Supporting Information for Hierarchical Emergence and Dynamic Control of Chirality in a Photoresponsive Dinuclear Complex Yuichiro Hashimoto, Takuya Nakashima,*, Miku Yamada, Junpei Yuasa, Gwénaël Rapenne,, and Tsuyoshi Kawai*,, Graduate School of Materials Science, Nara Institute of Science and Technology, Ikoma, Nara 630-0192, Japan. Department of Applied Chemistry, Tokyo University of Science, Kagurazaka, Shinjuku, Tokyo 162-8061, Japan NAIST-CEMES International Collaborative Laboratory, CEMES-CNRS, 29 rue Jeanne Marvig, BP94347, 31055 Toulouse, France Table of contents 1. Experimental details 1-1. General 1-2. Syntheis 1-2-1. 1 H and 13 C NMR spectra of 1-o 2. Conformational behavior and photoreaction of ligand 1. 2-1. VT- 1 H NMR analysis 2-2. CD and UV-vis spectral change of 1 upon photochromic reaction 2-3. NMR spectral study of photochromism of 1 3. X-ray crystal structure of a reference complex 4. Preparation and characterization of Ln(III) complexes (D- and L-X(Ln)-o) 5. CPL property of complexes with various -diketonate ligands S1
1. Experimental details 1-1 General All chemicals were purchased from commercial sources and used without further purification. Compounds were purified with a preparative HPLC with JAIGEL 1HR and 2HR (Japan Analytical Industry Co. Ltd) using LC-9110NEXT. Their chemical structures were confirmed by high-resolution mass spectroscopy (JEOL AccuTOF, JMS-T100LC (Electrospray ionization, ESI), Bruker Autoflex 2 (MALDI-TOF)), and 1 H NMR and 13 C NMR measurements (JEOL AL-300, JNM-ECX400 and ECA- 600). Absorption spectra in solution were studied with a JASCO V-670 spectrophotometer. The quantum yields of cyclization and cycloreversion for 1 were measured by a photoreaction quantum yield measure-ments system (Shimadzu QYM-01). [S1] Photoirradiation was carried out by using a 300 W xenon lamp system (Asahi spec-tra MAX-303). Irradiation wavelength of the light was selected by passing through band-pass filters. Fluorescence spectra were studied with a spectrofluorometer (HITACHI F-7000). CD spectra were recorded by a JASCO J-725 spectropolarimeter. CPL spectra were measured using a home-made CPL spectroscopy system. [S2] Absolute emission quantum yields were determined using a Hamamatsu C9920-02. Emission lifetime was studied by using a FluoroCube 3000U (Horiba). X-ray crystallographic analysis was carried out with Rigaku R-AXIS RAPID/s Imaging Plate diffractometer with Mo K iradiation. The crystal structure was solved by direct method (SHELXL-97) and refined by the full-matrix least-squares on F 2. All non-hydrogen atoms were refined an iso-tropically and all hydrogen atoms were placed using AFIX instructions. The molecular illustration was performed by Materials Studio 7.0 (Accelrys Software Inc.). S2
1-2. Syntheis 2,2':6',2''-Terpyridine-4'-carboxylic acid (72 mg, 0.26 mmol), benzotriazol-1-yloxytri(pyrrolidino)phosphonium hexafluorophosphate (PyBOP) (137.4 mg, 0.264 mmol) and Tetrathia-NH 2 (Dform) [S3] (88 mg, 0.09 mmol) in CHCl 3 (5 ml) were added in a two-necked flask (20-mL) with septum under Ar atomosphere. Diisopropylethanol amine (DIEA) (60 l, 0.28 mmol) was added to the reaction mixture and stirred for 1 day. MeOH was added to the reaction mixture and white solid was precipitated. This white powder was filtered and dried over the vacuum oven. The crude product was purified with GPC to yield 1-o (100 mg, 72% for D-1-o; 102 mg, 72 % for L-1-o). 1 H NMR (400 MHz, 1,1,2,2-tetrachloroethane-d2 at 60 C): (ppm) 9.12 (s, 2H), 8.68 (s, 4H), 8.63 (d, 4H, J = 4.0 Hz ), 8.50 (d, 4H, 7.6 Hz), 8.10 (m, 4H), 7.80 (t, 4H, J = 7.6 Hz), 7.81 (m, 4H), 7.53-7.51 (m, 6H), 7.42 (d, 4H, J = 6.8 Hz), 7.36-7.30 (m, 14H), 7.30-7.196 (m, 6H), 5.25 (m, 2H), 3.46-3.39 (m, 4H), 1.96 (s, 6H) 13 C NMR (150MHz, 1,1,2,2- tetrachloroethane-d2 at 60 ºC): (ppm) 169.67, 167.93, 163.56, 156.57, 155.18,, 149.35, 147.83, 142.92, 142.21, 138.80, 136.94, 136.40, 133.74, 132.10, 131.22, 130.45, 129.54, 129.18, 129.05, 127.34, 126.92, 126.34, 124.33, 121.29, 120.02, 118.40, 56.61, 38.46, 12.0; HRMS-MALDI- TOF(m/z): [M+H] + calc. for C88H65N14O4S4 +, 1509.41960 ; found 1509.41906 (for D-1-o), 1509.41953 (for L-1-o) S3
1-2-1. 1 H and 13 C NMR spectra of 1-o abundance 0 1.0 2.0 3.0 4.0 5.0 9.0 8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 0 X : parts per Million : Proton 0 0.1 0.2 0.3 abundance 180.0 170.0 160.0 150.0 140.0 130.0 120.0 110.0 100.0 90.0 80.0 70.0 60.0 50.0 40.0 30.0 20.0 10.0 0 169.676 167.923 163.557 156.558 155.170 X : parts per Million : Carbon13 149.339 147.826 142.206 136.930 136.403 133.741 132.095 131.223 130.448 129.538 129.184 129.050 127.346 126.915 126.350 124.320 121.294 120.011 118.393 74.349 74.273 74.091 73.909 56.607 38.473 11.998 Figure S1. 1 H (top, 400 MHz at room temperature, in CDCl3) and 13 C NMR (bottom, 150 MHz at 333K, in 1,1,2,2-tetrachloroethane-d2) of D-1-o. S4
abundance 0 1.0 2.0 3.0 4.0 10.0 9.0 8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 0 X : parts per Million : Proton abundance -0.03-0.02-0.01 0 0.01 0.02 0.03 0.04 0.05 0.06 0.07 0.08 0.09 0.1 0.11 0.12 0.13 0.14 0.15 180.0 170.0 160.0 150.0 140.0 130.0 120.0 110.0 100.0 90.0 80.0 70.0 60.0 50.0 40.0 30.0 20.0 10.0 0 169.666 167.933 163.557 156.568 155.179 X : parts per Million : Carbon13 149.348 147.826 142.206 136.939 136.403 133.741 132.104 131.223 130.448 129.538 129.184 129.050 127.336 126.915 126.340 124.329 121.294 120.021 118.403 74.349 74.273 74.091 73.909 56.607 38.463 11.998 Figure S2. 1 H (top, 400 MHz at room temperature, in CDCl3) and 13 C NMR (bottom, 150 MHz at 333K, in 1,1,2,2-tetrachloroethane-d2) of L-1-o. S5
Figure S3. 1 H NMR spectra above 1.8 ppm in 1,1,2,2-tetrachloroethane-d2 with peak assignment of D- 1-o (measured at 323 K). S6
2. Conformational behavior and photoreaction of ligand 1. 2-1. VT- 1 H NMR analysis Figure S4. VT- 1 H NMR spectra of D-1-o in the low magnetic field (aromatic region) in 1,1,2,2- tetrachloroethane-d2 with part of the chemical structure. 2-2. NMR spectral study of photochromism of 1 Figure S5. 1 H-NMR spectra of D-1-o (Top) and D-1-c (Bottom) in CDCl3 at room temparature. D-1-c was purified using a chiral column (DAICEL). Hc and Hm signals were splitted due to a change in the symmetry of the molecule from o-form to c-form. The methyl peaks at reactive carbon were shifted to low magnetic field, indicating the cancellation of CH- interaction as a consequence of the large conformational change induced. Two methyl signal are also splitted in D-1-c which was attributed to the configurational change of D-1-o. S7
(thousandths) -10.0 0 10.0 20.0 30.0 40.0 50.0 60.0 70.0 80.0 90.0 180.0 170.0 160.0 150.0 140.0 130.0 120.0 110.0 100.0 90.0 80.0 70.0 60.0 50.0 40.0 30.0 20.0 10.0 0-10.0 X : parts per Million : Carbon13 Figure S6. 1 H and 13 C NMR spectra of D-1-c in CDCl3 at room temperature. 1 H-NMR (400 MHz, CHCl 3 at room temerature): (ppm) 9.34-9.55 (broad signal, 2H), 8.66-8.63 (m, 4H), 8.50-8.47 (m, 4H), 7.98 (d, 2H, J = 7.0 Hz), 7.90 (d, 2H, J = 7.0 Hz), 7.74 (m, 2H), 7.74 (m, 2H), 7.63 (m, 2H), 7.48-7.17 (m, 32H), 5.49 (s, 1H), 5.10 (s, 1H), 3.31-3.29 (m, 4H), 2.36-2.33 (two singlets, 6H); 13 C-NMR (150 MHz, CHCl 3 at room temerature): (ppm) 170.82, 156.33,155.23, 155.12, 149.33, 149.25, 148.64, 142.53, 140.54, 138.56, 136.48, 136.65, 133.12, 132.81, 132.05, 131.73, 129.82, 128.83, 128.72, 128.61, 128.43 128.32, 128.25, 127.27, 127.16, 126.93, 126.82, 124.11, 124.04, 121.12, 121.05, 120.46, 118. 45, 118.32, 70.01, 55.94, 39.92, 39.81, 26.93, 12.84. S8
3. Structure of the reference complex Figure S7. ORTEP drawings of Eu(terpy)(tta)3, showing 50% probability displacement ellipsoids. Table S1. The crystal data of Eu(terpy)(tta)3. Eu(terpy)(tta) 3 Empirical Formula C 39 H 23 EuF 9 N 3 O 6 S 3 Formula Weight 1048.75 Crystal Color, Habit colorless, prism Crystal Dimensions (mm) 0.090 0.060 0.050 Crystal System triclinic Lattice Type Primitive Lattice Parameters a (Å) 14.03872(18) b (Å) 10.41729(19) c (Å) 19.6959(4) (deg) 76.455(5) (deg) 80.489(6) (deg) 88.925(6) V (Å 3 ) 1974.46(8) Space Group P-1(#2) Z Value 2 D calc (g/cm 3 ) 1.764 F000 1036.00 (MoK ) (cm -1 ) 18.375 Temeperature (K) 123 R 1 [I > 2.00 (I)] a) 0.0189 wr 2 (All reflections) b) 0.0493 a) R 1 = F o - F c / F o b) wr 2 = [ ( w (Fo 2 - Fc 2 ) 2 )/ w(fo 2 ) 2 ] 1/2 S9
Figure S8. Possible coordination structures of Eu(terpy)(tta)3. S10
4. Preparation and characterization of Ln(III) complexes (D- and L-X(Ln)-o) X(Eu) D/L-1-o D/L-X(Ln) Eu III complexes with -diketonate ligands were prepared as described in the literature. [S4] In a typical synthesis, chiral ligands (D-, L-1-o) (7 mg, 4.6 mol) and and tri( -diketonate) Eu III complexes (9.2 mol) were dissolved in a mixture of CHCl3 and MeOH (3:1 ratio) and vigorously stirred in a flask at 60 C for 6 hours. Evaporation of the solvents gave a colorless solid compound which was dried at 40 C under vacuum. No further purification was needed. Nd III complexes were also prepared following a similar procedure to compare CD properties (f-f transition) Figure S9 Positive ion ESI-mass spectra of [D-1(Eu)-o] 2+ (top) and [L-1(Eu)-o] 2+ (bottom). Calculated isotopic distribution for [D-1(Eu)-o] 2+ (gray bar chart) is shown. S11
Figure S10. Comparison of 1 H-NMR (300 MHz) spectra in CDCl3. The alphabet corresponds to the position of hydrogen in the molecular or complex structure. The arrow indicates the signal shift after formation of complex. Figure S11. Comparison of 1 H-NMR (300 MHz) spectra in CDCl3. The alphabet corresponds to the position of hydrogen in the molecular or complex structure. The arrow indicates the signal shift after formation of complex. The methyl-signal and j-signal gave the same integral values corresponding to 6-protons. S12
Figure S12. Emission decay profile change of D-1(Eu)-o upon photoreaction in CDCl3 (before the photoirradiation: black line; at PSS: green line). Figure S13. Temperature dependent CD spectra of L-1(Nd)-o (0.8 mm in CHCl3). 323 K; black line, 298 K; black dots line, 273 K; purple line S13
Figure S14. a) Comparison of 19 F-NMR spectra in CDCl3 (400 MHz, hexafluorobenzene as a standard: -162.9 ppm). b) The peak separation of D-1(Eu)-o using Lorentzian fitting function. The peak ratio of blue and green area is found to be 1:2. S14
Figure S15. Structure molel of D-1(Eu)-o caclulated by MM usign UFF. Green and orange circles indicate the CF3 groups in tta ligands. 5. CPL property of complexes with various -diketonate ligands Figure S16. Circularly polarized luminescence(cpl) spectra in CDCl3. The spectra for D-form and for L-form are shown with blue and red lines, respectively. a) D-, L-1(Eu)-o: c = 0.5 mm, b) D-, L-2(Eu)- o: c = 0.5 mm, c) D-, L-3(Eu)-o: c =0.1 mm, d) D-, L-6(Eu)-o: c = 0.1 mm. S15
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