Controllable monobromination of perylene ring system: synthesis of bay-functionalized perylene dyes

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1 Supporting Information Controllable monobromination of perylene ring system: synthesis of bay-functionalized perylene dyes Masaki Takahashi,* a Kyohei Asaba, a Trinh Thi Lua, a Toshiyasu Inuzuka, b Naohiro Uemura, c Masami Sakamoto, c Tetsuya Sengoku, a and Hidemi Yoda* a a Department of Applied Chemistry, Faculty of Engineering, Shizuoka University, Johoku, Naka-ku, Hamamatsu , Japan b Division of Instrumental Analysis, Life Science Research Center, Gifu University, 1-1 Yanagido, Gifu , Japan c Department of Applied Chemistry and Biotechnology, Graduate School of Engineering, Chiba University, 1-33 Yayoi-cho, Inage-ku, Chiba , Japan E mail: takahashi.masaki@shizuoka.ac.jp, yoda.hidemi@shizuoka.ac.jp The following data are included in this material: X-ray crystallographic structure for 4c (Figure S1) Absorption and fluorescence emission spectra of 5a and 5b (Figure S2) Absorption spectra of 6, 7, and 8 (Figure S3) Normalized fluorescence emission spectra of 6, 7, and 8 (Figure S4) Wavelengths of fluorescence maxima and quantum yields for 6-8 (Table S1) Structural assignment of regioisomeric products 1b (Scheme S1, Figure S5) References Copies of 1 H and 13 C NMR spectra S2 S2 S3 S3 S4 S4 S5 S6 S7 S37 S1

2 Figure S1. Four perspective views of X ray structure of 4c as RTEP drawings with 50% thermal probability ellipsoids, exhibiting disordered stacking of the perylene diimide systems that are randomly oriented with an almost equal distribution of two different isomeric forms, along with the presence of two chloroform molecules contained in the unit cells. Normalized A and Int / a.u λ/ nm Figure S2. Normalized absorption (solid lines) and fluorescence emission (dotted lines, λ ex 420 nm) spectra of 5a (top) and 5b (bottom) in MeCN at c 10 µm and 1.0 µm, respectively. S2

3 Figure S3. Absorption spectra of (a) 6, (b) 7, and (c) 8 in toluene (orange lines), chloroform (red lines), DCM (green lines), THF (cyan lines), and MeCN (blue lines) at c 10 µm. Normalized Int / a.u. Normalized Int / a.u. Normalized Int / a.u. Figure S4. Normalized fluorescence emission spectra of (a) 6 (λ ex 400 nm), (b) 7 (λ ex 400 nm), and (c) 8 (λ ex 420 nm) in toluene (orange lines), chloroform (red lines), DCM (green lines), THF (cyan lines), and MeCN (blue lines) at c 1.0 µm. S3

4 Table S1. Wavelengths of fluorescence emission maxima (λ F ) and quantum yields of fluorescence (ϕ F ) for 6-8 in various solvents dyads solvent λ F (nm) a ϕ F b toluene chloroform DCM THF MeCN 454, toluene 452, chloroform 459, DCM 456, THF 454, MeCN 454, toluene 507, chloroform 506, DCM THF 443, 470, MeCN 460, a Fluorescence emission spectra were measured upon excitation at λ ex 400 nm for 6 and 7 and 420 nm for 8 at c 1.0 µm. b Fluorescence quantum yields (ϕ F ) were determined by relative method employing a dilute solution of fluorescein in 0.1 M NaH aq (ϕ F = 0.925) as a standard. As for the reference, see ref 1. Structural assignment of regioisomeric products 1b The structural assignment for the major and minor components of 1b was made as follows (Scheme S1). The regioisomeric mixture of 1b (71.3 mg, mmol) was subjected to acid-mediated condensation [2] with p-toluenesulfonic acid (10.0 equiv, 143 mg, mmol) in toluene (4 ml, 0.02 M). The reaction mixture was refluxed with stirring for 9 h. After cooling to room temperature, the crude product was precipitated as dark red solids, which were collected by filtration and washed with toluene (10 ml), water (10 ml), and methanol (10 ml) to give the dibrominated derivative of 3,4,9,10-perylenetetracarboxylic dianhydride (PTCA) S1 as a dark red solid material (20.1 mg, mmol, 49%). This material was then treated with cyclohexylamine (3.0 equiv, 12.6 µl, S4

5 mmol) in a 0.4 ml NMP solution containing acetic acid (5.0 equiv, 10.3 µl, mmol). [3] The reaction mixture was heated at 85 C for 6 h, and then allowed to cool to room temperature. The formed precipitate was filtered, washed with methanol (10 ml), and dried in vacuo. The solid obtained was purified by column chromatography (silica-gel, DCM) to give the dibrominated derivative of N,N -dicyclohexyl perylene diimide S2 (22.9 mg, mmol, 88%). Further purification involved dissolving the product into a minimum volume of chloroform, followed by reprecipitation of the product by addition of hexane. This product was analyzed by 1 H NMR spectroscopy, which indicated the existence of two structurally distinct components corresponding to 1,7- and 1,6-regioisomers. Comparison of the observed spectrum to the authentic one [3] revealed that the major component was identified as the 1,7-regioisomer (Figure S5). Scheme S1. Synthesis of bay-monofunctionalized perylenes Bn Bn Bn Bn Br 1 Br 1 6 Br Br 7 1b' Bn Bn p-tsh (10 equiv) Bn Bn reflux, 9 h Br Br Br Br cyclohexylamine (3.0 equiv) acetic acid (5.0 equiv) / NMP, 85 o C, 6 h S1 (49%) S2 (88%) N N Br Br Br Br N major N minor Figure S5. 1 H NMR spectrum of the 1,7- and 1,6-dibrominated derivatives of N,N -dicyclohexyl perylene diimide S2, showing strong and weak signals assignable to the 1,7- and 1,6-regioisomers, respectively. S5

6 References [1] Magde, D.; Wong, R.; Seybold, P. G. Photochem. Photobiol. 2002, 75, [2] Sengupta, S.; Dubey, R. K.; Hoek, R. W. M.; van Eeden, S. P. P.; Gunbaş, D. D.; Grozema, F. C.; Sudhölter, E. J. R.; Jager, W. F. J. rg. Chem. 2014, 79, [3] Würthner, F.; Stepanenko, V.; Chen, Z.; Saha-Möller, C. R.; Kocher, N.; Stalke, D. J. rg. Chem. 2004, 69, S6

7 1 H NMR (300 MHz, CDCl 3 ) of 1b δ H / ppm S7

8 13 C NMR (75 MHz, CDCl 3 ) of 1b δ C / ppm S8

9 1 H NMR (300 MHz, CDCl 3 ) of 1b δ H / ppm S9

10 13 C NMR (75 MHz, CDCl 3 ) of 1b δ C / ppm S10

11 1 H NMR (300 MHz, CDCl 3 ) of 1c δ H / ppm S11

12 13 C NMR (75 MHz, CDCl 3 ) of 1c δ C / ppm S12

13 1 H NMR (300 MHz, CDCl 3 ) of 2a Bn Bn TBS Bn Bn 2a δ H / ppm S13

14 13 C NMR (75 MHz, CDCl 3 ) of 2a Bn Bn TBS Bn Bn 2a δ C / ppm S14

15 1 H NMR (300 MHz, CDCl 3 ) of 2b δ H / ppm S15

16 13 C NMR (75 MHz, CDCl 3 ) of 2b δ C / ppm S16

17 1 H NMR (300 MHz, CDCl 3 ) of 2c Bn Bn Ac Bn Bn 2c δ H / ppm S17

18 13 C NMR (75 MHz, CDCl 3 ) of 2c Bn Bn Ac Bn Bn 2c δ C / ppm S18

19 1 H NMR (300 MHz, CDCl 3 ) of 3a δ H / ppm S19

20 1 H NMR (300 MHz, DMS-d 6 ) of 3b H 3b δ H / ppm S20

21 13 C NMR (75 MHz, DMS-d 6 ) of 3b H 3b δ C / ppm S21

22 1 H NMR (300 MHz, CDCl 3 ) of 3c δ H / ppm S22

23 13 C NMR (75 MHz, CDCl 3 ) of 3c δ C / ppm S23

24 1 H NMR (300 MHz, CDCl 3 ) of 4a ipr N ipr ipr N ipr 4a δ H / ppm S24

25 1 H NMR (300 MHz, CDCl 3 ) of 4b δ H / ppm S25

26 1 H NMR (300 MHz, CDCl 3 ) of 4c δ H / ppm S26

27 13 C NMR (75 MHz, CDCl 3 ) of 4c δ C / ppm S27

28 1 H NMR (300 MHz, CDCl 3 ) of 5a δ H / ppm S28

29 13 C NMR (75 MHz, CDCl 3 ) of 5a δ C / ppm S29

30 1 H NMR (300 MHz, CDCl 3 ) of 5b δ H / ppm S30

31 13 C NMR (75 MHz, CDCl 3 ) of 5b δ C / ppm S31

32 1 H NMR (300 MHz, CDCl 3 ) of 6 Bn Bn Bn Bn Bn Bn Bn 6 Bn δ H / ppm S32

33 13 C NMR (75 MHz, CDCl 3 ) of 6 Bn Bn Bn Bn Bn Bn Bn 6 Bn δ C / ppm S33

34 1 H NMR (300 MHz, CDCl 3 ) of 7 δ H / ppm S34

35 13 C NMR (75 MHz, CDCl 3 ) of 7 δ C / ppm S35

36 1 H NMR (300 MHz, CDCl 3 ) of 8 δ H / ppm S36

37 13 C NMR (75 MHz, CDCl 3 ) of 8 δ C / ppm S37