 4, and the solvent was removed under reduced pressure. The crude product was chromatographed on silica gel (hexane : ethyl acetate = 19:1 as eluent) to afford (0.111 g, 61%) as pale yellow powder. 1 HNMR (400MHz, THF-d 8, Figure S5) δ = 5.41 (s, H), 5.8 (s, H), 5.98 (t, J = 7.3 Hz, H), 6.15 (s, H), (m, 4H), 6.69 (t, J = 7.3 Hz, H), 6.95 (s, H), (m, 14H), (m, 6H) 7.34 (d, J = 8.78 Hz, H), 7.56 (d, J = 8.9 Hz, 4H), 7.68 (d, J = 7.81 Hz, H), 7.78 (d, J = 8.9 Hz, H); 13 C NMR could not recorded S8

9 due to low solubility; HRMS (APCI, in dichloromethane solution, Figure S38): m/z calcd for C80H47N4O4: [M+H] + ; found mp: > (from 5): To a solution of 5 (0.10 g, 0.65 mmol) in CH Cl (100 ml), a solution of DDQ (0.074 g, 0.33 mmol) in CH Cl (0 ml) was added dropwise over 1.5 h and stirred for another 1 h at rt. The reaction was monitored by TLC and MALDI-MS, and the generation of 3 was observed. To the reaction solution, DDQ (0.04 g, 0.18 mmol) was added. After the addition of DDQ, the reaction mixture was kept stirring for 3 h. The reaction solution was washed with aqueous NaHCO 3. The organic layer was dried over Na SO 4, and the solvent was removed under reduced pressure. The crude product was chromatographed on silica gel (hexane : CH Cl = :1 as eluent) to afford 1 (0.179 g, 86%) as yellow powder. 1 HNMR (400 MHz, CD Cl, Figure S6) δ = 1.19 (t, J = 7.3 Hz, 6H), 1.34 (t, J = 7.3 Hz, 6H), (m, 4H), (m, 4H), (m, 4H), (m, 4H), 5.63 (s, H), 5.79 (s, H), 5.84 (t, J = 7.3 Hz, H), 6.15 (s, 1H), 6.1 (s, H), (m, 10H), 6.69 (s, H), (m, 8H), (m, 6H), 7.18 (d, J = 7.81 Hz, H), 7.1 (d, J = 7.81 Hz, H), 7.39 (d, J = 7.3 Hz, H), 7.53 (d, J = 8.9 Hz, H); 13 C NMR (100 MHz, CD Cl, Figure S30) δ =11.53, 11.61, 18.1 (two peaks are overlapped), 47.01, 48.34, , , , , , , 10.84, 1.69, 13.81, 14.16, 14.39, 14.4, 14.57, 14.64, 14.89, 15.71, S9

10 16.7, 16.45, 16.76, 17.6, 18.6, 19.47, , , , , , 13.6, 13.88, 13.96; HRMS (APCI, in dichloromethane solution, Figure S40): m/z calcd for C 9 H 75 N 8 : [M+H] + ; found ; elemental analysis calcd (%) for C 9 H 74 N 8 : C 85.55, H 5.77, N 8.68; found C 85.36, H 5.66, N 8.58; mp: > (from 3): To a solution of 3 (0.084 g, 0.13 mmol) in CH Cl (40 ml), was added dropwise a solution of DDQ (0.015 g, 0.06 mmol) in CH Cl (10 ml) for 1 h under an N atmosphere at rt. After the addition of DDQ, the reaction mixture was kept stirring for 1.5 h. The reaction solution was washed with aqueous NaHCO 3. The organic layer was dried over Na SO 4, and the solvent was removed under reduced pressure. The crude product was chromatographed on silica gel (hexane : CH Cl = 3:1 as eluent) to afford 1 (0.078 g, 9%) as yellow powder. S10

11 Figure S1. MALDI mass spectrum of the reaction solution of the oxidation reaction of 3 with DDQ as an oxidant (reaction time = 1 hours). Figure S. MALDI mass spectrum of the reaction solution of the oxidation reaction of S11

12 1 with DDQ as an oxidant (reaction time = 16 hours). X-ray Crystallography for 1,, 3, 5, and (S a )-1 + [SbCl 6 ] The single crystals were obtained by the slow evaporation of a mixed solution (toluene:n-hexane for 1, CH Cl :n-heptane for 3, CH Cl :n-hexane for and 5, acetone:n-hexane for (S a )-1 + [SbCl 6 ]). Data collections were performed on a Rigaku Saturn70 CCD diffractometer with Mo-Kα radiation (λ = Å) at 143 K. The non-hydrogen atoms were refined anisotropically. Hydrogen atoms were included in the refinement but restrained to ride on the atom to which they are bonded. All the calculations were performed by using Crystal Structure crystallographic software package, S except for refinement, which was performed by using SHELXL-97. S3 CCDC (1), (3), (5 ), ((S a )-1 + [SbCl 6 ]), and 1801 () contain the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via S1

13 Table S1: X-ray crystallographic data for 1 (CCDC 18008). empirical formula C 9 H 74 N 8 C 6 H 14 formula weight T [ C] 130 λ [Å] crystal system orthorhombic space group Fdd (#43) Z a [Å] (7) b [Å] 18.30(4) c [Å] 4.48(5) α [ ] β [ ] γ [ ] V [Å 3 ] 14963(5) ρ calcd [g cm 3 ] 1.3 collected data 991 unique data / R int 719/ no. of parameters 478 goodness-of-fit [a] R1 (I > σ), wr (all reflections) [b] , residual density [e Å 3 ] 0.30/ 0.1 [a] GOF = w( F 0 F c ) 1/ { ( n p), where n and p denote the number of data and parameters. } ( ) F 0 R1= F 0 F c { ( ) ( )} [b] and wr= w F 0 F c w F where 0 1/ S13

14 w= 1 σ ( F 0 )+( a P) + b P and P = ( Max;0,F 0 )+ F c 3. Table S: X-ray crystallographic data for 3 (CCDC 18009). empirical formula C 46 H 38 N 4 CH Cl formula weight T [ C] 130 λ [Å] crystal system monoclinic space group C/c (#15) Z 8 a [Å] (9) b [Å] (4) c [Å] (4) α [ ] β [ ] (5) γ [ ] V [Å 3 ] 7687(4) ρ calcd [g cm 3 ] 1.64 collected data unique data / R int 8754/0.047 no. of parameters 478 goodness-of-fit [a] 1. R1 (I > σ), wr (all reflections) [b] 0.101, residual density [e Å 3 ] 0.86/ 1.11 [a] GOF = w( F 0 F c ) 1/ { ( n p), where n and p denote the number of data and parameters. } ( ) F 0 R1= F 0 F c { ( ) ( )} [b] and wr= w F 0 F c w F where 0 1/ S14

15 w= 1 σ ( F 0 )+( a P) + b P and P = ( Max;0,F 0 )+ F c 3. Table S3: X-ray crystallographic data for 5 (CCDC 18010). empirical formula C 6 H 6 N formula weight T [ C] 130 λ [Å] crystal system monoclinic space group C1/c1 (#15) Z 4 a [Å] 4.051(10) b [Å] (19) c [Å] (7) α [ ] β [ ] 1.885(5) γ [ ] V [Å 3 ] 197.5(13) ρ calcd [g cm 3 ] 1.63 collected data 7304 unique data / R int 178/0.049 no. of parameters 145 goodness-of-fit [a] R1 (I > σ), wr (all reflections) [b] , 0.94 residual density [e Å 3 ] 0.63/ 0.50 [a] GOF = w( F 0 F c ) 1/ { ( n p), where n and p denote the number of data and parameters. } ( ) F 0 R1= F 0 F c { ( ) ( )} [b] and wr= w F 0 F c w F where 0 1/ S15

16 w= 1 σ ( F 0 )+( a P) + b P and P = ( Max;0,F 0 )+ F c 3. Table S4: X-ray crystallographic data for (S a )-1 + [SbCl 6 ] (CCDC 18011). empirical formula C 9 H 76 N 8 [SbCl 6 ] 3[C 3 H 6 O] 0.5[C 6 H 14 ] formula weight T [ C] 130 λ [Å] crystal system orthorhombic space group P 1 1 (#18) Z a [Å] b [Å] c [Å] α [ ] β [ ] γ [ ] V [Å 3 ] ρ calcd [g cm 3 ] collected data unique data / R int 11794/ no. of parameters 616 goodness-of-fit [a] R1 (I > σ), wr (all reflections) [b] , residual density [e Å 3 ] 1.31/ 0.80 Flack parameter 0.06(15) [a] GOF = w( F 0 F c ) 1/ { ( n p), where n and p denote the number of data and parameters. } S16

17 ( ) F 0 R1= F 0 F c [b] and wr= w F 0 F c w F where 0 w= 1 σ ( F 0 )+( a P) + b P and P = ( Max;0,F 0 )+ F c 3. { ( ) ( )} 1/ Table S5: X-ray crystallographic data for (CCDC 1801). empirical formula C 80 H 46 N 4 O 4 C 6 H 14 CH Cl formula weight T [ C] 130 λ [Å] crystal system triclinic space group P-1 (#) Z a [Å] (4) b [Å] (5) c [Å] (6) α [ ] (13) β [ ] (15) γ [ ] (14) V [Å 3 ] (17) ρ calcd [g cm 3 ] collected data unique data / R int 1045/ no. of parameters 89 goodness-of-fit [a] R1 (I > σ), wr (all reflections) [b] , residual density [e Å 3 ] 0.63/ 0.53 [a] GOF = w( F 0 F c ) 1/ { ( n p), where n and p denote the number of data and parameters. } ( ) F 0 R1= F 0 F c { ( ) ( )} [b] and wr= w F 0 F c w F where 0 1/ S17

18 w= 1 σ ( F 0 )+( a P) + b P and P = ( Max;0,F 0 )+ F c 3. Figure S3. X-ray crystal structures of a) 5 and b) 3. Hydrogen atoms are omitted for clarity. Thermal ellipsoids are set at 50% probability. S18

19 Figure S4. X-ray crystal structures of (R a )- in a racemic crystal. Hydrogen atoms are omitted for clarity. Thermal ellipsoids are set at 50% probability. S19

20 Figure S5. Packing structures of rac-1. (Purple and green) each enantiomer of 1, (blue) hexane. S0

21 Figure S6. Packing structures of (S a )-1 + [SbCl 6 ]. (Purple) (S a )-1 +, (green) SbCl 6, (blue) acetone, (yellow) hexane. S1

22 Figure S7. Frontier MOs of 5 (B3LYP/6-31G*). Figure S8. Frontier MOs of 3 (B3LYP/6-31G*). S

23 Figure S9. (a) Cyclic voltammogram and (b) Differential pulse voltammogram of 5 measured in CH Cl containing 0.1 M nbu 4 NBF 4 at 98 K (scan rate 100 m V s -1 ). S3

24 Figure S10. (a) Cyclic voltammogram and (b) Differential pulse voltammogram of 3 measured in CH Cl containing 0.1 M nbu 4 NBF 4 at 98 K (scan rate 100 m V s -1 ). S4

25 Figure S11. (a) Cyclic voltammogram and (b) Differential pulse voltammogram of 1 measured in CH Cl containing 0.1 M nbu 4 NBF 4 at 98 K (scan rate 100 m V s -1 ) S5

26 Figure S1. Absorption spectra of in CH Cl. Figure S13. The electronic transitions of 3 based on the TD-DFT calculations at B3LYP/6-31G* level (blue bars). The black line represents the UV-Vis absorption spectrum of 3 in CH Cl at 98 K. S6

27 Figure S14. The electronic transitions of 1 based on the TD-DFT calculations at B3LYP/6-31G* level (blue bars). The black line represents the UV-Vis absorption spectrum of 1 in CH Cl at 98 K. Table S6. The main electronic transitions of 1 based on the TD-DFT calculations at B3LYP/6-31G* level. Wavelength / nm f 1 (HO-)MO LUMO (HO-)MO (LU+1)MO (HO-3)MO (LU+1)MO (HO-3)MO LUMO HOMO (LU+)MO 5 (HO-1)MO (LU+3)MO S7

28 (HO-1)MO 6 (LU+)MO HOMO (LU+3)MO Table S7. Emission properties of 1, 3, and 5 (Excitation wavelength: 300 nm). Φ λ max / nm λ max / ev Figure S15. Emission spectra of in CHCl solution (Excitation wavelength: 300 nm). Table S8. Emission properties of, 4, and 6 (Excitation wavelength: 300 nm). Φ λ max / nm λ max / ev 6 [S4] [S4] S8

29 Figure S16. Decay profiles of the fluorescence of 1, 3 and 5 in CHCl at room temperature. S9

30 Figure S17. UV-Vis-NIR absorption spectra during the electrochemical oxidation of 1. (a) 1 to 1 + and (b) 1 + to further oxidation. The spectra were measured in CH Cl with 0.1 M nbu 4 NBF 4 at 98 K. S30

31 Figure S18. acetone at 98 K. UV-Vis-NIR absorption spectra of rac-1 + [SbCl 6 ] in CH Cl and S31

32 Figure S19. Chromatograms for the resolution of 1 using UV (54 nm) and CD detectors (30 nm) in n-hexane/ethyl acetate (75/5, v/v) at the flow rate of 1.4 ml/min. Optical resolution was carried out with a DAICEL CHIRALPAK-IE column (1.0(i.d.) 5 cm). Table S9. Chiroptical properties for 1. g abs [10-3 ] at 438 nm g CPL [10-3 ] at 44 nm (R a ) (S a ) Table S10. Chiroptical properties for 1 +. g abs [10-3 ] at 90 nm (R a ) (S a ) S3

33 Figure S0. The electronic transitions of 1 + based on the TD-DFT calculations at UB3LYP/6-31G* level (blue bars). The black line represents the UV-Vis-NIR absorption spectrum of 1 + [SbCl 6 - ] in CH Cl ( M) at 98 K. Figure S1 Frontier MOs of 1 + (UB3LYP/6-31G*). S33

34 Figure S. ESR spectrum of 1 + (g =.0030) in CH Cl at room temperature. Figure S3. ESR spectrum of 1 + in CH Cl at 13 K. (inset) Enlarged half-field region. S34

35 Simulation of Circular Dichroism Spectrum The excitation energies of 1 and 1 + were calculated by the TD-DFT method at B3LYP/6-31G* level for the optimized structure at B3LYP/6-31G* level. The 100 lowest transitions were calculated. The CD spectrum was simulated by using the Gauss function: where N is the normalization factor, σ is the standard deviation, E i and R i are the excitation energies and rotatory strengths for the ith transition. The σ value of 0.17 ev and R in the length form were used. Table S11. TD-DFT calculated transition energies and oscillator and rotatory strengths of (R a )-1 (B3LYP/6-31G* level, Nstate = 100). Excitation Excitation R(10-40 cgs) energy (ev) energy (ev) R(10-40 cgs) S35

36 S36

37 Table S1. TD-DFT calculated transition energies and oscillator and rotatory strengths of (R a )-1 + (UB3LYP/6-31G* level, Nstate = 100). Excitation Excitation R(10-40 cgs) energy (ev) energy (ev) R(10-40 cgs) S37

38 Figure S4. Simulated CD spectra of (R a )-1 and (S a )-1 based on TD-DFT calculations at the B3LYP/6-31G* level of theory. S38

39 Figure S5. Simulated CD spectra of (R a )-1 + and (S a )-1 + based on TD-DFT calculations at the UB3LYP/6-31G* level of theory. S39

40 Figure S6. 1 H NMR of 5 in acetone-d 6 at 98 K. Asterisk denotes the solvent residual peak. Figure S7. 1 H NMR of 5 in dichloromethane-d at 98 K. Asterisk denotes the solvent residual peak. S40

41 Figure S8. 1 H NMR of 3 in dichloromethane-d at 98 K. Asterisk denotes the solvent residual peak. S41

42 Figure S9. 1 H NMR of in THF-d 8 at 98 K. S4

43 Figure S30. 1 H NMR of 1 in dichloromethane-d at 98 K. Asterisk denotes the solvent residual peak. S43

44 Figure S C NMR of 5 in dichloromethane-d at 98 K. S44

45 Figure S3. 13 C NMR of 5 in dichloromethane-d at 98 K. S45

46 Figure S C NMR of 3 in dichloromethane-d at 98 K. S46

47 Figure S C NMR of 1 in dichloromethane-d at 98 K. S47

48 Figure S35. MALDI mass spectrum of 5. Figure S36. High-resolution APCI-MS of 5 dissolved in CH Cl. S48

49 Figure S37. MALDI mass spectrum of 5. Figure S38. High-resolution APCI-MS of 5 dissolved in CH Cl. S49

50 Figure S39. MALDI mass spectrum of 3. Figure S40. High-resolution APCI-MS of 3 dissolved in CH Cl. S50

51 Figure S41. MALDI mass spectrum of. Figure S4. High-resolution APCI-MS of dissolved in CH Cl. S51

52 Figure S43. MALDI mass spectrum of 1. Figure S44. High-resolution APCI-MS of 1 dissolved in CH Cl. S5

53 References [S1] Itoh, T.; Aomori, A.; Oh-e, M.; Koden, M.; Arakawa, Y. Synth. Met. 01, 16, [S] CrystalStructure 4.0, Crystal Structure Analysis Package, Rigaku Corporation ( ). Tokyo , Japan [S3] Sheldrick, G. M. Acta Cryst. A 008, 64, 11. [S4] Sakamaki, D.; Kumano, D.; Yashima, E.; Seki, S. Angew. Chem. Int. Ed. 015, 54, S53