Supporting Information

© Copyright Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, 2008

Superstructure-Dependent Optical and Electrical Properties of Unusual

Face-to-Face ππππ-Stacked One-Dimensional Assembly of

Dehydrobenzo[12]annulene in Crystalline State

Ichiro Hisaki,*[a] Yuu Sakamoto,[a] Hajime Shigemitsu,[a] Norimitsu Tohnai,[a] Mikiji

Miyata,*[a] Shu Seki,[b] Akinori Saeki,[c] and Seiichi Tagawa[c]

[a] Dr. I. Hisaki, Y. Sakamoto, H. Shigemitsu, Dr. N. Tohnai, Prof. Dr. M. Miyata

Department of Material and Life Science

Graduate School of Engineering, Osaka University

2-1 Yamadaoka, Suita, Osaka, 565-0871 (Japan)

Fax: (+81)-6-6879-7404

E-mail: hisaki@mls.eng.osaka-u.ac.jp, miyata@mls.eng.osaka-u.ac.jp

[b] Prof. Dr. S. Seki

Department of Applied Chemistry

Graduate School of Engineering, Osaka University

2-1 Yamadaoka, Suita, Osaka, 565-0871 (Japan)

Fax (+81)-6-6879-4588

E-mail: seki@chem.eng.osaka-u.ac.jp

[c] Dr. A. Saeki, Prof. Dr. S. Tagawa

The Institute of Scientific and Industrial Research, Osaka University

8-1 Mihogaoka, Ibaraki, Osaka, 567-0047 (Japan)

Fax: (+81)-6-6879-8500

E-mail: tagawa@sanken.osaka-u.ac.jp

Contents: 1. Powder X-ray diffraction (PXRD) pattern of the crystalline powder of [12]DBA 3. (Figure S1)

2. Thermal gravimetric (TG) analysis of crystalline powder of 2•(3DMSO). (Figure S2)

3. 1H NMR spectra of 1 and 2 in DMSO-d6 with various concentrations. (Figures S3 and S4)

4. UV-vis spectra of 1 and 2 in DMSO with various concentrations. (Figures S5 and S6)

5. Solid state fluorescent spectrum of 2•(3DMSO) after DMSO removed. (Figure S7)

6. Observed transient current monitored for thin films of 1 and 2. (Figure S8)

7. Energy levels of frontier orbitals of 1, 2, and DMSO solvate of 2. (Figure S9)

8. Coordinates of the optimized structures of 1, 2, and the DMSO solvate of 2.

Table S1. Coordinate of 1. Table S2. Coordinate of 2. Table S3. Coordinate of 2 solvated by DMSO

9. Excitation energies calculated by TDDFT method.

Table S4. Excitation energies of 1 in vacuo. Table S5. Excitation energies of 1 in DMSO. Table S6. Excitation energies of 2 in vacuo. Table S7. Excitation energies of 2 in DMSO.

10. Reference and notes.

TG

DTA -22.61 %

-7.34 %

110.5 ℃

172.1 ℃

Temperature/℃+00

27.9 50.0 100.0 150.0 200.0 250.0 300.0

Wei

ght

/%

+00

-37.11

-30.00

-25.00

-20.00

-15.00

-10.00

-5.00

0.00

5.00

Hea

t Flo

w/μ

V

+00

-10.0

-8.0

-6.0

-4.0

-2.0

0.0

2.0

4.0

6.0

8.0

10.0

Figure S2. TG (green) and DTA (blue) curves of crystalline solid of 2•(3DMSO). The TG curve indicates that, in the first stage, two equivalents of the DMSO molecules (calc.: 23.4%, obs. 22.6%) were released at ca. 111°C, then the remaining molecules are gradually released upon heating.

Figure S1. Powder X-ray diffraction (PXRD) pattern of the crystalline powder of [12]DBA 3.

Figure S3. 1H NMR spectra (270 MHz, 303 K) of 1in [D6]DMSO with various concentrations (a: 3.3 ×10−5 M, b: 1.7 × 10−4 M, and c: 2.0 × 10−3 M)

Figure S6. UV-vis spectra of 2 with various concentrations (green: 1.0 × 10−5 M, blue: 5.0 × 10−6 M, red: 2.5 × 10−6 M) Vertical axes of (a) and (b) were scaled in absorbance and ε, respectively.

Figure S4. 1H NMR spectra (270 MHz, 303 K) of 2 in [D6]DMSO with various concentrations (a: 5.4 × 10−5

M, b: 2.7 × 10−4 M, and c: 1.6 × 10−3 M)

Figure S5. UV-vis spectra of 1 with various concentrations (green: 5.9 × 10−6 M, blue: 2.9 × 10−6 M, red: 1.5 × 10−6 M). Vertical axes of (a) and (b) were scaled in absorbance and ε, respectively.

Figure S8. Observed transient current monitored for thin films of 1 (red line) and 2 (blue line). The film is casted from DMSO solution on Al substrate at ~3 mm thick. The film was overcoated by Au semitransparent electrode, and the excitation was carried out through the electrode by 355 nm at 5 mJcm−2. The transient was obtained under applied 5 V bias voltage between the electrode.

Figure S7. Fluorescence spectrum of the powder of 2•(3DMSO) after removal of the DMSO molecules.Excitation wavelength is 449 nm.

Figure S9. Orbital energies of DBAs 1 and 2 and the DMSO solvate of 2 calculated by DFT method at B3LYP/6-31G* level.[1]

Coordinates of the optimized structures of 1, 2, and the DMSO solvate of 2.

Table S1. Coordinate of 2 ------------------------------------------------------------------------------------------------------ Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z ---------------------------------------------------------------------------------------------------- 1 1 0 -4.531718 1.206936 0.000000 2 6 0 -3.741381 1.948036 0.000000 3 6 0 -1.705729 3.863060 0.000000 4 6 0 -2.404888 1.522506 0.000000 5 6 0 -4.060012 3.308933 0.000000 6 6 0 -3.034097 4.264988 0.000000 7 6 0 -1.362985 2.498223 0.000000 8 1 0 -3.300202 5.316562 0.000000 9 1 0 -0.909866 4.600684 0.000000 10 6 0 0.000000 2.099010 0.000000 11 6 0 1.163938 1.747544 0.000000 12 6 0 -2.095386 0.134228 0.000000 13 6 0 -1.817796 -1.049505 0.000000 14 6 0 2.520973 1.321441 0.000000 15 6 0 5.210636 0.495111 0.000000 16 6 0 2.845017 -0.068732 0.000000 17 6 0 3.557739 2.266113 0.000000 18 6 0 4.895626 1.861607 0.000000 19 6 0 4.198372 -0.454325 0.000000 20 1 0 3.311096 3.321115 0.000000 21 1 0 4.439242 -1.512375 0.000000 22 1 0 6.254379 0.199778 0.000000 23 6 0 -1.482032 -2.429491 0.000000 24 6 0 -0.835614 -5.170540 0.000000 25 6 0 -2.492643 -3.408735 0.000000 26 6 0 -0.116085 -2.843947 0.000000 27 6 0 0.183642 -4.214148 0.000000 28 6 0 -2.176539 -4.760099 0.000000 29 1 0 -3.529376 -3.088309 0.000000 30 1 0 1.220621 -4.528051 0.000000 31 1 0 -2.954177 -5.516340 0.000000 32 6 0 0.931448 -1.881772 0.000000 33 6 0 1.817796 -1.049505 0.000000 34 6 0 -5.465426 3.792968 0.000000 35 6 0 -0.552093 -6.629681 0.000000 36 6 0 6.017519 2.836714 0.000000 37 8 0 -1.400217 -7.499193 0.000000 38 8 0 -5.794383 4.962220 0.000000 39 8 0 7.194600 2.536973 0.000000 40 8 0 0.775318 -6.912979 0.000000 41 1 0 0.838245 -7.886079 0.000000 42 8 0 -6.374474 2.785045 0.000000 43 1 0 -7.248668 3.217098 0.000000 44 8 0 5.599157 4.127934 0.000000 45 1 0 6.410422 4.668982 0.000000 ----------------------------------------------------------------------------------------------------- E(RB+HF-LYP) = -1487.35207893 point group C3h

Table S2. Coordinate of 1 --------------------------------------------------------------------------------------------------- Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z ------------------------------------------------------------------------------------------------------- 1 1 0 -4.530838 1.203540 0.000000 2 6 0 -3.744545 1.952007 0.000000 3 6 0 -1.710464 3.861156 0.000000 4 6 0 -2.406024 1.522015 0.000000 5 6 0 -4.062147 3.307485 0.000000 6 6 0 -3.043174 4.263898 0.000000 7 6 0 -1.366039 2.498054 0.000000 8 1 0 -3.287092 5.322469 0.000000 9 1 0 -0.913517 4.598278 0.000000 10 6 0 0.000000 2.100787 0.000000 11 6 0 1.163849 1.748973 0.000000 12 6 0 -2.096580 0.133436 0.000000 13 6 0 -1.819335 -1.050394 0.000000 14 6 0 2.521115 1.322671 0.000000 15 6 0 5.214231 0.503517 0.000000 16 6 0 2.846398 -0.066002 0.000000 17 6 0 3.562760 2.266868 0.000000 18 6 0 4.895440 1.864180 0.000000 19 6 0 4.199091 -0.449273 0.000000 20 1 0 3.307716 3.322051 0.000000 21 1 0 4.438984 -1.508010 0.000000 22 1 0 6.252939 0.185471 0.000000 23 6 0 -1.480358 -2.432052 0.000000 24 6 0 -0.833293 -5.171665 0.000000 25 6 0 -2.488627 -3.411883 0.000000 26 6 0 -0.115091 -2.844685 0.000000 27 6 0 0.181785 -4.218875 0.000000 28 6 0 -2.171057 -4.767415 0.000000 29 1 0 -3.525467 -3.090268 0.000000 30 1 0 1.223123 -4.525591 0.000000 31 1 0 -2.965847 -5.507940 0.000000 32 6 0 0.932731 -1.882409 0.000000 33 6 0 1.819335 -1.050394 0.000000 34 1 0 -5.103159 3.617939 0.000000 35 1 0 -0.581648 -6.228434 0.000000 36 1 0 5.684806 2.610496 0.000000 ---------------------------------------------------------------------------------------------------- E(RB+HF-LYP) = -921.634536446 point group C3h

Table S3. Coordinate of 2 solvated by DMSO molecules ----------------------------------------------------------------------------------------------------------- Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z ----------------------------------------------------------------------------------------------------------- 1 6 0 2.668667 0.987768 0.000000 2 6 0 3.864752 3.540251 0.000000 3 6 0 1.854641 2.160990 0.000000 4 6 0 4.068072 1.130037 0.000000 5 6 0 4.661946 2.386482 0.000000 6 6 0 2.473120 3.418335 0.000000 7 1 0 4.681930 0.235031 0.000000 8 1 0 5.741521 2.483942 0.000000 9 1 0 1.869149 4.318637 0.000000 10 6 0 0.435790 2.057044 0.000000 11 6 0 -0.775458 1.950374 0.000000 12 6 0 2.076802 -0.303620 0.000000 13 6 0 1.563557 -1.405927 0.000000 14 6 0 -2.189766 1.817250 0.000000 15 6 0 -4.998323 1.576847 0.000000 16 6 0 -2.798793 0.525671 0.000000 17 6 0 -3.012677 2.958035 0.000000 18 6 0 -4.397727 2.844123 0.000000 19 6 0 -4.196925 0.432617 0.000000 20 1 0 -2.544508 3.937154 0.000000 21 1 0 -5.021918 3.730332 0.000000 22 1 0 -4.674623 -0.540588 0.000000 23 6 0 0.944152 -2.686662 0.000000 24 6 0 -0.264219 -5.230605 0.000000 25 6 0 1.723805 -3.850952 0.000000 26 6 0 -0.478902 -2.805018 0.000000 27 6 0 -1.055395 -4.088072 0.000000 28 6 0 1.133572 -5.117099 0.000000 29 1 0 2.805475 -3.778049 0.000000 30 1 0 -2.137422 -4.172186 0.000000 31 1 0 -0.719603 -6.214274 0.000000 32 6 0 -1.301344 -1.646753 0.000000 33 6 0 -1.999347 -0.651117 0.000000 34 6 0 -6.481402 1.403666 0.000000 35 6 0 2.025091 -6.314892 0.000000 36 6 0 4.456311 4.911226 0.000000 37 8 0 -7.013531 0.296069 0.000000 38 8 0 3.250362 -6.221930 0.000000 39 8 0 3.763169 5.925861 0.000000

40 8 0 -7.146486 2.551706 0.000000 41 8 0 1.363401 -7.464891 0.000000 42 8 0 5.783085 4.913185 0.000000 43 1 0 2.007060 -8.243980 0.000000 44 1 0 6.135967 5.860155 0.000000 45 1 0 -8.143026 2.383826 0.000000 46 8 0 2.880106 -9.637405 0.000000 47 8 0 6.906184 7.312948 0.000000 48 8 0 -9.786290 2.324457 0.000000 49 16 0 4.409659 -9.730035 0.000000 50 16 0 6.221628 8.683895 0.000000 51 16 0 -10.631287 1.046141 0.000000 52 6 0 -10.028218 0.000000 1.372397 53 1 0 -10.569523 -0.951046 1.360494 54 1 0 -10.246248 0.536680 2.298920 55 1 0 -8.952172 -0.150306 1.256228 56 6 0 -10.028218 0.000000 -1.372397 57 1 0 -10.246248 0.536680 -2.298920 58 1 0 -10.569523 -0.951046 -1.360494 59 1 0 -8.952172 -0.150306 -1.256228 60 6 0 5.014109 -8.684692 -1.372397 61 1 0 6.108392 -8.677952 -1.360494 62 1 0 4.606255 -7.677655 -1.256228 63 1 0 4.658346 -9.141851 -2.298920 64 6 0 5.014109 -8.684692 1.372397 65 1 0 4.658346 -9.141851 2.298920 66 1 0 4.606255 -7.677655 1.256228 67 1 0 6.108392 -8.677952 1.360494 68 6 0 5.014109 8.684692 1.372397 69 1 0 4.461131 9.628999 1.360494 70 1 0 5.587902 8.605171 2.298920 71 1 0 4.345917 7.827961 1.256228 72 6 0 5.014109 8.684692 -1.372397 73 1 0 4.345917 7.827961 -1.256228 74 1 0 5.587902 8.605171 -2.298920 75 1 0 4.461131 9.628999 -1.360494 ----------------------------------------------------------------------------------------------------- Point group C3h

E(RB+HF-LYP) = -3146.99781910

9. Excitation energies calculated by TDDFT method.

Table S4. Excitation energies of [12]DBA 1 in vacuo Excited State 2:00 Singlet-E' 3.531 eV 351.13 nm f=0.0193

76 -> 79 0.4792577 -> 79 -0.2623478 -> 80 0.43881

Excited State 3:00 Singlet-E' 3.531 eV 351.13 nm f=0.019376 -> 79 0.2623477 -> 79 0.4792578 -> 81 0.43881

Excited State 4:00 Singlet-E' 4.0745 eV 304.29 nm f=0.969476 -> 79 0.2121577 -> 79 -0.3209778 -> 80 -0.4820378 -> 81 0.13644

Excited State 5:00 Singlet-E' 4.0745 eV 304.29 nm f=0.969476 -> 79 -0.3209777 -> 79 -0.2121578 -> 80 0.1364478 -> 81 0.48203

Excited State 12:00 Singlet-E' 4.736 eV 261.79 nm f=0.017171 -> 79 -0.1652272 -> 79 0.4771576 -> 80 -0.1640677 -> 81 0.1640678 -> 83 -0.3479878 -> 84 0.19895

Excited State 13:00 Singlet-E' 4.736 eV 261.79 nm f=0.017171 -> 79 0.4771772 -> 79 0.1652376 -> 81 0.1640377 -> 80 0.1640378 -> 83 0.1989578 -> 84 0.34798

Excited state symmetry could not be determined.Excited State 14:00 Singlet-?Sy 4.7538 eV 260.81 nm f=0.1711

76 -> 80 0.1224476 -> 81 0.3801777 -> 80 0.3801777 -> 81 -0.1224478 -> 83 -0.1219678 -> 84 -0.36317

Excited state symmetry could not be determined.Excited State 15:00 Singlet-?Sy 4.7538 eV 260.81 nm f=0.1710

76 -> 80 -0.3801676 -> 81 0.1224477 -> 80 0.1224377 -> 81 0.3801678 -> 83 0.3631878 -> 84 -0.12196

Table S5. Excitation energies of [12]DBA 1 in DMSO Excited State 2:00 Singlet-E' 3.5426 eV 349.98 nm f=0.1154

76 -> 79 0.4982477 -> 79 0.3424678 -> 80 0.3007378 -> 81 -0.19507

Excited State 3:00 Singlet-E' 3.5426 eV 349.98 nm f=0.115476 -> 79 -0.3424677 -> 79 0.4982478 -> 80 -0.1950778 -> 81 -0.30073

Excited State 4:00 Singlet-E' 4.0004 eV 309.93 nm f=1.254676 -> 79 -0.3033578 -> 80 0.57698

Excited State 5:00 Singlet-E' 4.0004 eV 309.93 nm f=1.254677 -> 79 0.3033578 -> 81 0.57698

Excited State 12:00 Singlet-E' 4.7335 eV 261.93 nm f=0.088871 -> 79 0.4762576 -> 80 -0.2699876 -> 81 0.2052277 -> 80 -0.2052177 -> 81 -0.2699878 -> 83 -0.16151

Excited State 13:00 Singlet-E' 4.7335 eV 261.93 nm f=0.088872 -> 79 0.4762576 -> 80 0.2052276 -> 81 0.2699977 -> 80 -0.2699877 -> 81 0.2052278 -> 84 0.16149

Excited State 14:00 Singlet-E' 4.7903 eV 258.82 nm f=0.074372 -> 79 0.2771676 -> 80 -0.1896676 -> 81 -0.2281777 -> 80 0.2281677 -> 81 -0.1896578 -> 84 0.474

Excited State 15:00 Singlet-E' 4.7903 eV 258.82 nm f=0.074371 -> 79 -0.2771476 -> 80 -0.2281776 -> 81 0.1896677 -> 80 -0.1896677 -> 81 -0.2281778 -> 83 0.474

Excited State 19:00 Singlet-A" 5.2854 eV 234.58 nm f=0.012378 -> 85 0.6909678 -> 92 -0.11062

Table S6. Excitation energies of [12]DBA 2 in vacuo

Excited State 2:00 Singlet-E' 3.2857 eV 377.35 nm f=0.0001109 ->112 0.48685111 ->114 0.50045

Excited State 3:00 Singlet-E' 3.2857 eV 377.35 nm f=0.0001110 ->112 0.48685111 ->113 0.50045

Excited State 4:00 Singlet-E' 3.7189 eV 333.39 nm f=1.0644109 ->112 0.452111 ->114 -0.43733

Excited State 5:00 Singlet-E' 3.7189 eV 333.39 nm f=1.0644110 ->112 0.452111 ->113 -0.43733

Excited state symmetry could not be determined.Excited State 11:00 Singlet-?Sy 4.3277 eV 286.49 nm f=0.2347

109 ->113 0.43514109 ->114 0.11809110 ->113 -0.1181110 ->114 0.43512111 ->116 -0.16703111 ->117 -0.14409

Excited state symmetry could not be determined.Excited State 12:00 Singlet-?Sy 4.3277 eV 286.49 nm f=0.2347

109 ->113 0.1181109 ->114 -0.43512110 ->113 0.43514110 ->114 0.1181111 ->116 -0.14408111 ->117 0.16703

Excited State 14:00 Singlet-E' 4.4624 eV 277.84 nm f=0.1375103 ->112 -0.40281111 ->116 -0.33523111 ->117 0.42506

Excited State 15:00 Singlet-E' 4.4624 eV 277.84 nm f=0.1375104 ->112 -0.40281111 ->116 0.42506111 ->117 0.33522

Table S7. Excitation energies of [12]DBA 2 in DMSO

Excited State 2:00 Singlet-A' 3.2973 eV 376.02 nm f=0.0098110 ->112 0.5219111 ->113 0.26894111 ->114 -0.38372

Excited State 3:00 Singlet-A' 3.2973 eV 376.01 nm f=0.0097109 ->112 0.52178111 ->113 -0.38384111 ->114 -0.26901

Excited State 4:00 Singlet-A' 3.6051 eV 343.91 nm f=1.4338109 ->112 0.16525110 ->112 -0.39401111 ->113 0.41984111 ->114 -0.25961

Excited State 5:00 Singlet-A' 3.6052 eV 343.9 nm f=1.4340109 ->112 0.39412110 ->112 0.16516111 ->113 0.25948111 ->114 0.41983

Excited State 11:00 Singlet-A' 4.2899 eV 289.01 nm f=0.2297109 ->114 0.45957110 ->113 0.45913111 ->116 -0.12213

Excited State 12:00 Singlet-A' 4.2899 eV 289.01 nm f=0.2296109 ->113 -0.45931110 ->114 0.45942111 ->117 -0.12201

Excited State 14:00 Singlet-A' 4.4845 eV 276.48 nm f=0.1061104 ->112 0.41179111 ->116 0.55304

Excited State 15:00 Singlet-A' 4.4847 eV 276.46 nm f=0.1061103 ->112 -0.41203111 ->117 0.55288

Excited State 20:00 Singlet-A' 4.8557 eV 255.34 nm f=0.0126104 ->112 0.50824111 ->116 -0.36384

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