Bulletin of the Chemical Society of Japan

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1 Supporting Information Bulletin of the Chemical Society of Japan Effects of ortho-phenyl Substitution on Molecular Arrangements of Octadehydrodibenzo[12]annulene Ichiro Hisaki,* 1 Noriko Manabe, 1 Keisuke Osaka, 1 Akinori Saeki, 2 Shu Seki, 2 Norimitsu Tohnai, 1 and Mikiji Miyata* 1 1 Department of Material and Life Science, Osaka University, 2-1 Yamadaoka, Suita, Osaka Department of Applied Chemistry, Graduate School of Engineering, Osaka University, 2-1 Yamadaoka, Suita, Osaka (Received October 9, 2013; hisaki@mls.eng.osaka-u.ac.jp) Copyright The Chemical Society of Japan

2 Supporting Information for Effects of ortho-phenyl Substitution on Molecular Arrangements of Octadehydrodibenzo[12]annulene Ichiro Hisaki, * Noriko Manabe, Keisuke Osaka, Akinori Saeki, Shu Seki, Norimitsu Tohnai, Mikiji Miyata * Contents 1. Stacking geometries of [12]DBAs in conventionally reported crystals. Figure S1. Examples of molecular arrangements of representative [12]DBA derivatives ever reported 2. Calculated structure of the expected ene-yne polyer Figure S2. Optimized structure of the hexamer. 3. Crystallographic analysis of crystals. Figure S3. Crystal structure of triangular DBA 6 Table S1. Crystal data of DBA 6 Figure S4. Crystal structures of IV(AcOEt) Figure S5. Crystal structures of IV(DCE) 4. Structural Change of III(DCM), IV(DCM), and IV(AcOEt) upon the guest release. Figure S6. PXRD patterns of III(DCM), IV(DCM), and IV(AcOEt) before and after guest release. 5. Photoluminescence properties of the crystals. Figure S7. Photos of crystals (a) I-GF, (b) II(CHCl 3 ), (c) III(DCM), (d) IV(DCM) under ambient light (top) and UV light with a wavelength of 356 nm (bottom). 6. NMR spectra of the new comdpounds Figure S8-S15 7. Atomic coordinates for theoretical calculation. Table S2. Atomic coordinate of [12]DBA 2 Table S3. Atomic coordinate of the ene-yne hexamer. 8. References 1

3 1. Stacking geometries of [12]DBAs in conventionally reported crystals. Figure S1. Examples of molecular arrangements of representative [12]DBA derivatives ever reported. Refcodes: (a) JOCQUN, S1 (b) SUMVUR, S2 (c) WUVVIS, S3 (d) WUVVOY, S4 (e) WUVVUE, S5 and (f) KEVRUZ. S6 All of them have slipped stacked structures along both the short and long molecular directions. 2

4 2. Calculated structure of the expected ene-yne polymer Figure S2. Optimized structure of the hexamer, whose edges are bonded by vinyl groups. Theoretical calculation was performed at B3LYP/6-31G* level with C 2h symmetry. 3

5 3. Crystallographic analysis of crystals. Figure S3. Crystal structure of triangular DBA 6, drawn with thermal ellipsoids in 50% probability (left) and spacefill model (right). Table S1. Crystal data of DBA 6 Formula C 66 H 36 Z 8 Fw collected reflection. no crystal system orthorhombic unique reflection. no space group Pbca R int a [Å] (3) d [g cm -3 ] b [Å] (2) R1 F 2 >2.0 (F 2 ) c [Å] (2) Rw (all data) α [ ] 90 GOF β [ ] 90 T [K] 100 γ [ ] 90 CCDC V [Å 3 ] (18) 4

6 Figure S4. Crystal structures of IV(AcOEt). (a) Side and (b) top views of the packing. (c) Side and (d) top views of the stacked column. Guest molecules (ethyl acetate) are disordered. 5

7 Figure S5. Crystal structures of IV(DCE). (a) Side and (b) top views of the packing. (c) Side and (d) top views of the stacked column. Guest molecules (1,2-dichloroethane) are disordered. 6

8 4. Structural change of III(DCM), IV(DCM), and IV(AcOEt) upon the guest release. Figure S6. PXRD patterns of (a) III(DCM), (b) IV(DCM), and (c) IV(AcOEt) and the corresponding patterns after guest release (d), (e), and (f), respectively. 7

9 5. Photoluminescence properties of the crystals. Figure S7. Photos of crystals (a) I-GF, (b) II(CHCl 3 ), (c) III(DCM), (d) IV(DCM) under ambient light (top) and UV light with a wavelength of 356 nm (bottom). 8

10 6. NMR spectra of the new compounds 4 Figure S8. 1 H NMR (270 MHz, CDCl 3 ) spectrum of 4. 4 Figure S9. 13 C NMR (65 MHz, CDCl 3 ) spectrum of 4. 9

11 5 Figure S10. 1 H NMR (270 MHz, CDCl 3 ) spectrum of 5. 5 Figure S C NMR (65 MHz, CDCl 3 ) spectrum of 5. 10

12 2 Figure S12. 1 H NMR (400 MHz, CDCl 3, 30 C) spectrum of 2. 2 Figure S C NMR (100 MHz, CDCl 3, 50 C) spectrum of 2. 11

13 6 Figure S14. 1 H NMR (400 MHz, CDCl 3, 30 C) spectrum of 6. 6 Figure S C NMR (150 MHz, pyridine-d 5, 80 C) spectrum of 6. 12

14 7. Atomic coordinates for theoretical calculation. Table S2. Atomic coordinate of [12]DBA 2 Stoichiometry C44H24 Framework group D2[X(C44H24)] Deg. of freedom 51 Full point group D2 Largest Abelian subgroup D2 NOp 4 Largest concise Abelian subgroup D2 NOp 4 Standard orientation: Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z

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16 Table S3. Atomic coordinate of the ene-yne hexamer. Stoichiometry C124H56 Framework group C2H[X(C124H56)] Deg. of freedom 134 Full point group C2H NOp 4 Largest Abelian subgroup C2H NOp 4 Largest concise Abelian subgroup C2H NOp 4 Standard orientation: Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z

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20 8. References S1. JOCQUN: Bunz, U. H. F.; Enkelmann, V. Chem. Eur. J. 1999, 5, S2. SUMVUR: Zhou, Q.; Carroll, P. J.; Swager, T. M. J. Org. Chem. 1994, 59, S3. WUVVIS, WUVVOY, WUVVUE: Nishinaga, T.; Nodera, N.; Miyata, Y.; Komatsu, K. J. Org. Chem. 2002, 67, S4. KEVRUZ: Setaka, W.; Kanai, S.; Kabuto, C.; Kira, M. Chem. Lett. 2006, 35,