Hierarchical Emergence and Dynamic Control of Chirality in a Photoresponsive Dinuclear Complex

Transcription

1 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 , Japan. Department of Applied Chemistry, Tokyo University of Science, Kagurazaka, Shinjuku, Tokyo , Japan NAIST-CEMES International Collaborative Laboratory, CEMES-CNRS, 29 rue Jeanne Marvig, BP94347, Toulouse, France Table of contents 1. Experimental details 1-1. General 1-2. Syntheis H and 13 C NMR spectra of 1-o 2. Conformational behavior and photoreaction of ligand 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

2 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 C 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

3 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, 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), (m, 6H), 7.42 (d, 4H, J = 6.8 Hz), (m, 14H), (m, 6H), 5.25 (m, 2H), (m, 4H), 1.96 (s, 6H) 13 C NMR (150MHz, 1,1,2,2- tetrachloroethane-d2 at 60 ºC): (ppm) , , , , ,, , , , , , , , , , , , , , , , , , , , , , 56.61, 38.46, 12.0; HRMS-MALDI- TOF(m/z): [M+H] + calc. for C88H65N14O4S4 +, ; found (for D-1-o), (for L-1-o) S3

4 H and 13 C NMR spectra of 1-o abundance X : parts per Million : Proton abundance X : parts per Million : Carbon 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

5 abundance X : parts per Million : Proton abundance X : parts per Million : Carbon 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

6 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

7 2. Conformational behavior and photoreaction of ligand 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 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

8 (thousandths) 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) (broad signal, 2H), (m, 4H), (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), (m, 32H), 5.49 (s, 1H), 5.10 (s, 1H), (m, 4H), (two singlets, 6H); 13 C-NMR (150 MHz, CHCl 3 at room temerature): (ppm) , ,155.23, , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , 70.01, 55.94, 39.92, 39.81, 26.93, S8

9 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 Crystal Color, Habit colorless, prism Crystal Dimensions (mm) Crystal System triclinic Lattice Type Primitive Lattice Parameters a (Å) (18) b (Å) (19) c (Å) (4) (deg) (5) (deg) (6) (deg) (6) V (Å 3 ) (8) Space Group P-1(#2) Z Value 2 D calc (g/cm 3 ) F (MoK ) (cm -1 ) Temeperature (K) 123 R 1 [I > 2.00 (I)] a) wr 2 (All reflections) b) 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

10 Figure S8. Possible coordination structures of Eu(terpy)(tta)3. S10

11 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

12 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

13 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

14 Figure S14. a) Comparison of 19 F-NMR spectra in CDCl3 (400 MHz, hexafluorobenzene as a standard: 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

15 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

16 References S1. Sumi, T.; Takagi, Y.; Yagi, A.; Morimoto, M.; Irie, M. Photoirradiation Wavelength Dependence of Cycloreversion Quantum Yields of Diarylethenes. Chem. Commun. 2014, 50, S2. Tsumatori, H.; Nakashima, T.; Kawai, T. Observation of Chiral Aggregate Growth of Perylene Derivative in Opaque Solution by Circularly Polarized Luminescence. Org. Lett. 2010, 12, S3. Hashimoto, Y.; Nakashima, T.; Shimizu, D.; Kawai, T. Photoswitching of an Intramolecular Chiral Stack in a Helical Tetrathiazole. Chem. Commun. 2016, 52, S4. Nakagawa, T.; Hasegawa, T.; Kawai, T. Photoresponsive Europium(III) Complex Based on Photochromic Reaction. J. Phys. Chem. A 2008, 112, S16