Supplementary Information Thermochromism in an organic crystal based on the co-existence of σ- and π-dimers YASUSHI MORITA 1,2 *, SHUICHI SUZUKI 1, KOZO FUKUI 2, SHIGEAKI NAKAZAWA 3, HIROSHI KITAGAWA 4, HIDEO KISHIDA 5, HIROSHI OKAMOTO 5, AKIRA NAITO 6, AKIKO SEKINE 7, YUJI OHASHI 7, MOTOO SHIRO 8, KATSUNARI SASAKI 8, DAISUKE SHIOMI 3, KAZUNOBU SATO 3, TAKEJI TAKUI 3 *, KAZUHIRO NAKASUJI 1 1 Department of Chemistry, Graduate School of Science, Osaka University, Toyonaka, Osaka 560-0043, Japan. 2 PRESTO, Japan Science and Technology Agency, Kawaguchi, Saitama 332-0012, Japan. 3 Departments of Chemistry and Materials Science, Graduate School of Science, Osaka City University, Sumiyoshi-ku, Osaka 558-8585, Japan. 4 Department of Chemistry, Graduate School of Science, Kyushu University, Fukuoka, Fukuoka 812-8581, Japan. 5 Department of Advanced Materials Science, Graduate School of Frontier Sciences, University of Tokyo, Kashiwa, Chiba 277-8561, Japan. 6 Faculty of Engineering, Yokohama National University, Hodogaya-ku, Yokohama 240-0085, Japan. 7 Department of Chemistry and Materials Science, Graduate School of Science and Engineering, Tokyo Institute of Technology, Meguro-ku, Tokyo 152-8550, Japan. 8 Rigaku Corporation, Akishima, Tokyo 196-8666, Japan. e-mail: morita@chem.sci.osaka-u.ac.jp; takui@sci.osaka-cu.ac.jp S1
Figure S1 The colour change of the crystal in Figure 2 depending on the temperature. S2
p / mm q / mm r / mm The crystal in Figure 2 0.22 0.83 0.15 The crystal using measurements of the polarized electronic spectra 0.13 0.24 0.05 Figure S2 A schematic structure of the crystal habit: The table shows approximate lengths of the crystal used in Figure 2 and in the measurements of the polarized electronic spectra at various temperatures. S3
Figure S3 The disordered arrangement and numbers of atoms for definition method for setting two atoms. The distances of C1 C2, C1 C12, C26 C27, and C26 C37 were defined to be 1.51 Å S1. The distances of C101 C2, C101 C12, C126 C27, and C126 C37 were defined to be 1.40 Å S1. The occupancy of C1 was refined by the least-square method. The occupancy of C26 was defined to be equal to that of C1. The sum of the occupancies of C1 and C101, and C26 and C126 was fixed to be 1. S4
Table S1 Crystal data of 2 at 93 K. empirical formula C 46 H 62 N 4 formula weight 671.02 crystal colour, habit colourless, block crystal dimensions, mm 0.20 0.20 0.10 crystal system monoclinic space group P2 1 /n (#14) a, Å 12.715(3) b, Å 21.450(5) c, Å 15.047(3) α, deg 90 β, deg 106.71(1) γ, deg 90 V, Å 3 3930(1) Z 4 D calc, g cm 3 1.134 F(000) 1464.00 µ, cm 1 (Cu Kα) 4.96 diffractometer Rigaku RAXIS-RAPID Imaging Plate radiation (λ, Å) 1.54187 (graphite monochromated) 2θ max, deg 136.2 temperature, K 93 structure solution direct methods (SIR2003) refinement full matrix least-squares using all reflections number of unique reflections 6962 number of observed reflections with I > 2σ(I) 3069 number of variables 453 R1 (calculated on F) 0.088 (I > 2σ(I)) wr2 (calculated on F 2 ) 0.265 (all reflections) S, goodness of fit 0.905 final max/min Δρ, eå 3 0.90/ 0.41 S5
Table S2 Atomic coordinates and equivalent isotopic displacement parameters (Å 2 ) for the crystal structural analysis of 2 at 93 K. atom x y z Beq occ N(9) 0.9642(3) 0.3729(2) 0.7444(3) 4.17(9) N(11) 1.0888(3) 0.2929(2) 0.7279(3) 3.86(8) N(30) 1.0299(3) 0.3231(2) 0.9819(3) 3.78(8) N(32) 0.8491(4) 0.2843(2) 0.9811(3) 4.9(1) C(1) 1.0406(3) 0.1808(1) 0.7294(4) 3.0(1) 0.811(10) C(2) 0.9429(3) 0.1433(2) 0.6743(3) 3.39(9) C(3) 0.8398(3) 0.1611(2) 0.6700(3) 2.25(7) C(4) 0.8176(3) 0.2216(2) 0.6998(3) 2.38(7) C(5) 0.7143(3) 0.2404(2) 0.7020(3) 2.32(7) C(6) 0.6939(4) 0.3017(2) 0.7241(3) 3.31(9) C(7) 0.7753(4) 0.3462(2) 0.7346(3) 3.66(9) C(8) 0.8830(4) 0.3285(2) 0.7361(3) 3.30(9) C(10) 1.0635(3) 0.3540(2) 0.7393(3) 2.67(8) C(12) 1.0090(3) 0.2488(2) 0.7203(3) 2.82(8) C(13) 0.9037(3) 0.2658(2) 0.7197(3) 2.23(7) C(14) 0.9638(4) 0.0821(2) 0.6287(3) 3.36(9) C(15) 0.5824(4) 0.3226(2) 0.7290(3) 3.04(8) C(16) 1.1510(3) 0.4032(2) 0.7466(3) 2.76(8) C(17) 1.0009(4) 0.0997(2) 0.5444(4) 4.3(1) C(18) 1.0535(4) 0.0433(2) 0.6952(4) 4.4(1) C(19) 0.8608(4) 0.0420(2) 0.5968(3) 3.09(8) C(20) 0.4990(4) 0.2701(2) 0.7096(4) 4.0(1) C(21) 0.5398(5) 0.3733(3) 0.6549(4) 5.3(1) C(22) 0.5883(4) 0.3499(3) 0.8236(4) 4.7(1) C(23) 1.1011(4) 0.4603(2) 0.6872(4) 3.8(1) C(24) 1.1938(4) 0.4236(2) 0.8485(3) 3.8(1) C(25) 1.2471(4) 0.3795(2) 0.7152(3) 3.6(1) C(26) 1.0895(3) 0.1615(2) 0.8432(3) 3.2(1) 0.811(10) C(27) 1.1848(3) 0.2001(2) 0.8998(3) 3.6(1) C(28) 1.1625(4) 0.2544(2) 0.9395(3) 3.20(9) C(29) 1.0547(4) 0.2676(2) 0.9461(3) 2.96(8) C(31) 0.9275(4) 0.3311(2) 0.9937(3) 3.11(9) C(33) 0.8750(4) 0.2275(2) 0.9441(3) 3.33(9) C(34) 0.8040(3) 0.1778(2) 0.9349(3) 2.85(8) C(35) 0.8328(4) 0.1215(2) 0.9082(3) 3.00(8) C(36) 0.9294(3) 0.1137(2) 0.8846(3) 2.65(8) C(37) 1.0006(4) 0.1616(2) 0.8915(3) 3.54(9) C38) 0.9759(4) 0.2195(2) 0.9246(3) 2.63(8) C(39) 1.3031(4) 0.1838(2) 0.9041(3) 3.14(9) S6
C(40) 0.9042(4) 0.3931(2) 1.0332(3) 2.73(8) C(41) 0.7606(4) 0.0644(2) 0.9041(3) 3.04(8) C(42) 1.3368(5) 0.1269(2) 0.9665(4) 4.7(1) C(43) 1.3134(4) 0.1671(2) 0.8083(3) 3.54(9) C(44) 1.3847(4) 0.2364(2) 0.9439(3) 3.69(9) C(45) 1.0003(4) 0.4108(2) 1.1171(3) 3.7(1) C(46) 0.8899(4) 0.4433(2) 0.9585(3) 3.28(9) C(47) 0.7999(4) 0.3901(2) 1.0633(3) 3.9(1) C(48) 0.8216(5) 0.0186(2) 0.9796(4) 5.3(1) C(49) 0.7362(4) 0.0331(2) 0.8094(3) 3.9(1) C(50) 0.6493(4) 0.0811(3) 0.9196(4) 5.5(1) C(101) 1.016(1) 0.1925(4) 0.675(1) 1.2(3) 0.188 C(126) 1.1131(4) 0.1517(3) 0.905(1) 1.4(3) 0.188 H(1) 0.7808 0.1328 0.6468 2.703 H(2) 0.6559 0.2111 0.6881 2.786 H(3) 0.7588 0.3889 0.7409 4.388 H(4) 1.0672 0.1254 0.5642 5.168 H(5) 0.9425 0.1232 0.5005 5.168 H(6) 1.0168 0.0618 0.5144 5.168 H(7) 1.0322 0.0343 0.7515 5.234 H(8) 1.1226 0.0667 0.7117 5.234 H(9) 1.0632 0.0041 0.6650 5.234 H(10) 0.8005 0.0670 0.5576 3.704 H(11) 0.8404 0.0268 0.6510 3.704 H(12) 0.8751 0.0064 0.5611 3.704 H(13) 0.5215 0.2385 0.7583 4.773 H(14) 0.4948 0.2513 0.6493 4.773 H(15) 0.4269 0.2867 0.7086 4.773 H(16) 0.5346 0.3562 0.5934 6.352 H(17) 0.5906 0.4088 0.6674 6.352 H(18) 0.4670 0.3872 0.6567 6.352 H(19) 0.6273 0.3898 0.8313 5.696 H(20) 0.6276 0.3209 0.8723 5.696 H(21) 0.5138 0.3564 0.8282 5.696 H(22) 1.0701 0.4475 0.6224 4.591 H(23) 1.1585 0.4916 0.6912 4.591 H(24) 1.0430 0.4783 0.7102 4.591 H(25) 1.1329 0.4401 0.8691 4.530 H(26) 1.2498 0.4559 0.8545 4.530 H(27) 1.2260 0.3876 0.8869 4.530 H(28) 1.2209 0.3664 0.6501 4.368 H(29) 1.2809 0.3438 0.7537 4.368 H(30) 1.3015 0.4128 0.7216 4.368 S7
H(31) 1.2199 0.2836 0.9630 3.843 H(32) 0.7353 0.1829 0.9473 3.420 H(33) 0.9459 0.0743 0.8632 3.176 H(34) 1.3247 0.1351 1.0269 5.656 H(35) 1.4148 0.1180 0.9753 5.656 H(36) 1.2927 0.0909 0.9375 5.656 H(37) 1.2888 0.2024 0.7660 4.252 H(38) 1.2678 0.1306 0.7843 4.252 H(39) 1.3902 0.1576 0.8131 4.252 H(40) 1.3764 0.2497 1.0039 4.423 H(41) 1.3702 0.2718 0.9009 4.423 H(42) 1.4598 0.2213 0.9525 4.423 H(43) 0.9886 0.4528 1.1379 4.437 H(44) 1.0688 0.4098 1.0995 4.437 H(45) 1.0050 0.3810 1.1674 4.437 H(46) 0.9578 0.4471 0.9404 3.937 H(47) 0.8734 0.4833 0.9829 3.937 H(48) 0.8293 0.4318 0.9042 3.937 H(49) 0.8073 0.3574 1.1102 4.682 H(50) 0.7373 0.3806 1.0095 4.682 H(51) 0.7879 0.4304 1.0896 4.682 H(52) 0.8698 0.0418 1.0316 6.329 H(53) 0.8658-0.0099 0.9540 6.329 H(54) 0.7683-0.0054 1.0015 6.329 H(55) 0.6688 0.0508 0.7678 4.720 H(56) 0.7265-0.0118 0.8162 4.720 H(57) 0.7975 0.0403 0.7834 4.720 H(58) 0.6282 0.1234 0.8968 6.611 H(59) 0.6557 0.0790 0.9860 6.611 H(60) 0.5933 0.0514 0.8859 6.611 *B eq = 8/3π 2 (U 11 (aa*) 2 + U 22 (bb*) 2 + U 33 (cc*) 2 + 2U 12 (aa*bb*)cosγ + 2U 13 (aa*cc*)cosβ + 2U 23 (bb*cc*)cosα S8
Table S3 Crystal data of 2 at 153 K. empirical formula C 46 H 62 N 4 formula weight 671.02 crystal colour, habit light green, block crystal dimensions, mm 0.20 0.20 0.10 crystal system monoclinic space group P21/n (#14) a, Å 12.740(3) b, Å 21.521(5) c, Å 15.124(3) α, deg 90 β, deg 106.57(1) γ, deg 90 V, Å 3 3974(1) Z 4 D calc, g cm 3 1.121 F(000) 1464.00 µ, cm 1 (Cu Kα) 4.90 diffractometer Rigaku RAXIS-RAPID Imaging Plate radiation (λ, Å) 1.54187 (graphite monochromated) 2θ max, deg 136.3 temperature, K 153 structure solution direct methods (SIR2003) refinement full matrix least-squares using all reflections number of unique reflections 7056 number of observed reflections with I > 2σ(I) 3430 number of variables 453 R1(calculated on F) 0.097 (I > 2σ(I)) wr2 (calculated on F 2 ) 0.310 (all reflections) S, goodness of fit 0.976 final max/min Δρ, eå 3 0.81/ 0.31 S9
Table S4 Atomic coordinates and equivalent isotopic displacement parameters (Å 2 ) for the crystal structural analysis of 2 at 153 K. atom x y z Beq occ N(9) 0.9643(3) 0.3727(2) 0.7437(3) 4.80(9) N(11) 1.0887(3) 0.2928(2) 0.7279(3) 4.53(8) N(30) 1.0292(3) 0.3222(2) 0.9804(3) 4.44(8) N(32) 0.8492(4) 0.2841(2) 0.9801(3) 5.32(9) C(1) 1.0398(3) 0.1811(1) 0.7299(4) 3.2(1) 0.762(10) C(2) 0.9430(3) 0.1439(2) 0.6743(3) 4.01(9) C(3) 0.8398(3) 0.1617(2) 0.6694(3) 2.95(7) C(4) 0.8181(3) 0.2217(2) 0.6998(3) 3.02(7) C(5) 0.7144(3) 0.2408(2) 0.7018(3) 3.02(7) C(6) 0.6944(4) 0.3019(2) 0.7233(3) 3.99(9) C(7) 0.7763(4) 0.3462(2) 0.7340(3) 4.23(9) C(8) 0.8833(4) 0.3286(2) 0.7359(3) 3.91(9) C(10) 1.0636(3) 0.3535(2) 0.7395(3) 3.35(8) C(12) 1.0090(3) 0.2490(1) 0.7199(3) 3.36(8) C(13) 0.9038(3) 0.2660(2) 0.7195(3) 2.81(7) C(14) 0.9635(4) 0.0832(2) 0.6284(3) 4.03(9) C(15) 0.5834(3) 0.3225(2) 0.7289(3) 3.79(8) C(16) 1.1507(3) 0.4027(2) 0.7460(3) 3.56(8) C(17) 1.0004(5) 0.1009(2) 0.5447(4) 5.6(1) C(18) 1.0528(4) 0.0443(2) 0.6940(4) 5.5(1) C(19) 0.8613(4) 0.0435(2) 0.5964(3) 4.07(9) C(20) 0.4999(4) 0.2706(3) 0.7077(4) 5.9(1) C(21) 0.5409(6) 0.3728(3) 0.6548(5) 7.5(2) C(22) 0.5881(4) 0.3500(3) 0.8211(4) 7.2(2) C(23) 1.1014(4) 0.4595(2) 0.6877(4) 5.4(1) C(24) 1.1938(4) 0.4230(2) 0.8478(4) 5.4(1) C(25) 1.2458(4) 0.3790(2) 0.7150(4) 5.1(1) C(26) 1.0873(3) 0.1625(2) 0.8414(3) 3.3(1) 0.762(10) C(27) 1.1829(3) 0.1999(2) 0.8988(3) 4.2(1) C(28) 1.1610(4) 0.2536(2) 0.9383(3) 3.97(9) C(29) 1.0536(4) 0.2675(2) 0.9449(3) 3.58(8) C(31) 0.9270(4) 0.3304(2) 0.9922(3) 3.84(9) C(33) 0.8740(4) 0.2276(2) 0.9428(3) 3.93(9) C(34) 0.8031(3) 0.1781(2) 0.9335(3) 3.55(8) C(35) 0.8312(4) 0.1221(2) 0.9064(3) 3.65(8) C(36) 0.9270(3) 0.1144(2) 0.8827(3) 3.48(8) C(37) 0.9987(4) 0.1620(2) 0.8897(3) 4.15(9) C(38) 0.9742(4) 0.2195(2) 0.9231(3) 3.25(8) C(39) 1.3012(4) 0.1829(2) 0.9042(3) 3.91(9) S10
C(40) 0.9040(3) 0.3924(2) 1.0327(3) 3.55(8) C(41) 0.7585(4) 0.0654(2) 0.9022(3) 4.09(9) C(42) 1.3324(5) 0.1260(3) 0.9652(4) 6.2(1) C(43) 1.3123(4) 0.1673(2) 0.8086(3) 4.6(1) C(44) 1.3828(4) 0.2347(2) 0.9452(4) 4.9(1) C(45) 1.0001(4) 0.4099(2) 1.1152(3) 4.9(1) C(46) 0.8903(4) 0.4427(2) 0.9583(3) 4.20(9) C(47) 0.7999(4) 0.3900(2) 1.0625(4) 5.1(1) C(48) 0.8188(5) 0.0205(3) 0.9788(4) 7.5(2) C(49) 0.7351(4) 0.0341(2) 0.8089(4) 5.2(1) C(50) 0.6468(5) 0.0825(3) 0.9160(5) 7.5(2) C(101) 1.017(1) 0.1926(3) 0.676(1) 3.1(3) 0.238 C(126) 1.1103(4) 0.1515(3) 0.901(1) 3.2(3) 0.238 H(1) 0.7808 0.1338 0.6454 3.537 H(2) 0.6561 0.2116 0.6882 3.630 H(3) 0.7600 0.3888 0.7402 5.070 H(4) 1.0665 0.1266 0.5643 6.725 H(5) 0.9421 0.1244 0.5012 6.725 H(6) 1.0163 0.0632 0.5146 6.725 H(7) 1.0316 0.0353 0.7501 6.562 H(8) 1.1219 0.0674 0.7102 6.562 H(9) 1.0620 0.0053 0.6638 6.562 H(10) 0.8015 0.0685 0.5574 4.883 H(11) 0.8406 0.0284 0.6501 4.883 H(12) 0.8759 0.0081 0.5609 4.883 H(13) 0.5210 0.2387 0.7556 7.120 H(14) 0.4968 0.2524 0.6476 7.120 H(15) 0.4277 0.2873 0.7060 7.120 H(16) 0.5359 0.3556 0.5938 8.974 H(17) 0.5914 0.4082 0.6670 8.974 H(18) 0.4682 0.3867 0.6565 8.974 H(19) 0.6271 0.3898 0.8284 8.620 H(20) 0.6268 0.3215 0.8701 8.620 H(21) 0.5135 0.3568 0.8251 8.620 H(22) 1.0704 0.4469 0.6233 6.463 H(23) 1.1587 0.4906 0.6918 6.463 H(24) 1.0435 0.4773 0.7109 6.463 H(25) 1.1331 0.4395 0.8685 6.478 H(26) 1.2497 0.4552 0.8537 6.478 H(27) 1.2259 0.3871 0.8859 6.478 H(28) 1.2198 0.3660 0.6503 6.120 H(29) 1.2793 0.3435 0.7532 6.120 H(30) 1.3003 0.4121 0.7213 6.120 S11
H(31) 1.2186 0.2825 0.9620 4.759 H(32) 0.7347 0.1833 0.9459 4.259 H(33) 0.9432 0.0751 0.8611 4.178 H(34) 1.3203 0.1343 1.0252 7.405 H(35) 1.4098 0.1162 0.9739 7.405 H(36) 1.2872 0.0906 0.9359 7.405 H(37) 1.2876 0.2028 0.7673 5.574 H(38) 1.2672 0.1309 0.7840 5.574 H(39) 1.3891 0.1583 0.8134 5.574 H(40) 1.3738 0.2475 1.0048 5.921 H(41) 1.3694 0.2703 0.9031 5.921 H(42) 1.4576 0.2195 0.9541 5.921 H(43) 0.9886 0.4518 1.1361 5.833 H(44) 1.0680 0.4091 1.0970 5.833 H(45) 1.0054 0.3802 1.1653 5.833 H(46) 0.9582 0.4462 0.9405 5.042 H(47) 0.8740 0.4826 0.9827 5.042 H(48) 0.8300 0.4313 0.9043 5.042 H(49) 0.8067 0.3575 1.1092 6.096 H(50) 0.7375 0.3806 1.0090 6.096 H(51) 0.7882 0.4302 1.0884 6.096 H(52) 0.8664 0.0442 1.0300 9.029 H(53) 0.8633-0.0083 0.9544 9.029 H(54) 0.7653-0.0029 1.0007 9.029 H(55) 0.6681 0.0515 0.7672 6.292 H(56) 0.7255-0.0107 0.8159 6.292 H(57) 0.7965 0.0411 0.7832 6.292 H(58) 0.6265 0.1247 0.8930 8.996 H(59) 0.6517 0.0805 0.9818 8.996 H(60) 0.5911 0.0531 0.8819 8.996 *B eq = 8/3π 2 (U 11 (aa*) 2 + U 22 (bb*) 2 + U 33 (cc*) 2 + 2U 12 (aa*bb*)cosγ + 2U 13 (aa*cc*)cosβ + 2U 23 (bb*cc*)cosα S12
Table S5 Crystal data of 2 at 213 K. empirical formula C 46 H 62 N 4 formula weight 671.02 crystal colour, habit green, block crystal dimensions, mm 0.20 0.20 0.10 crystal system monoclinic space group P2 1 /n (#14) a, Å 12.764(3) b, Å 21.610(6) c, Å 15.239(4) α, deg 90 β, deg 106.35(2) γ, deg 90 V, Å 3 4033(1) Z 4 D calc, g cm 3 1.105 F(000) 1464.00 µ, cm 1 (Cu Kα) 4.83 diffractometer Rigaku RAXIS-RAPID Imaging Plate radiation (λ, Å) 1.54187 (graphite monochromated) 2θ max, deg 136.3 temperature, K 213 structure solution direct methods (SIR2003) refinement full matrix least-squares using all reflections number of unique reflections 7145 number of observed reflections with I > 2σ(I) 3351 number of variables 453 R1 (calculated on F) 0.100 (I > 2σ(I)) wr2 (calculated on F 2 ) 0.330 (all reflections) S, goodness of fit 0.977 final max/min Δρ, eå 3 0.87/ 0.42 S13
Table S6 Atomic coordinates and equivalent isotopic displacement parameters (Å 2 ) for the crystal structural analysis of 2 at 213 K. atom x y z Beq occ N(9) 0.9641(3) 0.3720(2) 0.7428(3) 5.37(9) N(11) 1.0885(3) 0.2929(2) 0.7279(3) 5.01(8) N(30) 1.0278(3) 0.3214(2) 0.9779(3) 5.12(8) N(32) 0.8488(4) 0.2838(2) 0.9770(3) 6.1(1) C(1) 1.0388(3) 0.1816(1) 0.7285(4) 3.9(1) 0.766(10) C(2) 0.9426(3) 0.1448(2) 0.6722(3) 4.57(9) C(3) 0.8388(3) 0.1625(2) 0.6669(3) 3.64(8) C(4) 0.8182(3) 0.2223(2) 0.6988(3) 3.52(7) C(5) 0.7148(3) 0.2414(2) 0.7006(3) 3.59(8) C(6) 0.6943(4) 0.3022(2) 0.7220(3) 4.61(9) C(7) 0.7765(4) 0.3464(2) 0.7336(3) 4.73(9) C(8) 0.8832(3) 0.3287(2) 0.7350(3) 4.38(9) C(10) 1.0631(3) 0.3529(2) 0.7390(3) 3.96(8) C(12) 1.0084(3) 0.2492(1) 0.7187(3) 3.94(8) C(13) 0.9033(3) 0.2659(2) 0.7186(3) 3.36(7) C(14) 0.9630(4) 0.0846(2) 0.6261(4) 4.8(1) C(15) 0.5834(3) 0.3224(2) 0.7277(3) 4.41(9) C(16) 1.1500(3) 0.4020(2) 0.7450(3) 4.32(9) C(17) 1.0006(5) 0.1021(3) 0.5436(4) 7.0(2) C(18) 1.0517(5) 0.0455(2) 0.6907(4) 6.9(1) C(19) 0.8612(4) 0.0445(2) 0.5952(4) 5.1(1) C(20) 0.5000(5) 0.2724(3) 0.7023(6) 9.3(2) C(21) 0.5433(7) 0.3722(4) 0.6552(6) 10.5(2) C(22) 0.5867(5) 0.3500(5) 0.8162(5) 12.8(3) C(23) 1.1019(5) 0.4585(3) 0.6895(6) 8.4(2) C(24) 1.1933(5) 0.4219(3) 0.8462(5) 8.5(2) C(25) 1.2441(5) 0.3789(3) 0.7142(5) 7.7(2) C(26) 1.0849(3) 0.1623(2) 0.8394(3) 3.9(1) 0.766(10) C(27) 1.1805(3) 0.1990(2) 0.8969(3) 4.8(1) C(28) 1.1590(4) 0.2526(2) 0.9358(3) 4.59(9) C(29) 1.0520(4) 0.2667(2) 0.9419(3) 4.15(8) C(31) 0.9262(3) 0.3296(2) 0.9899(3) 4.30(9) C(33) 0.8725(4) 0.2275(2) 0.9401(3) 4.25(9) C(34) 0.8015(3) 0.1788(2) 0.9302(3) 4.14(9) C(35) 0.8285(4) 0.1226(2) 0.9027(3) 4.25(9) C(36) 0.9234(3) 0.1150(2) 0.8792(3) 4.19(9) C(37) 0.9957(4) 0.1621(2) 0.8867(3) 4.8(1) C(38) 0.9722(3) 0.2190(2) 0.9207(3) 3.69(8) C(39) 1.2987(4) 0.1814(2) 0.9034(3) 4.55(9) S14
C(40) 0.9032(4) 0.3914(2) 1.0299(3) 4.23(8) C(41) 0.7554(4) 0.0667(2) 0.8983(4) 5.0(1) C(42) 1.3270(5) 0.1237(3) 0.9626(5) 8.0(2) C(43) 1.3121(4) 0.1677(3) 0.8088(4) 6.0(1) C(44) 1.3811(4) 0.2322(3) 0.9454(4) 6.4(1) C(45) 0.9992(4) 0.4092(2) 1.1111(4) 6.2(1) C(46) 0.8897(4) 0.4412(2) 0.9565(4) 5.3(1) C(47) 0.8002(5) 0.3889(3) 1.0602(4) 6.5(1) C(48) 0.8138(6) 0.0231(3) 0.9752(5) 10.2(2) C(49) 0.7326(5) 0.0351(2) 0.8053(4) 6.7(1) C(50) 0.6433(5) 0.0849(3) 0.9102(6) 10.1(2) C(101) 1.0172(9) 0.1932(3) 0.6738(9) 2.7(3) 0.234 C(126) 1.1078(4) 0.1503(3) 0.899(1) 3.4(3) 0.234 H(1) 0.7803 0.1354 0.6420 4.369 H(2) 0.6572 0.2126 0.6869 4.313 H(3) 0.7607 0.3883 0.7405 5.672 H(4) 1.0658 0.1274 0.5631 8.392 H(5) 0.9433 0.1252 0.5008 8.392 H(6) 1.0167 0.0649 0.5143 8.392 H(7) 1.0308 0.0367 0.7459 8.299 H(8) 1.1201 0.0681 0.7064 8.299 H(9) 1.0604 0.0070 0.6609 8.299 H(10) 0.8019 0.0688 0.5568 6.090 H(11) 0.8409 0.0299 0.6483 6.090 H(12) 0.8759 0.0094 0.5608 6.090 H(13) 0.5178 0.2398 0.7479 11.101 H(14) 0.4992 0.2556 0.6431 11.101 H(15) 0.4286 0.2893 0.6993 11.101 H(16) 0.5385 0.3552 0.5953 12.631 H(17) 0.5940 0.4067 0.6674 12.631 H(18) 0.4718 0.3865 0.6568 12.631 H(19) 0.6253 0.3892 0.8228 15.304 H(20) 0.6242 0.3223 0.8650 15.304 H(21) 0.5128 0.3569 0.8195 15.304 H(22) 1.0712 0.4468 0.6260 10.040 H(23) 1.1587 0.4892 0.6941 10.040 H(24) 1.0449 0.4758 0.7130 10.040 H(25) 1.1336 0.4383 0.8669 10.216 H(26) 1.2488 0.4536 0.8520 10.216 H(27) 1.2247 0.3864 0.8832 10.216 H(28) 1.2185 0.3661 0.6507 9.188 H(29) 1.2772 0.3438 0.7516 9.188 H(30) 1.2977 0.4116 0.7204 9.188 S15
H(31) 1.2159 0.2809 0.9592 5.507 H(32) 0.7339 0.1843 0.9424 4.970 H(33) 0.9390 0.0764 0.8574 5.025 H(34) 1.3152 0.1315 1.0217 9.644 H(35) 1.4029 0.1129 0.9707 9.644 H(36) 1.2808 0.0897 0.9329 9.644 H(37) 1.2874 0.2031 0.7691 7.240 H(38) 1.2690 0.1317 0.7832 7.240 H(39) 1.3884 0.1597 0.8140 7.240 H(40) 1.3716 0.2445 1.0039 7.700 H(41) 1.3692 0.2676 0.9047 7.700 H(42) 1.4546 0.2166 0.9542 7.700 H(43) 0.9878 0.4505 1.1317 7.398 H(44) 1.0661 0.4084 1.0928 7.398 H(45) 1.0049 0.3800 1.1605 7.398 H(46) 0.9568 0.4448 0.9388 6.352 H(47) 0.8735 0.4805 0.9805 6.352 H(48) 0.8303 0.4300 0.9035 6.352 H(49) 0.8074 0.3569 1.1062 7.830 H(50) 0.7385 0.3796 1.0080 7.830 H(51) 0.7888 0.4286 1.0858 7.830 H(52) 0.8603 0.0469 1.0251 12.211 H(53) 0.8580-0.0060 0.9526 12.211 H(54) 0.7603 0.0005 0.9969 12.211 H(55) 0.6666 0.0521 0.7642 8.040 H(56) 0.7232-0.0090 0.8124 8.040 H(57) 0.7935 0.0420 0.7802 8.040 H(58) 0.6249 0.1266 0.8872 12.110 H(59) 0.6465 0.0834 0.9745 12.110 H(60) 0.5881 0.0563 0.8764 12.110 *B eq = 8/3π 2 (U 11 (aa*) 2 + U 22 (bb*) 2 + U 33 (cc*) 2 + 2U 12 (aa*bb*)cosγ + 2U 13 (aa*cc*)cosβ + 2U 23 (bb*cc*)cosα S16
Table S7 Crystal data of 2 at 273 K. empirical formula C 46 H 62 N 4 formula weight 671.02 crystal colour, habit deep green, block crystal dimensions, mm 0.20 0.20 0.10 crystal system monoclinic space group P2 1 /n (#14) a, Å 12.783(4) b, Å 21.692(7) c, Å 15.379(4) α, deg 90 β, deg 106.17(2) γ, deg 90 V, Å 3 4096(2) Z 4 D calc, g cm 3 1.088 F(000) 1464.00 µ, cm 1 (Cu Kα) 4.76 diffractometer Rigaku RAXIS-RAPID Imaging Plate radiation (λ, Å) 1.54187 (graphite monochromated) 2θ max, deg 136.5 temperature, K 273 structure solution direct methods (SIR2003) refinement full matrix least-squares using all reflections number of unique reflections 7251 number of observed reflections with I > 2σ(I) 2441 number of variables 453 R1 (calculated on F) 0.104 (I > 2σ(I)) wr2 (calculated on F 2 ) 0.350 (all reflections) S, goodness of fit 0.971 final max/min Δρ, eå 3 0.64/ 0.27 S17
Table S8 Atomic coordinates and equivalent isotopic displacement parameters (Å 2 ) for the crystal structural analysis of 2 at 273 K. atom x y z Beq occ N(9) 0.9647(3) 0.3712(2) 0.7450(3) 6.6(1) N(11) 1.0883(3) 0.2930(2) 0.7282(3) 6.19(9) N(30) 1.0278(4) 0.3201(2) 0.9765(3) 6.6(1) N(32) 0.8483(4) 0.2838(2) 0.9733(4) 7.7(1) C(1) 1.0382(3) 0.1816(1) 0.7282(4) 4.1(2) 0.629(10) C(2) 0.9427(3) 0.1459(2) 0.6702(3) 5.7(1) C(3) 0.8399(4) 0.1632(2) 0.6664(3) 5.01(9) C(4) 0.8186(3) 0.2228(2) 0.6985(3) 4.52(8) C(5) 0.7162(3) 0.2416(2) 0.7006(3) 4.81(9) C(6) 0.6957(4) 0.3011(2) 0.7239(4) 6.0(1) C(7) 0.7783(4) 0.3452(2) 0.7361(4) 6.6(1) C(8) 0.8844(3) 0.3278(2) 0.7367(3) 5.3(1) C(10) 1.0636(3) 0.3524(2) 0.7399(3) 4.96(9) C(12) 1.0086(3) 0.2491(1) 0.7179(3) 4.80(9) C(13) 0.9038(3) 0.2658(2) 0.7187(3) 4.13(8) C(14) 0.9628(4) 0.0856(2) 0.6246(4) 6.1(1) C(15) 0.5848(4) 0.3217(2) 0.7280(4) 5.7(1) C(16) 1.1493(4) 0.4010(2) 0.7451(4) 5.6(1) C(17) 1.0004(5) 0.1026(3) 0.5423(5) 9.2(2) C(18) 1.0507(5) 0.0465(3) 0.6887(5) 9.4(2) C(19) 0.8619(4) 0.0467(2) 0.5942(4) 7.3(1) C(20) 0.4999(5) 0.2738(4) 0.6950(7) 14.2(3) C(21) 0.5450(8) 0.3719(5) 0.6569(7) 15.9(4) C(22) 0.5841(5) 0.3475(7) 0.8117(7) 22.6(7) C(23) 1.1029(6) 0.4571(3) 0.6940(8) 16.0(4) C(24) 1.1920(7) 0.4217(5) 0.8429(6) 16.3(4) C(25) 1.2413(6) 0.3799(3) 0.7133(7) 12.9(3) C(26) 1.0842(3) 0.1625(3) 0.8377(3) 4.2(2) 0.629(10) C(27) 1.1803(3) 0.1971(2) 0.8973(3) 6.1(1) C(28) 1.1586(4) 0.2510(2) 0.9349(4) 5.7(1) C(29) 1.0521(4) 0.2649(2) 0.9402(3) 5.17(9) C(31) 0.9263(4) 0.3292(2) 0.9877(3) 5.5(1) C(33) 0.8720(4) 0.2274(2) 0.9362(3) 5.18(9) C(34) 0.8000(3) 0.1794(2) 0.9254(3) 5.3(1) C(35) 0.8271(4) 0.1233(2) 0.8993(3) 5.21(9) C(36) 0.9220(4) 0.1151(2) 0.8779(3) 5.5(1) C(37) 0.9968(4) 0.1611(2) 0.8864(4) 5.9(1) C(38) 0.9725(4) 0.2185(2) 0.9190(3) 4.46(8) C(39) 1.2971(4) 0.1791(2) 0.9043(4) 5.7(1) S18
C(40) 0.9037(4) 0.3897(2) 1.0273(3) 5.6(1) C(41) 0.7519(4) 0.0680(2) 0.8941(4) 6.1(1) C(42) 1.3211(6) 0.1206(4) 0.9574(6) 11.6(2) C(43) 1.3130(4) 0.1675(3) 0.8111(4) 8.9(2) C(44) 1.3798(5) 0.2292(3) 0.9465(5) 9.4(2) C(45) 1.0011(5) 0.4084(3) 1.1057(5) 9.2(2) C(46) 0.8876(5) 0.4397(2) 0.9553(4) 7.6(1) C(47) 0.8008(5) 0.3880(3) 1.0572(5) 9.5(2) C(48) 0.8088(7) 0.0248(4) 0.9694(6) 14.8(3) C(49) 0.7306(6) 0.0365(3) 0.8033(5) 9.9(2) C(50) 0.6408(6) 0.0866(3) 0.9032(6) 12.9(3) C(101) 1.0181(7) 0.1934(3) 0.6745(8) 5.0(2) 0.371 C(126) 1.1073(4) 0.1488(3) 0.8969(9) 5.5(3) 0.371 H(1) 0.7824 0.1362 0.6427 6.009 H(2) 0.6591 0.2134 0.6859 5.773 H(3) 0.7630 0.3864 0.7439 7.874 H(4) 1.0648 0.1276 0.5608 11.088 H(5) 0.9439 0.1252 0.5002 11.088 H(6) 1.0163 0.0657 0.5138 11.088 H(7) 1.0297 0.0380 0.7427 11.229 H(8) 1.1184 0.0685 0.7040 11.229 H(9) 1.0590 0.0084 0.6595 11.229 H(10) 0.8039 0.0708 0.5565 8.720 H(11) 0.8412 0.0324 0.6462 8.720 H(12) 0.8762 0.0119 0.5605 8.720 H(13) 0.5125 0.2400 0.7370 17.029 H(14) 0.5030 0.2591 0.6368 17.029 H(15) 0.4293 0.2912 0.6897 17.029 H(16) 0.5401 0.3555 0.5979 19.122 H(17) 0.5953 0.4058 0.6692 19.122 H(18) 0.4745 0.3860 0.6589 19.122 H(19) 0.6220 0.3862 0.8197 27.067 H(20) 0.6197 0.3200 0.8597 27.067 H(21) 0.5103 0.3540 0.8130 27.067 H(22) 1.0721 0.4467 0.6314 19.156 H(23) 1.1593 0.4872 0.6994 19.156 H(24) 1.0471 0.4736 0.7181 19.156 H(25) 1.1330 0.4379 0.8633 19.590 H(26) 1.2461 0.4531 0.8473 19.590 H(27) 1.2239 0.3872 0.8799 19.590 H(28) 1.2154 0.3675 0.6511 15.476 H(29) 1.2759 0.3455 0.7493 15.476 H(30) 1.2929 0.4129 0.7188 15.476 S19
H(31) 1.2147 0.2790 0.9575 6.872 H(32) 0.7325 0.1853 0.9359 6.354 H(33) 0.9365 0.0768 0.8566 6.551 H(34) 1.3104 0.1268 1.0161 13.963 H(35) 1.3952 0.1086 0.9640 13.963 H(36) 1.2730 0.0887 0.9262 13.963 H(37) 1.2882 0.2028 0.7732 10.650 H(38) 1.2718 0.1319 0.7845 10.650 H(39) 1.3888 0.1606 0.8169 10.650 H(40) 1.3702 0.2412 1.0039 11.266 H(41) 1.3688 0.2643 0.9070 11.266 H(42) 1.4522 0.2136 0.9552 11.266 H(43) 0.9895 0.4491 1.1257 11.037 H(44) 1.0659 0.4080 1.0858 11.037 H(45) 1.0090 0.3798 1.1547 11.037 H(46) 0.9530 0.4440 0.9368 9.176 H(47) 0.8713 0.4781 0.9798 9.176 H(48) 0.8284 0.4285 0.9040 9.176 H(49) 0.8071 0.3567 1.1025 11.393 H(50) 0.7399 0.3790 1.0062 11.393 H(51) 0.7901 0.4274 1.0821 11.393 H(52) 0.8545 0.0481 1.0185 17.727 H(53) 0.8526-0.0039 0.9472 17.727 H(54) 0.7555 0.0026 0.9903 17.727 H(55) 0.6656 0.0532 0.7626 11.899 H(56) 0.7214-0.0069 0.8105 11.899 H(57) 0.7911 0.0433 0.7790 11.899 H(58) 0.6238 0.1276 0.8803 15.472 H(59) 0.6418 0.0853 0.9658 15.472 H(60) 0.5866 0.0585 0.8693 15.472 *B eq = 8/3π 2 (U 11 (aa*) 2 + U 22 (bb*) 2 + U 33 (cc*) 2 + 2U 12 (aa*bb*)cosγ + 2U 13 (aa*cc*)cosβ + 2U 23 (bb*cc*)cosα S20
Table S9 Crystal data of 2 at 333 K. empirical formula C 46 H 62 N 4 formula weight 671.02 crystal colour, habit dark green, block crystal dimensions, mm 0.20 0.20 0.10 crystal system monoclinic space group P2 1 /n (#14) a, Å 12.809(1) b, Å 21.813(2) c, Å 15.499(1) α, deg 90 β, deg 106.006(5) γ, deg 90 V, Å 3 4162.9(6) Z 4 D calc, g cm 3 1.071 F(000) 1464.00 µ, cm 1 (Cu Kα) 4.68 diffractometer Rigaku RAXIS-RAPID Imaging Plate radiation (λ, Å) 1.54187 (graphite monochromated) 2θ max, deg 136.5 temperature, K 333 structure solution direct methods (SIR2003) refinement full matrix least-squares using all reflections number of unique reflections 7538 number of observed reflections with I > 2σ(I) 3499 number of variables 453 R1 (calculated on F) 0.120 (I > 2σ(I)) wr2 (calculated on F 2 ) 0.397 (all reflections) S, goodness of fit 1.222 final max/min Δρ, eå 3 0.0/0.0 S21
Table S10 Atomic coordinates and equivalent isotopic displacement parameters (Å 2 ) for the crystal structural analysis of 2 at 333 K. atom x y z Beq occ N(9) 0.9669(3) 0.3703(2) 0.7488(3) 7.8(1) N(11) 1.0883(3) 0.2935(2) 0.7277(3) 7.43(9) N(30) 1.0301(4) 0.3186(2) 0.9775(3) 7.9(1) N(32) 0.8504(4) 0.2837(2) 0.9731(4) 9.4(1) C(1) 1.0386(4) 0.1818(1) 0.7300(4) 4.9(2) 0.548(11) C(2) 0.9446(3) 0.1467(2) 0.6700(3) 7.0(1) C(3) 0.8426(4) 0.1633(2) 0.6678(3) 6.7(1) C(4) 0.8208(3) 0.2223(2) 0.6995(3) 5.80(8) C(5) 0.7173(3) 0.2417(2) 0.7022(3) 6.13(9) C(6) 0.6980(4) 0.3003(2) 0.7258(4) 7.4(1) C(7) 0.7801(4) 0.3446(2) 0.7377(4) 8.0(1) C(8) 0.8855(3) 0.3267(2) 0.7387(3) 6.4(1) C(10) 1.0641(3) 0.3519(2) 0.7417(3) 5.96(9) C(12) 1.0094(3) 0.2488(1) 0.7166(3) 6.13(9) C(13) 0.9057(3) 0.2655(2) 0.7204(3) 5.06(7) C(14) 0.9638(4) 0.0869(2) 0.6243(4) 7.5(1) C(15) 0.5861(4) 0.3208(2) 0.7285(4) 7.0(1) C(16) 1.1500(4) 0.4010(2) 0.7480(4) 6.9(1) C(17) 1.0016(7) 0.1037(3) 0.5438(6) 12.6(2) C(18) 1.0494(6) 0.0475(3) 0.6881(6) 13.1(3) C(19) 0.8631(5) 0.0485(3) 0.5944(5) 10.1(2) C(20) 0.5021(5) 0.2760(5) 0.6887(8) 18.1(5) C(21) 0.554(1) 0.3743(6) 0.667(1) 26.3(9) C(22) 0.5825(6) 0.3416(8) 0.8122(7) 27.8(9) C(23) 1.1027(7) 0.4555(4) 0.695(1) 20.2(6) C(24) 1.188(1) 0.4219(6) 0.8420(7) 22.5(6) C(25) 1.2427(7) 0.3800(3) 0.7196(9) 17.4(4) C(26) 1.0848(3) 0.1631(3) 0.8386(3) 5.1(2) 0.548(11) C(27) 1.1810(3) 0.1953(2) 0.9005(4) 7.7(1) C(28) 1.1607(4) 0.2495(2) 0.9365(4) 7.2(1) C(29) 1.0531(4) 0.2640(2) 0.9412(3) 6.30(9) C(31) 0.9282(4) 0.3281(2) 0.9862(3) 6.9(1) C(33) 0.8727(4) 0.2272(2) 0.9346(3) 6.36(9) C(34) 0.7992(3) 0.1801(2) 0.9230(3) 6.6(1) C(35) 0.8253(4) 0.1239(2) 0.8970(3) 6.41(9) C(36) 0.9220(4) 0.1151(2) 0.8769(3) 7.0(1) C(37) 0.9984(3) 0.1610(2) 0.8879(3) 7.1(1) C(38) 0.9738(3) 0.2181(2) 0.9190(3) 5.49(8) C(39) 1.2985(4) 0.1767(2) 0.9075(3) 7.1(1) S22
C(40) 0.9057(4) 0.3885(2) 1.0277(4) 7.1(1) C(41) 0.7499(4) 0.0694(2) 0.8914(4) 7.7(1) C(42) 1.3202(7) 0.1181(4) 0.9556(7) 15.9(3) C(43) 1.3144(5) 0.1678(4) 0.8145(5) 11.9(2) C(44) 1.3809(5) 0.2262(4) 0.9504(6) 12.3(2) C(45) 1.0022(6) 0.4088(3) 1.0989(6) 13.3(3) C(46) 0.8816(6) 0.4371(3) 0.9554(5) 11.1(2) C(47) 0.8039(7) 0.3849(4) 1.0598(6) 13.6(3) C(48) 0.8046(9) 0.0267(5) 0.9646(8) 20.5(5) C(49) 0.7303(6) 0.0369(3) 0.8031(6) 13.4(3) C(50) 0.6421(7) 0.0881(4) 0.9038(8) 17.2(4) C(101) 1.0205(6) 0.1936(2) 0.6738(6) 5.8(2) 0.452 C(126) 1.1082(3) 0.1472(2) 0.8990(7) 6.7(2) 0.452 H(1) 0.7857 0.1361 0.6453 7.990 H(2) 0.6600 0.2139 0.6875 7.360 H(3) 0.7647 0.3856 0.7448 9.544 H(4) 1.0657 0.1286 0.5624 15.070 H(5) 0.9455 0.1262 0.5020 15.070 H(6) 1.0177 0.0671 0.5157 15.070 H(7) 1.0274 0.0394 0.7414 15.746 H(8) 1.1176 0.0687 0.7038 15.746 H(9) 1.0569 0.0094 0.6593 15.746 H(10) 0.8055 0.0725 0.5569 12.083 H(11) 0.8422 0.0345 0.6460 12.083 H(12) 0.8772 0.0138 0.5612 12.083 H(13) 0.5099 0.2409 0.7273 21.703 H(14) 0.5093 0.2636 0.6312 21.703 H(15) 0.4319 0.2940 0.6815 21.703 H(16) 0.5475 0.3615 0.6064 31.588 H(17) 0.6090 0.4056 0.6838 31.588 H(18) 0.4861 0.3903 0.6713 31.588 H(19) 0.6188 0.3805 0.8244 33.407 H(20) 0.6179 0.3125 0.8573 33.407 H(21) 0.5081 0.3463 0.8128 33.407 H(22) 1.0728 0.4441 0.6337 24.241 H(23) 1.1583 0.4858 0.6998 24.241 H(24) 1.0463 0.4719 0.7185 24.241 H(25) 1.1274 0.4376 0.8605 26.958 H(26) 1.2412 0.4536 0.8469 26.958 H(27) 1.2195 0.3880 0.8798 26.958 H(28) 1.2192 0.3674 0.6579 20.909 H(29) 1.2761 0.3460 0.7562 20.909 H(30) 1.2944 0.4128 0.7260 20.909 S23
H(31) 1.2170 0.2772 0.9583 8.585 H(32) 0.7317 0.1865 0.9328 7.904 H(33) 0.9364 0.0771 0.8552 8.383 H(34) 1.3102 0.1228 1.0144 19.061 H(35) 1.3935 0.1056 0.9608 19.061 H(36) 1.2709 0.0875 0.9230 19.061 H(37) 1.2893 0.2036 0.7787 14.270 H(38) 1.2739 0.1327 0.7865 14.270 H(39) 1.3901 0.1616 0.8198 14.270 H(40) 1.3708 0.2377 1.0073 14.800 H(41) 1.3706 0.2614 0.9118 14.800 H(42) 1.4531 0.2105 0.9591 14.800 H(43) 0.9898 0.4493 1.1182 16.015 H(44) 1.0644 0.4093 1.0757 16.015 H(45) 1.0149 0.3811 1.1488 16.015 H(46) 0.9445 0.4434 0.9343 13.368 H(47) 0.8629 0.4748 0.9795 13.368 H(48) 0.8219 0.4240 0.9064 13.368 H(49) 0.8127 0.3534 1.1046 16.314 H(50) 0.7426 0.3753 1.0100 16.314 H(51) 0.7922 0.4235 1.0852 16.314 H(52) 0.8502 0.0496 1.0136 24.632 H(53) 0.8482-0.0019 0.9425 24.632 H(54) 0.7509 0.0047 0.9850 24.632 H(55) 0.6659 0.0529 0.7618 16.072 H(56) 0.7212-0.0062 0.8117 16.072 H(57) 0.7913 0.0431 0.7794 16.072 H(58) 0.6247 0.1288 0.8810 20.693 H(59) 0.6458 0.0871 0.9665 20.693 H(60) 0.5870 0.0602 0.8717 20.693 *B eq = 8/3π 2 (U 11 (aa*) 2 + U 22 (bb*) 2 + U 33 (cc*) 2 + 2U 12 (aa*bb*)cosγ + 2U 13 (aa*cc*)cosβ + 2U 23 (bb*cc*)cosα S24
Table S11 Intermolecular distances in units of Å between the diazaphenalenyl skeletons without disordered carbon atoms. a 93 K 153 K 213 K 273 K 333 K N9 N30 b 3.590(6) 3.605(6) 3.613(6) 3.599(7) 3.593(6) N11 C28 b 3.160(6) 3.164(6) 3.162(6) 3.187(7) 3.257(7) N32 C7 b 3.795(6) 3.812(6) 3.810(6) 3.750(7) 3.752(7) C3 C36 b 3.262(6) 3.261(6) 3.275(6) 3.297(7) 3.291(7) C5 C34 b 3.618(6) 3.622(6) 3.621(6) 3.586(7) 3.554(6) C13 C38 b 3.116(5) 3.116(5) 3.124(5) 3.132(6) 3.134(5) a Uncertainties of the distances between the disordered carbon atoms remain due to the restriction based on the suppositions in the legend of Figure S3. b The numbering of atoms is given in the following picture. S25
Figure S4 Two types of the disordered dimer structures for 2 at 153 K in the crystal (right), and their occupancies at five different temperatures determined by X-ray structure analyses. The orange and the green crosses denote the occupancies of the σ-dimer and π-dimer with error bars (2.5 standard uncertainty), respectively. Each dimer structure is not influenced by temperature variation. The crystal structure analyses suggest that an occupancy of the π-dimer increases on raising the temperature. We have noted that small changes in the occupancies of σ- and π-dimers from 93 K to 213 K occur and the experimental occupancy around 0.2 of the π-dimer at 93 K is seemingly too large on the assumption that the ratio of the π-dimer to all the dimers obeys Boltzmann distribution. These observations were due to the restrictions based on the suppositions in the legend of Figure S3. S26
Figure S5 a, Temperature-dependent electronic absorption spectra of 2 in the crystal using KBr pellet: 100, 150, 200, 250, and 300 K (from bottom to top). b, Polarized absorption spectra of 2 with polarized light parallel to the c axis (solid line) and perpendicular to the c axis (dashed line) on the crystal plane (010) at 300 K. S27
Figure S6 Pictures of the crystal of 2 at 300 K under polarized light: The directions of the polarized light are (a) parallel and (b) perpendicular to the c axis. S28
Figure S7 Optimized σ-dimer and π-dimer structures of 2 and the difference of the total energy between two dimers. The dimer structures were optimized at B3LYP/6-31G* level with Gaussian 03 by using the crystal structures of the σ- and π-dimers as the initial structures S2. The calculated ΔE σ-π value (3.0 kcal mol 1 ) is surprisingly good agreement with the experimental one (2.6 kcal mol 1 ). S29
Relative ESR intensity 1 0.8 0.6 0.4 0.2 336 337 338 339 340 341 Magnetic Field/mT 0 180 200 220 240 260 280 Temperature/K 300 320 Figure S8 Temperature dependence of the ESR intensity of 2 in hexane (1 10 3 M). Open squares denote the experimental values normalized at 320 K. Solid line shows the calculated values with the following thermodynamic parameters: ΔH = 12.2(9) kcal mol 1 and ΔS = 31(3) eu. Inset shows an observed spectrum at 320 K. S30
Figure S9 Temperature-dependent electronic spectra of 2 in hexane (1 10 4 M). In the spectra, a broad absorption band around 550 nm decreased with lowering the temperature, and finally disappeared at 200 K, which indicates that the radical 2 forms the σ-dimer structure at low temperature S3,4. S31
Figure S10 Pictures of the calculated highest occupied molecular orbital (HOMO) and the calculated lowest unoccupied molecular orbital (LUMO) of 1 and 2. The dimer structures were optimized by using Gaussian 03 at the B3LYP/6-31G* level of theory S2. The vanishing E value derived from the fine-structure triplet-state ESR spectrum is also in good agreement with the predicted symmetrical electronic structures of the HOMO and the LUMO for the π-dimer of 2. S32
Figure S11 a. Temperature dependence of χ para T (product of magnetic susceptibility and temperature) of 2 in the solid state S5. Open squares denote the experimental values. Solid line shows the estimated paramagnetic contributions from S =1/2 monoradical impurities (0.1%). The result shows that the molecular assemblages of 2 in the crystal are in the spin-singlet state. On raising the temperature to 350 K, a small but a significant increase in χ para T was observed, suggesting the existence of a thermally accessible triplet state. b. Temperature dependence of triplet signal intensity. Open squares denote the experimental values. Solid line shows the calculated values by the modified singlet-triplet model with ΔE S T = 4.19(2) 10 3 K. Inset shows the observed triplet-state ESR spectrum of the powdered crystalline sample of 2 at 350 K. The intensity of the triplet signal is proportional to the number of the triplet π-dimer. S33
Figure S12 Temperature dependence of triplet signal intensity of 1. Open circles denote the experimental values. Solid line shows the calculated values by the singlet triplet model with ΔE S T = 3.34(3) 10 3 K. Inset shows the observed triplet ESR spectrum of the powdered crystalline sample of 1 at 300 K (g = 2.003, D /hc = 0.0167 cm 1, and E /hc < 10 3 cm 1 ). S34
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