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[SI_20250724.pdf](https://mdr.nims.go.jp/filesets/be90c12c-5a60-470e-bc88-a841d2d481dd/download)

## Creator

Yotaro Kasahara, [Takashi Takeda](https://orcid.org/0000-0002-5254-2819), [Shun Dekura](https://orcid.org/0000-0003-2498-6428), [Hayato Anetai](https://orcid.org/0000-0001-7469-8489), [Atsuro Takai](https://orcid.org/0000-0003-3457-3352), [Ichiro Hisaki](https://orcid.org/0000-0002-8170-5605), [Masayuki Takeuchi](https://orcid.org/0000-0002-0207-0665), [Tomoyuki Akutagawa](https://orcid.org/0000-0003-3040-1078)

## Rights

This document is the Accepted Manuscript version of a Published Work that appeared in final form in The Journal of Physical Chemistry B, copyright © 2025 American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://doi.org/10.1021/acs.jpcb.5c04027.[In Copyright](http://rightsstatements.org/vocab/InC/1.0/)

## Other metadata

[Ring-Size Effect on Molecular Assembly Structures and Optical Properties of <i>C</i><sub>3</sub>-Symmetrical Dehydrobenzoannulene Derivatives](https://mdr.nims.go.jp/datasets/8ef1b2b0-0a5b-4679-9671-33629254c04c)

## Fulltext

S1  Supporting Information Ring-Size Effect on Molecular Assembly Structures and Optical Properties of C3-Symmetrical Dehydrobenzoannulene Derivatives Yotaro Kasahara,a,b Takashi Takeda,a, b, c* Shun Dekura,a, b Hayato Anetai,d Atsuro Takai,d Ichiro Hisaki,e Masayuki Takeuchi,d and Tomoyuki Akutagawa a, b*  a Graduate School of Engineering, Tohoku University, Sendai 980-8579, Japan. b Institute of Multidisciplinary Research for Advanced Materials (IMRAM), Tohoku University, 2-1-1 Katahira, Aoba-ku, Sendai 980-8577, Japan. c Faculty of Science, Shinshu University, 3-1-1 Asahi, Matsumoto 390-8621, Japan, and d National Institute for Material Science (NIMS), 1-2-1 Tsukuba, 305-0047, Japan. d National Institute for Materials Science (NIMS), 1-2-1 Tsukuba, 305-0047, Japan.  e Graduate School of Engineering Science, The University of Osaka, Toyonaka, Osaka 560-8531, Japan.  f Research Center for Autonomous Systems Materialogy (ASMat), Institute of Integrated Research (IIR), Institute of Science Tokyo, 4259 Nagatsuta-cho, Midori-ku, Yokohama, 226-8501 Japan.  Phone:  +81-22-217-5653, Fax: +81-22-217-5655 E-mail: takashi@shinshu-u.ac.jp and akutagawa@tohoku.ac.jp  mailto:takashi@shinshu-u.ac.jpmailto:akutagawa@tohoku.ac.jpS2  Contents 1. Experimental Section (Scheme S1, S2, Figures S1–4) 2. Electronic structures of C1[n]DBA and C1Trip (Figure S5–7) 3. TG curves of C8[n]DBA and C8Trip (Figure S8)  4. PXRD pattern of C8[18]DBA after polymerization and crystal phase (Figure S9) 5. POM images of C8[12]DBA (Figure S10) 6. Molecular assembly structures of C8[n]DBAs and C8Trip (Table S1) 7. Single crystal structures of C1[n]DBAs and C1Trip (Figure S11) 8. PXRD patterns of C8[n]DBAs and C8Trip (Tables S2, 3) 9. Dielectric constants of C8[n]DBAs and C8Trip (Figure S12 – 15) 10. Optical properties of C8[n]DBAs and C8Trip (Table S4, Figure S16) 11. Fluorescence lifetime of C8[n]DBAs and C8Trip (Figures S17-18, Tables S5, 6) 12. NMR spectra (Figure S19–27)  13. HRMS spectrum (Figure S28)  14. Cartesian coordinates for optimized structures of C8[n]DBA and C8Trip   S3    Fig. S1.  Emission lifetime of Br–FL–CHO (red: 4  10–5 M) and instrumental response function (black: IRF) observed at 370 nm in CHCl3 at 298 K. The solid line is a fitted line for the fluorescence emission of Br–FL–CHO. Excitation wavelength is 333 nm.    Scheme S1. Preparation of C8Trip. Condition and reagents: 1) SOCl2, reflux, 15 h; 2) C8H17OH, Et3N, CH2Cl2, RT, 25 h, 50 %.  S4     Scheme S2. Synthesis of C8[18]DBA a: K2CO3, C8H17Br, dry DMF; b: I2, NaIO3, conc. H2SO4; c: TIPS acetylene, CuI, Pd(PPh3)4, i-Pr2NH, dry THF; d: Na2CO3, Pd(dppf)Cl2, toluene, H2O, 1,4-dioxane; e: TBAF, THF; f: (AcO)2Cu, pyridine, methanol, Et2O.   S5   Figure S2. Estimation of the intermolecular intradimer interaction (Eintra). Model structures used for calculations of Eintra in a) C1[18]DBA, b) C1Trip, and c) C1[12]DBA. (Legend) Red: monomer A, blue: monomer B. Hydrogen atoms are omitted for clarity. The interaction energy between dimers (Einter) was calculated from the difference between the energy of the tetramer and the sum of the energies of the two dimers, using equation (S2) (Figure S2).   Figure S3. Estimation of the interdimer interaction (Einter). Model structures using calculations of Einter in a) (C1[18]DBA)2, b) (C1Trip)2, and c) (C1[12]DBA)2. (Legend) Red: dimer A, blue: dimer B. Hydrogen atoms are omitted for clarity.  S6   Figure S4. Estimation of intermolecular interactions of the π-electrons at the π-planar molecules. Single-point energy calculations were performed for the structures excluding the terminal methylbenzoate groups. Model structures using calculations of interaction within intradimer Eπintra for a) [18]DBA, b) Trip, and c) [12]DBA. (Legend) Red: monomer A, blue: Monomer B.Model structures using calculations of interaction within interdimer Eπinter for d) ([18]DBA)2, e) (Trip)2, and f) ([12]DBA)2. (Legend) Red: dimer A, blue: dimer B. Hydrogen atoms are omitted for clarity.    S7  Electronic structures of C1[n]DBA and C1Trip  Figure S5. Frontier orbitals of C1[12]DBA estimated by B3LYP/6-31 G(d,p). Isovalue was 0.04.  Figure S6. Frontier orbitals of C1[18]DBA estimated by B3LYP/6-31 G(d,p). Isovalue was 0.04.   S8   Figure S7. Frontier orbitals of C1Trip estimated by B3LYP/6-31 G(d,p). Isovalue was 0.04.  S9   TG curves of C8[n]DBA and C8Trip   Figure S8. TG curves of a) C8[18]DBA, b) C8Trip, and c) C8[12]DBA. S10  PXRD pattern of C8[18]DBA after polymerization and crystal phase   Figure S9. PXRD patterns of C8[18]DBA in crystalline phase (red) and after polymerization (black).  POM images of C8[12]DBA   Figure S10. Variable temperature microscopic observations of C8[12]DBA.S1 Upper are the optical microscopic (OM) images and down are the polarized optical microscopic (POM) images. Scale bar is 300 μm. S11  Molecular assembly structures of C8[n]DBAs and C8Trip Table S1. Molecular assembly structures, phase transition behaviors, and the transition enthalpy changes of the phase transition (ΔH) of C8[n]DBA and C8Trip.  Compounds Molecular assemblies T, K ΔH, kJ/mol C8[18]DBA Crystal (Hexagonal columnar) 440, Polymerization − [b] C8Trip Crystal (Dimer columnar) 450, Cr → IL −23.8 (+16.7) C8[12]DBAS6 Glass 320, G → IL − [a] [a] Glass transition. [b] Polymerization.   Single crystal structures of C1[n]DBAs and C1Trip  Figure S11. Single crystal structures of C1[n]DBA and C1Trip. Viewed from the vertical (top) and horizontal (bottom) directions of the π plane. a) C1[12]DBAS1; b) C1[18]DBAS2; c) C1Trip. (Legend) Gray: carbon atoms, red: oxygen atoms. Hydrogen atoms are omitted for clarity.   S12  PXRD patterns of C8[n]DBA and C8Trip Table S2. The diffraction peak angle 2θ, correlation length (d), and the ratio of correlation length (d1 / dn) of the PXRD pattern of C8[18]DBA. Hexagonal arrangement (∘) Dimer columnar (•) 2θ /  d / Å d1 / dn ○ 3.12 28.3 1.0 ○ 5.41 16.3 1.7 ○ 6.16 14.4 2.0 ○ 8.40 10.5 2.7 ○ 9.37 9.44 3.0 ○ 11.7 7.59 3.7 ○ 12.6 7.04 4.0 ● 7.74 11.4 1.0 ● 14.8 5.99 1.9  Table S3. The diffraction peak angle 2θ, correlation length (d), and the ratio of correlation length (d1 / dn) of the PXRD pattern of C8Trip. Columnar arrangement (∘) Dimer columnar (•) 2θ /  d / Å d1 /dn ○ 3.93 22.6 1.0 ○ 7.90 11.2 2.0 ● 6.30 14.0 –    S13  Dielectric constants of C8[n]DBAs and C8Trip  Figure S12. Real part ε1 (a) and imaginary part ε2 (b) of the dielectric constant of C8Trip measured under N2 atmosphere.   Figure S13. Real part ε1 (a) and imaginary part ε2 (b) of the dielectric constant of C8[18]DBA measured under N2 atmosphere.   S14   Figure S14. Temperature dependence of the dielectric relaxation time τ of C8Trip and C8[12]DBAS1.   Figure S15. Real part ε1 (a) and imaginary part ε2 (b) of the dielectric constant of C8[12]DBA measured under vacuum atmosphere.S1  S15  Optical properties of C8[n]DBAs Table S4. Optical properties of C8[12]DBA, C8[18]DBA, and C8Trip in CHCl3 and solid state. Compounds Solution (in CHCl3) Solid   Absorption λmax, nm Fluorescent λmax, nm a φFL, % Absorption bλmax, nm Fluorescent λmax, nm c φFL, % C8Trip 310 391 11 313 413 5.7 C8[12]DBAS1 332 511 13 332 535 10 C8[18]DBA 356 452 29 361 471 1.9 a The excitation wavelength λex for the fluorescence spectra of C8[12]DBA, C8[18]DBA, and C8Trip in CHCl3 were 350, 395, and 310 nm, respectively. b Absorption spectra measured in the transmission configuration of the sample in KBr pellets. c The excitation wavelength λex for the fluorescence spectra of C8[12]DBA, C8[18]DBA, and C8Trip in solids were 340, 395, and 310 nm, respectively.   S16   Figure S16. Optical properties of CHCl3 solutions. a) C8[12]DBA (λex = 350 nm)S1, b) C8[18]DBA (λex = 395 nm), c) Absorption-emission spectra of C8Trip in CHCl3 solution and solid (λex = 310 nm). The vertical axis of the fluorescence spectrum is normalized based on the quantum yield (29%) of C8[18]DBA. In these figures,  the molar absorption coefficient.  S17   Figure S17. Fluorescence lifetime measurements of C8[n]DBAs and C8Trip. Fluorescence decay curves of a) C8[12]DBA (ex: 375 nm), b) C8Trip (ex: 279 nm), c) C8[18]DBA (ex: 279 nm). In parentheses are the observed emission wavelengths.  S18   Figure S18. Observed emission wavelength-dependent fluorescence lifetime measurements of C8[18]DBA (ex: 279 nm).  Table S5. Values of time constants () obtained from a global multiexponential fit of the emission decays of C8[n]DBAs and C8Trip in CHCl3 soln. and aggregated state.  Compounds Solution (in CHCl3) a Solid   Excitation λex, nm Observed λob, nm  / ns Excitation λex, nm Observed λob, nm  / ns C8[12]DBA 375 511 7.55 375 532 6.36    17.1   27.7    1.43    C8Trip 273 390 11.5 273 410 5.7       15.3 C8[18]DBA 273 455 1.03 273 473 0.654    2.18   1.34 a: The concentrations of the solvents were 1.49×10−4 M (C8[12]DBA), 1.26×10−4 M (C8[18]DBA), 1.24×10−4 M (C8Trip), S19  Table S6. Observed emission wavelength-dependent values of time constants () obtained from a global multiexponential fit of the emission decays of C8[18]DBAs in CHCl3 soln.  Solution (in CHCl3)a Excitation λex, nm Observed λob, nm  / ns 273 410 1.02   2.20 273 440 1.03   2.20 273 455 1.03   2.18 a: The concentrations of the solvents was 1.26×10−4 M (C8[18]DBA).    S20  NMR spectra.  Figure S19. 1H NMR spectrum of 3 in CDCl3.    Figure S20. 1H NMR spectrum of 5 in CDCl3. S21   Figure S21. 1H NMR spectrum of 6 in CDCl3.    Figure S22. 1H NMR spectrum of 7 in CDCl3.   S22   Figure S23. 1H NMR spectrum of 8 in CDCl3.   Figure S24. 1H NMR spectrum of C8[18]DBA in CDCl3.  S23   Figure S25. 13C NMR spectrum of C8[18]DBA in CDCl3.   Figure S26. 1H NMR spectrum of C8Trip in CDCl3.  S24    Figure S27. 13C NMR spectrum of C8Trip in CDCl3.   S25  HRMS of C8[18]DBA    Figure S28. HRMS of C8[18]DBA (FAB in the matrix of m-nitrobenzylalchol).   C8[18]DBA-FAB-LR-NBA-01  Mass Spectrum #1 6 * 1.00500 1000 1500 2000x10m/z020406080100[%]77107136217307349 460176616372891542891524 16776960C8[18]DBA-FAB-LR-NBA-01  Mass Spectrum #1 6 * 19.461400 1500 1600 1700 1800 1900 2000m/z012345[%]17661637152414811653178116091368 862336C8[18]DBA-FAB-HR-NBA-01  Mass Spectrum #7 21 * 1.001750 1755 1760 1765 1770 1775 1780 1785 1790 1795m/z020406080100[%]1765.97981766.98141767.98041778.95141764.9718 36729S26  Cartesian coordinates for optimized structures of C8[n]DBA and C8Trip C8[18]DBA E(B3LYP) = −3903.788484 a. u. Number of imaginary frequencies: 0       Atom Number Element X Y Z  Atom Number Element X Y Z 1 O 12.547807 −1.419174 −0.387215  28 C −6.154722 −2.717392 0.047694 2 O 12.494354 −2.850572 1.360081  29 C −5.429798 −1.522009 0.032779 3 O 7.552188 −10.099969 0.513207  30 C −4.025497 −1.483835 0.024135 4 O 8.772509 −9.343948 −1.231523  31 C −3.343900 −0.243956 0.014456 5 O −7.530046 −10.117469 0.497652  32 C −2.749525 0.824112 0.004202 6 O −8.752380 −9.359012 −1.244611  33 C −2.072892 1.999148 −0.008042 7 O −12.544497 −1.444266 −0.372267  34 C −1.447810 3.049526 −0.019845 8 O −12.486724 −2.882638 1.369151  35 C −0.717255 4.261173 −0.034927 9 O −3.849011 12.301623 −1.398574  36 C −1.388582 5.495055 −0.053986 10 O −5.022290 11.525736 0.369623  37 C −0.718179 6.721759 −0.077577 11 O 3.820040 12.344562 1.109309  38 C 0.703763 6.723623 −0.064001 12 O 4.994509 11.525961 −0.638734  39 C 1.377082 5.498309 −0.056281 13 C 2.748512 0.830150 −0.005018  40 C 0.708688 4.262743 −0.044297 S27  14 C 3.345146 −0.236654 0.006037  41 C 1.442032 3.052770 −0.029974 15 C 4.029311 −1.475105 0.017455  42 C 2.069277 2.003682 −0.017895 16 C 5.433699 −1.510331 0.024997  43 C 7.645881 −2.609006 0.119256 17 C 6.161112 −2.704165 0.042428  44 C 8.345788 −1.765414 −0.760911 18 C 5.451900 −3.936678 0.033484  45 C 9.726185 −1.626430 −0.668312 19 C 4.054115 −3.907557 0.038754  46 C 10.440882 −2.322703 0.313821 20 C 3.318043 −2.710961 0.033757  47 C 9.752422 −3.161513 1.201124 21 C 1.903455 −2.741334 0.032614  48 C 8.372720 −3.303275 1.101447 22 C 0.681245 −2.760298 0.032559  49 C 11.917651 −2.133770 0.367994 23 C −0.674736 −2.761857 0.033357  50 C 13.919665 −2.709756 1.466503 24 C −1.896984 −2.745614 0.034539  51 C 6.116546 −5.268429 −0.031289 25 C −3.311629 −2.718234 0.036860  52 C 7.089300 −5.552647 −1.004924 26 C −4.045199 −3.916371 0.039427  53 C 7.661449 −6.816905 −1.093634 27 C −5.442920 −3.948391 0.034957  54 C 7.276539 −7.828971 −0.203440 55 C 6.308121 −7.556262 0.770199  90 C 5.834900 12.688374 −0.565457 56 C 5.733019 −6.292892 0.851619  91 H 5.968820 −0.567435 0.052435 57 C 7.856912 −9.200441 −0.245725  92 H 3.508025 −4.844151 0.011449 58 C 9.369004 −10.646990 −1.326296  93 H −3.497183 −4.851753 0.009293 59 C −6.104794 −5.281351 −0.033304  94 H −5.966848 −0.580290 0.062792 60 C −5.718734 −6.307573 0.846446  95 H −2.472585 5.487124 −0.085963 61 C −6.291195 −7.571916 0.761556  96 H 2.461100 5.493775 −0.024160 62 C −7.259413 −7.843827 −0.212505  97 H 7.800926 −1.229591 −1.532355 63 C −7.646818 −6.829981 −1.099589  98 H 10.271727 −0.983854 −1.350784 64 C −7.077326 −5.564775 −1.007394  99 H 10.301390 −3.694995 1.968127 65 C −7.836878 −9.216402 −0.258605  100 H 7.849021 −3.948941 1.798129 66 C −9.346103 −10.663046 −1.343067  101 H 14.190107 −1.668531 1.657985 67 C −7.639621 −2.625583 0.125976  102 H 14.408338 −3.035906 0.545187 68 C −8.364224 −3.324777 1.106343  103 H 14.215780 −3.342862 2.302533 69 C −9.744152 −3.186382 1.207530  104 H 7.388977 −4.778987 −1.703639 70 C −10.435098 −2.345976 0.323672  105 H 8.404134 −7.027188 −1.854202 71 C −9.722647 −1.644741 −0.656571  106 H 6.022303 −8.347234 1.455005 72 C −8.342023 −1.780458 −0.750739  107 H 4.990064 −6.087465 1.616427 73 C −11.912234 −2.160506 0.379594  108 H 8.606654 −11.406060 −1.517569 74 C −13.912310 −2.745633 1.476768  109 H 9.891368 −10.899286 −0.400291 75 C −1.542478 7.959603 −0.166211  110 H 10.070043 −10.589298 −2.158567 S28      76 C −2.623901 8.150839 0.710438  111 H −4.975875 −6.102819 1.611531 77 C −3.437957 9.275393 0.609738  112 H −6.003420 −8.364291 1.443917 78 C −3.190374 10.233170 −0.381427  113 H −8.389334 −7.039614 −1.860501 79 C −2.118016 10.048248 −1.264359  114 H −7.378896 −4.789716 −1.703740 80 C −1.303245 8.928335 −1.156536  115 H −9.867424 −10.919321 −0.417569 81 C −4.027222 11.454953 −0.544819  116 H −8.582206 −11.419867 −1.537076 82 C −5.866051 12.683324 0.265249  117 H −10.047695 −10.604325 −2.174800 83 C 1.525015 7.965372 −0.007724  118 H −7.838618 −3.971742 1.800378 84 C 1.283441 8.959106 0.956925  119 H −10.291392 −3.723774 1.973038 85 C 2.095209 10.083660 1.035025  120 H −10.270056 −1.000985 −1.336434 86 C 3.166793 10.248275 0.147148  121 H −7.798978 −1.240850 −1.520821 87 C 3.416755 9.265448 −0.818567  122 H −14.400641 −3.069497 0.554464 88 C 2.605732 8.136438 −0.889406  123 H −14.185183 −1.705784 1.672247 89 C 4.000220 11.476302 0.277944  124 H −14.206525 −3.382587 2.310545 125 H −2.815570 7.417227 1.487765  132 H 0.461774 8.839795 1.654874 126 H −4.263492 9.416410 1.297445  133 H 1.919062 10.849033 1.782908 127 H −1.943730 10.794182 −2.032056  134 H 4.241703 9.390608 −1.510033 128 H −0.481071 8.792921 −1.850941  135 H 2.799162 7.383232 −1.647316 129 H −6.358337 12.713940 −0.709784  136 H 6.327388 12.746331 0.408229 130 H −5.281803 13.597843 0.392750  137 H 5.247925 13.597466 −0.716992 131 H −6.601484 12.583729 1.063194  138 H 6.570370 12.569783 −1.360767 S29  C8Trip E(B3LYP) = −3446.859594 a. u. Number of imaginary frequencies: 0     Atom Number Element X Y Z  Atom Number Element X Y Z 1 O 6.201622 −7.885557 1.339379  29 C −2.848581 −0.087548 0.054231 2 O 4.950529 −8.683298 −0.364447  30 H −3.412450 0.834871 0.112865 3 O 9.970101 −1.401598 −1.416485  31 C −3.578961 −1.272459 0.056331 4 O 9.897768 0.059221 0.305541  32 C −2.868032 −2.504075 0.006965 5 O 5.016818 8.506580 0.367949  33 C −1.476852 −2.462920 −0.008414 6 O 3.799966 9.298633 −1.363132  34 H −0.959978 −3.411794 −0.077113 7 O −3.800002 9.298599 1.363145  35 C −0.732432 −1.267683 0.008020 8 O −5.016849 8.506543 −0.367937  36 C 0.732443 −1.267683 −0.008035 9 O −9.897761 0.059211 −0.305522  37 C 3.530841 −3.835444 0.081386 10 O −9.970081 −1.401589 1.416520  38 C 4.518763 −4.098228 1.045845 11 O −4.950538 −8.683291 0.364440  39 H 4.831288 −3.307719 1.719744 12 O −6.201654 −7.885539 −1.339363  40 C 5.090750 −5.360821 1.156994 13 C 1.476864 −2.462919 0.008395  41 H 5.846064 −5.553278 1.909848 14 H 0.959990 −3.411794 0.077087  42 C 4.689949 −6.394486 0.299180 15 C 2.868044 −2.504073 −0.006979  43 C 3.706836 −6.143891 −0.665601 16 C 3.578972 −1.272457 −0.056339  44 H 3.409506 −6.950921 −1.326396 17 C 2.848591 −0.087547 −0.054238  45 C 3.133587 −4.881308 −0.769995 18 H 3.412460 0.834873 −0.112868  46 H 2.381192 −4.692384 −1.529852 19 C 1.441505 −0.039607 −0.025058  47 C 5.269216 −7.765132 0.365952 20 C 0.709019 1.229255 −0.015102  48 C 5.062557 −1.181256 −0.158725 21 C 1.371310 2.471772 −0.038707  49 C 5.778702 −0.322038 0.692134 S30  22 H 2.451670 2.499124 −0.104551  50 H 5.246091 0.227975 1.462260 23 C 0.710861 3.696929 −0.026970  51 C 7.158898 −0.183111 0.576995 24 C −0.710847 3.696929 0.026954  52 H 7.700262 0.476753 1.244836 25 C −1.371298 2.471773 0.038696  53 C 7.856181 −0.901965 −0.401919 26 H −2.451658 2.499126 0.104545  54 C 7.151122 −1.758827 −1.258022 27 C −0.709008 1.229256 0.015093  55 H 7.702917 −2.303374 −2.016461 28 C −1.441495 −0.039608 0.025047  56 C 5.774320 −1.898283 −1.136530 57 H 5.239685 −2.558869 −1.810592  92 C −3.133571 −4.881312 0.769972 58 C 9.331116 −0.795865 −0.578312  93 H −2.381172 −4.692391 1.529825 59 C 1.531413 4.936868 −0.122511  94 C −3.706821 −6.143894 0.665577 60 C 1.267221 5.916332 −1.095897  95 H −3.409488 −6.950927 1.326367 61 H 0.428460 5.786607 −1.771387  96 C −4.689941 −6.394485 −0.299198 62 C 2.076577 7.039442 −1.211443  97 C −5.090747 −5.360817 −1.157006 63 C 3.169850 7.217794 −0.353004  98 H −5.846066 −5.553270 −1.909855 64 C 3.442426 6.250267 0.622052  99 C −4.518758 −4.098224 −1.045856 65 H 4.283299 6.386622 1.291992  100 H −4.831286 −3.307713 −1.719752 66 C 2.632435 5.123461 0.730589  101 C −5.269208 −7.765131 −0.365972 67 H 2.841659 4.383349 1.497236  102 C 5.853913 9.667976 0.255651 68 C 3.999654 8.442796 −0.523278  103 H 6.608041 9.563297 1.035369 69 C −1.531403 4.936867 0.122496  104 H 6.323550 9.710257 −0.730105 70 C −2.632424 5.123457 −0.730607  105 H 5.269962 10.579283 0.405649 71 H −2.841641 4.383345 −1.497258  106 C 11.321182 0.205601 0.185288 72 C −3.442421 6.250259 −0.622070  107 H 11.586969 0.585361 −0.804245 73 H −4.283291 6.386610 −1.292014  108 H 11.610040 0.916659 0.958981 74 C −3.169852 7.217785 0.352988  109 H 11.821343 −0.753722 0.338868 75 C −2.076580 7.039435 1.211429  110 C 6.800328 −9.185847 1.453675 76 H −1.881956 7.793209 1.966523  111 H 7.306614 −9.459310 0.524759 77 C −1.267217 5.916330 1.095883  112 H 7.515986 −9.108899 2.271877 78 H −0.428454 5.786611 1.771371  113 H 6.042007 −9.940602 1.675752 79 C −3.999661 8.442782 0.523265  114 C −6.800395 −9.185816 −1.453630 80 C −5.062545 −1.181259 0.158724  115 H −7.516087 −9.108853 −2.271801 81 C −5.774304 −1.898291 1.136528  116 H −6.042100 −9.940587 −1.675739 82 H −5.239667 −2.558882 1.810584  117 H −7.306646 −9.459265 −0.524692 83 C −7.151105 −1.758834 1.258028  118 C −11.321173 0.205594 −0.185260 84 H −7.702896 −2.303385 2.016468  119 H −11.610043 0.916612 −0.958985 S31   Reference (S1) Kasahara, Y.; Hisaki, I.; Akutagawa, T.; Takeda, T. Fluorescent Molecular Glass Based on Hexadehydrotribenzo[12]Annulene. Chem. Commun. 2021, 57, 5374–5377. (S2) Hisaki, I.; Nakagawa, S.; Tohnai, N.; Miyata, M. A C3-Symmetric Macrocycle-Based, Hydrogen-Bonded, Multiporous Hexagonal Network as a Motif of Porous Molecular Crystals. Angew. Chem. Int. Ed. 2015, 54, 3008–3012.  85 C −7.856168 −0.901967 0.401934  120 H −11.821334 −0.753739 −0.338783 86 C −7.158889 −0.183108 −0.576980  121 H −11.586948 0.585405 0.804258 87 H −7.700257 0.476760 −1.244815  122 C −5.853980 9.667910 −0.255608 88 C −5.778694 −0.322035 −0.692126  123 H −6.608127 9.563210 −1.035304 89 H −5.246087 0.227983 −1.462253  124 H −6.323588 9.710170 0.730163 90 C −9.331101 −0.795863 0.578338  125 H −5.270062 10.579237 −0.405619 91 C −3.530830 −3.835445 −0.081403  126 H 1.881950 7.793216 −1.966535