Supplementary Figures

Transcription

1 Supplementary Figures Supplementary Figure 1 The synthesis procedures of PMI-1DTE, PMI-2DTE and PMI-3DTE.

2 PMI- 1DTE in Toluene PMI- 1DTE in Toluene PMI- 1DTE in THF PMI-1DTE in THF PMI-1DTE in DMF 6 PMI-1DTE in DMF Wavelength(nm) Supplementary Figure 2 Absorption and PL spectra of PMI-1DTE in toluene, THF and DMF (1x1-6 M) before and after 32 nm UV light irradiation. The excitation wavelength for PL is 514 nm.

3 PMI-2DTE in toluene PMI-2DTE in toluene PMI-2DTE in THF PMI-2DTE in THF PMI-2DTE in DMF PMI-2DTE in DMF Wavelength(nm) Supplementary Figure 3 Absorption and PL spectra of PMI-2DTE in toluene, THF and DMF (.75x1-6 M) before and after 32 nm UV light irradiation. The excitation wavelength for PL is 514 nm.

4 PMI-3DTE in toluene PMI-3DTE in toluene PMI-3DTE in THF PMI-3DTE in THF PMI-3DTE in DMF PMI-3DTE in DMF Supplementary Figure 4 Absorption and PL spectra of PMI-3DTE in toluene, THF and DMF (1x1-6 M) before and after 32 nm UV light irradiation. The excitation wavelength for PL is 514 nm.

5 Normalised Absorbance 4 3 Open form in THF PMI-1DTE PMI-2DTE PMI-3DTE.8 PSS in THF PMI-1DTE PMI-2DTE PMI-3DTE PMI-1DTE open form.4 PMI-1DTE closed form Toluene THF DMF Toluene THF DMF PMI-2DTE open form PMI-2DTE closed form.6.4 Toluene THF DMF.4 Toluene THF DMF.2.2 PMI-3DTE open form.1 PMI-3DTE closed form.1 Toluene THF DMF Toluene THF DMF.5.5 Supplementary Figure 5 Absorption spectra of PMI-1DTE, PMI-2DTE, PMI-3DTE in toluene, THF and DMF in open form and photostationary state under 32 nm UV light irradiation.

6 Normalised intensity Open form in THF PSS in THF 1. PMI-1DTE PMI-2DTE PMI-3DTE 3 PMI-1DTE PMI-2DTE PMI-3DTE PMI-1DTE open form Toluene THF DMF 3 PMI-1DTE closed form In toluen In THF In DMF toluene solvent THF solvent DMF solvent PMI-2DTE open form Toluene THF DMF 15 1 PMI-2DTE closed form In toluen In THF In DMF toluene solvent THF solvent DMF solvent PMI-3DTE open form Toluene THF DMF 1 5 PMI-3DTE closed form toluene In THF In DMF Toluene solvent THF solvent DMF solvent Supplementary Figure 6 PL spectra of PMI-1DTE, PMI-2DTE, PMI-3DTE in toluene, THF and DMF at open form and photostationary state (32 nm UV light irradiation). The excitation wavelength for PL is 514 nm.

7 Supplementary Figure 7 HOMO/LUMO levels and the twist angle calculation for PMI-nDTEs.

8 In toluene 1..8 PMI PMI-2DTE PMI-1DTE PMI-3DTE Supplementary Figure 8 PL spectra of PMI and PMI-nDTE in toluene PMI-3DTE in PMMA 32 nm UV ligth irradiation s 2s 12s 4s 6s 12s 18s 24s 3s PMI-3DTE in PMMA(2.4mg/.1g) 32nm UV ligth irradiation time 584 nm 1634 times s 5s 1s 2s 4s 6s 575 nm PMI-3DTE in PMA 32 nm UV ligth irradiation s 2s 5s 1s 2s 4s 6s 12s 18s PMI-3DTE in PMA (2.4mg/.1g) 32nm UV ligth irradiation time 634nm times s 2s 5s 1s 2s 4s. 566 nm PMI-3DTE solid film PMI-3DTE in pure film Supplementary Figure 9 Absorption and PL spectra of PMI-3DTE in PMA, PMMA and pure films before and after 32 nm UV light irradiation. The excitation wavelength for PL is 514 nm.

9 2x1 5 1x1 5 Open form 1 UV Number of cycles Supplementary Figure 1 Reversible fluorescence switching for PMI-3DTE in PMMA film (d) at 64 nm upon alternating irradiation with 32 nm (1) and visible light greater than 495 nm (5 min). The Excitation wavelength for PL is 514 nm. Supplementary Figure 11 Scanning electronic microscopic images for block copolymer vesicles of PSt-b-PEO staining by PMI-3DTE.

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17 Supplementary Figure 12 1 H and 13 C NMR spectra of all the structurally-novel compounds.

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22 Supplementary Figure 13 Normal MS, MALDI-TOF-MS and HR-MS of all the structurally-novel compounds.

23 Supplementary Figure 14 The 1 H-NMR spectra of PMI-nDTEs (n =1, 2, 3) change with the time of 32 nm UV light irradiation. The concentrations are 5. mg/ml for PMI-1DTE and PMI-3DTE while 2.5 mg/ml for PMI-2DTE. The conversion efficiencies of PMI-nDTE at PSS were measured about 96.2%, 97.2% and 95.4% respectively according to the integrate value change of the methyl groups on thiophene rings in 1 H-NMR spectra before and after UV irradiation.

24 Absorbance at 6 nm Absorbance at 6 nm.12 y = y +Ae -kt.8.4 PMI-1DTE PMI-2DTE PMI-3DTE Exponential fit of PMI-1DTE Exponential fit of PMI-2DTE Exponential fit of PMI-3DTE y A k Value Value Value Statistic s Adj. R-S quare PMI-1DTE PMI-2DTE PMI-3DTE Time (s) y = y +Ae -kt y A R Value Value Value PMI-1DTE PMI-2DTE PMI-3DTE Statistic s Adj. R-S quare PMI-1DTE PMI-2DTE PMI-3DTE Exponential fit of PMI-1DTE Exponential fit of PMI-2DTE Exponential fit of PMI-3DTE Time (s) Supplementary Figure 15 Time-resolved spectroscopic monitoring of the forward and backward photochromic interconversions between open and closed forms of PMI-nDTE. The curves were fitted with monoexponential functions. The concentrations for PMI-1DTE, PMI-2DTE and PMI-3DTE in toluene are M, M and M respectively.

25 Supplementary Tables Supplementary Table 1 The relevant optical data between the works reported previously and our results of PMI-3DTE. Reference Link mode Cyclization yields at PSS in solution Cyclization/ cyloreversion quantum yields in solution Fluorescence quantum yields of open form / closed form/ PSS on/off ratios (PSS) Fluoresence quenching time / efficiency / matrix Applications One DTE can be closed Chem. Commun (21) Two DTEs conjugated one fluorophore with a individual yields of 14 % (Opt. Mater. 21, - 83% /.1% / - Less than 1.25 : 1 - / < 25% / in solution Laser emission (23) ) The value seems large in CHCl 3 Adv. Mater. 14, (22) Four DTEs fused one fluorophore Half DTEs can be closed with a total yields of 16% 31. % / 39.4 % 9.8% / - / - but no details was given, and there is no fluorescence for 45 min / - / in solution None open form in PC film J. Photoch. Photobio. A 2, (28) Two DTEs conjugated one fluorophore One DTE can be closed with a individual yields of 99% - 12% / - / - 99:1 in solution 49:1 in PMMA 3 / 99% / in solution 24 / 98% / in PMMA None Dyes and Two DTEs linked with Both two DTEs can be Pigments 89, one fluorophore with closed with a total yields of 18. % / 26. % 5% / - / 37% 1 : 7.5 in solution 4 min / - /in solution None (211) an oxygen bridge about 5% Three DTEs linked All DTEs can be closed > 3 : 1 in toluene / 98% / in solution Photo-rewritable data storage PMI-3DTE with one fluorophore with a total yields of 49.5% /.7% 97%/~% /~% > 1:1 in PMA 2- / 97% / in solid All-optical transistor with an oxygen bridge 95.4% Absolutely quenched in pure film film Super-resolution imaging - means the data is not given in the corresponding literatures.

26 Supplementary Table 2 Optical properties of PMI-1DTE, PMI-2DTE and PMI-3DTE. / nm Abs FL Time / nm Sample Solvent (Open Abs em / FL QY (%) on/off for 5% (Closed form) nm on/off a form) ratio b PSS c Time for 9% PSS Toluene 295, , 511, /3 3 1 s PMI-1DTE THF 294, , 57, / s DMF 295, , 514, /2 17 Toluene 297, , 57, ~1/~ PMI-2DTE THF 298, , 53, /~ DMF 296, , 512, /~.5 63 Toluene 298, , 535, /~ THF 295, , 538, /~ PMI-3DTE DMF 298, , 537, /~ 17 PMA 295, , 538, PMMA 295, , Pure film 293, abs is the absorption maximum wavelength a. Fluorescence quantum yields of PMI-nDTE at open form and PSS (32 nm irradiation) were estimated relative to rhodamine B (.7, in ethanol). b Fluorescence on/off quenching ratios are calculated by comparing the intensity at maximum emission wavelength em before and after 32nm UV irradiation. The fluorescence intensity of PMI-3DTE in PSS at 64 nm is detected (Supplementary Fig. 9), so the fluorescence on/off quenching ratios is. c The time was taken to obtain 5 % PSS. d The time was taken to obtain 9 % PSS. d Supplementary Table 3 Molar extinction coefficients and photoconversion yields of PMI-nDTEs in toluene under 32 nm UV irradiation Compounds (L mol -1 cm -1 ) Open form Closed form (32 nm) (617 nm) pss, 32nm P open (%) R calc R meas PMI-1DTE % PMI-2DTE % PMI-3DTE % is the molar extinction coefficient at a given wavelength. pss, 32nm is the fractional population of closed form in PSS under 32 nm irradiation and calculated from 1 H NMR (Supplementary Fig. 14). P open = (1 - pss) n, means the probability of open-form PMI-nDTE in 32 nm PSS, n =1, 2, 3. R calc = 1/ P open, the calculated fluorescence quenching ratio with the hypothesis that only one closed DTE in PMI-nDTE can quenching the fluorescence completely. R meas is measured by comparing the intensity of PMI-nDTE before and after 32 nm UV irradiation. The greatest difference of R meas and R calc for PMI-3DTE was related to the background of solvents and the baseline of the PL equipment even the noise intensity signal is around 2.The fluorescence of PMI-3DTE is out of limit of detection.

27 Supplementary Table 4. Photoisomerization kinetic parameters and photoisomerization quantum yields. Reaction Compounds irr eq o c c-o pss ex PMI-1DTE-O 32 nm ±8 Cyclization PMI-2DTE-O 32 nm ±9 PMI-3DTE-O 32 nm ±9 PMI-1DTE-C 617 nm ±2 Cycloreversion PMI-2DTE-C 617 nm ±2 PMI-3DTE-C 617 nm ±1 irr = irradiation wavelength, the intensity of irradiation light is 2.67 mw/cm 2 for 32 nm and 2.28 mw/cm 2 for 617 nm. k eq = rate constant of equilibration, which was fit with a monoexponential curve from the kinetics of reequilibration from an arbitrary initial photostationary state ( o ) to a new photostationary state ( pss ). o c = cyclization rate constant. o c = cycloreversion rate constant. pss = the fractional population of closed form in PSS irradiated under given wavelengths. ex = the excitation rate constants. = Cyclization/ Cycloreversion quantum yields. Supplementary Table 5 The fluorescence lifetime of PMI-nDTE in toluene. Compounds State a 2 Open form 3.98 ns 1.17 PMI-1DTE PSS 3.84 ns 1.16 Closed form ~ ns - Open form 3.96 ns 1.26 PMI-2DTE PSS - - Closed form ~ ns Open form 3.95 ns 1.26 PMI-3DTE PSS - - Closed form ~ ns - a The fluorescence signal is too weak to calculate the lifetime of PMI-2DTE and PMI-3DTE at PSS. The lifetime of PSS was a single component and reasonably contributed by the open form, the lifetime of closed form is too small to detectable under current conditions (the pulse width of the laser is 95.3 ps). The excitation wavelength is 445 nm. The monitoring emission wavelength is 565 nm.

28 Supplementary Notes Supplementary Note 1 The cyclization and cycloreversion quantum yields calculation. The quantum yields of photoisomerization reactions were measured following the reported method (Supplementary Equation 1-7). 1, 2 The kinetics of re-equilibration from an arbitrary initial photostationary state (A ) to a new phostationary state (A pss ) dictated by exposure to light of a given wavelength, is monoexponential (Supplementary Fig.15 and Supplementary Equation 1). The rate constant of equilibration ( eq ) is given by the sum of the two apparent first-order rate constants defining the overall transition and the equilibrium constant ( pss ) by their ratio. ex is the rate constants for absorption at excitation wavelength. ex (cm 2 molecule -1 ) is the absorption cross-section at excitation wavelength λ irr (nm). ex (photons s -1 cm -2 ) is the photon flux. I (W cm -2 ) is the intensity of irradiation light, it is 2.67 mw/cm 2 for 32 nm and 2.28 mw/cm 2 for 617 nm. N a is the Avogadro's constant. The concentration for PMI-1DTE, PMI-2DTE and PMI-3DTE in toluene are M, M and M respectively. A(t) = A pss + (A - A pss ) e - eq t (1) eq = o c + c o, (2) pss = [Open form] / [closed form] = o c / c o (3) a pss = pss / (1 + pss ) = o c / eq (4) ex =σ ex ψ ex, σ ex = (1 3 ln1/n a ) ε irr, ex = λ irr I (5) Φ o c = o c / ex,o (6) Φ c o = c o / ex,c (7) Supplementary Note 2 The explain of the same photochromism speeds for PMI-nDTES. According to the Beer Lambert law, A = lg(i/i ) (8) ΔI = I -I =(1-1 A ) I (9) in which A is the absorbance, I, I and ΔI are the intensity (power per unit area) of the incident light, the transmitted light and the absorbed light respectively. In dilute toluene solutions ( M), the absorbance values of PMI-nDTEs at 32 nm are as low as.4n (Supplementary Fig. 5), Thus, the average absorbed light intensity value for each kind of DTE on PMI-nDTEs is ΔI n /n = (1-1.4n ) I / n (1) in which ΔI n /n for PMI-nDTEs are considered approximate equal with each other in dilute solutions conditions. The equal absorbed light for DTE means the same photochromic speeds.

29 That is why Supplementary Note 3 The energy transfer (ET) efficiency calculation. The ET efficiency (E) has been estimated according to Supplementary Equation 11: 3 6 E = R / (R 6 +r 6 ) = 1 - (I D,FRET / I D, ) = 1 - D,FRET / D, (11) Experimentally, the amount of energy transferred can be calculated from the observed quenching of donor intensity (I D,FRET versus I D, ), by the corresponding lifetime ratios D,FRET versus τ D,, or from the ratio of the intensities from the donor and acceptor channels. The lifetimes of donor at the beginning (open form) τ D, and photostationary state (PSS, 97% closed form) τ D,pss are 3.98 ns and 3.64 ns respectively with no significant changes (Supplementary Table 5). In both cases, only a single component sufficed for the analysis of the data ( 2 < 1.3 and symmetrical residuals). This indicated that τ D,FRET ( ns) was too small to be detectable under our equipment condition (we use a picosecond pulsed diode laser with a of period 95.3 ps), and D,pss = 3.84 ns was come from the 3% unconverted open form. Thus from equation S1, the conclusion was drawn that the ET efficiency for closed form DTE is about 1%. Only one DTE could completely quench the fluorescence of PMI. Supplementary Methods. Materials. Compound 1 and 7 were synthesized according to the reported procedures 4. The synthesis of compound 4 was performed as described before. 5 Compound 5 was synthesized according to the reported procedures with a little modified 6. Other commercially available starting materials, reagents and solvents were used as supplied, unless otherwise stated, and were obtained from Alladin Chemicals and Sinopharm Chemical Reagent Co., Ltd. Chloroform was dried over CaH 2 with stirring overnight followed by distillation under reduced pressure. THF was dried using sodium wire-benzophenone system and distillation. Dimethoxyethane (DME) was bubbled with N 2 for 3 mins before use. N-Bromosuccinimide (NBS) was recrystallized from water. Compounds characterization and identification. 1 H-NMR and 13 C-NMR spectra were recorded using a 4 M Bruker AV4 or 6 M Bruker AscendTM 6 MHZ in CDCl 3 or CD 2 Cl 2 and an internal standard of tetramethylsilane was used. Normal Mass spectra were recorded using an Agilent 11 LC/MSD Trap, while High-resolution mass spectra were obtained with a Bruker microtof spectrometer. MALDI-TOF mass spectra were recorded on a MALDI-TOF-TOF (Bruker ultraflextreme). Purification of intermediates and final products was accomplished

30 mainly by gravity column chromatography, using silica gel (2-3 mesh). The purity of all final compounds was checked by elemental analysis (Elementar Vario Micro-cube). The purity of PMI-nDTE was obtained on a Waters Breeze 2 HPLC with UV detector (254 nm) using a 5 μm CN column and eluting with DCM/hexane binary mixed solvent). For the elemental analysis equipment of our analytical and testing center which is limited to test the compounds containing F that is harmful, HR-MS and HPLC date were used instead to identify final products and check the purity. Synthesis procedures of PMI-nDTE (n = 1, 2, 3) from the start materials. N-(2,6-Diisopropylphenyl)-9-[4-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)-phenyl]-peryle ne-3,4-dicarboximide (3). N-(2,6-diisopropylphenyl)-9-bromo-perylene-3,4-dicarboximide (.29 g,.52 mmol), 4-bromophenol (.13 g,.78 mmol) and potassium carbonate (.82 g,.78 mmol) were stirred in NMP (1 ml) at 13 C for 5 h. After cooling down to room temperature, the reaction mixture was poured into hydrochloric acid aqueous(1m,1 ml). The resulting precipitate was washed with water and dried. The crude product was purified by column chromatography on silica gel using 6% dichloromethane in hexane as eluent, and the first fraction was collected to get.19 g red solid. Since debromolation reaction was happened during this reaction, and the polarity of resulting debromination product (PMI) was so similar with that of target molecular N-(2,6-diisopropylphenyl)-9-(4-bromophenoxyl)-perylene-3,4-dicarboximide compound (PMI-OPh-Br) that the first fraction of column chromotography containing both PMI and PMI-OPh-Br. Although PMI-OPh-Br could not be separated from the mixture, the mixture was used without farther purification. That is because PMI would not take participate in next reaction step while PMI-OPh-Br transform to larger polarity compound (3) which could be easily separated from reactant and PMI. The above mixture (.19 g) and bis(pinacolato)diboron(.11 g,.44 mmol) were mixed together with potassium acetate (..71 g,.725 mmol) in dioxane (6 ml) under a light stream of nitrogen. Finally, PdCl 2 (dppf) catalyst (1 mg,.15 mmol) was added, and the reaction mixture was stirred under nitrogen atmosphere for 16 h at 9 C. After cooling down, the reaction mixture was extracted with DCM, washed with water three times, dried over with MgSO 4, concentrated under reduced pressure. The crude product was chromatographed on silica gel eluting with DCM/hexane 6:4 to yield a red solid (.9 g, total yield: 25%).

31 1 H NMR (4 MHz, CDCl 3 ): δ (m, 2H), 8.52 (d, J = 7.5 Hz, 1H), 8.45 (d, J = 8.1 Hz, 1H), (m, 3H), 7.89 (d, J = 8.4 Hz, 2H), 7.66 (t, J = 7.9 Hz, 1H), 7.47 (t, J = 7.8 Hz, 1H ), 7.33 (d, J = 7.8 Hz, 2H), 7.17 (d, J = 8.5 Hz, 2H), 7.3 (d, J = 8.3 Hz, 1H), 2.77 (dt, J 1 = 13.7, J 2 = 6.8 Hz, 2H), 1.37 (s, 11H), 1.18 (d, 12H), J = 6.8 Hz; 13 C NMR (151 MHz, CDCl3) δ 164.1, 159.1, 155.8, 145.7, 137.6, 137., 132.2, 132., 131.1, 13.7, 129.4, 127.2, 127.1, 126.8, 125.1, 124.7, 124.5, 124., 121.1, 12.3, 12.2, 119.5, 118.8, 113.7, 84., 29.71, 29.1, 24.9, 24.; HRMS (APCI) (m/z): [M+1] + calcd. for C 46 H 42 BNO 5, ; found, [5-(4-hydroxyphenyl)-2-methyl-3-thienyl]-2-{2-methyl-5-[4-(octyloxy)phenyl]-3-thienyl}per fluorocyclopentene (C 8 H 17 OPh-DTE-Ph-OH, 6). To a 1 ml two-neck round flask, compound 4 (.3 g,.46 mmol), compound 5 (.2 g,.92 mmol), Na 2 CO 3 (.24g, 2.26 mmol), water (2.5 ml) and dimethoxyethane (1mL) were added under N 2 atmosphere, then the catalyst Pd(PPh 3 ) 4 (26.6 mg,.23 mmol) was added under N tream. The reaction mixture was refluxed at 9 C for 24 hours. After cooling down, Water (5 ml) and ethyl ether (5 ml) were added and the organic layer was washed with water (5 ml 3), dried over Na 2 SO 4 and concentrated under reduced pressure. The crude product was purified by gravity silica-gel column chromatography (silica gel) eluting with hexane DCM: hexane (3:2) to yield a light grey solid (.15 g, 49 %). 1 H NMR (4 MHz, CDCl3) δ : (m, 4H), 7.14 (s, 2H), 6.9 (d, J = 8.7 Hz, 2H), 6.84 (d, J = 8.6 Hz, 2H), 5.9 (s, 1H), 3.97 (t, J = 6.6 Hz, 2H), 1.95 (s, 6H), (m, 2H), 1.45 (dd, J 1 = 14.2, J 2 = 6.5 Hz, 2H), (m, 8H),.89 (t, 3H, J = 6.7 Hz); 13 C NMR (151 MHz, CDCl 3 ) δ= 159.1, 155.6, 142.2, 142., 14.3, 14.2, 127.1, 126.9, 126.4, 126., 125.8, 121.3, 121.2, 115.9, 115., 68.2, 31.8, 29.4, 29.2, 29.2, 26., 22.7, 14.5, 14.1; HRMS (APCI) (m/z): [M+1]+ calcd. for C 35 H 34 F 6 O 2 S 2, ; found, N-(2,6-diisopropylphenyl)-1,6,9-tris(4-bromophenoxyl)-perylene-3,4-dicarboximide compound (8). Compound 7 (.36 g,.5 mmol), 4-bromophenol (.35 g, 2. mmol) and potassium carbonate (.21 g, 2. mmol) were stirred, in NMP (2 ml) at 13 C for 4 h. After cooling down to room temperature, the reaction mixture was poured into hydrochloric acid aqueous(1m, 2 ml). The resulting precipitate was washed with water and dried. The crude product was purified by column chromatography on silica gel using 5 % dichloromethane in hexane as eluent, and the first fraction was collected to get.2 g red solid with a yield of 4%. 1 H NMR (6 MHz, CDCl 3 ): δ 9.31 (d, J = 7.8 Hz, 1H), 9.13 (d, J = 8.8 Hz, 1H), 8.42 (d, J = 8.2

32 Hz, 1H), 8.32 (s, 1H), 8.29 (s, 1H), 7.64 (t, J = 8.1 Hz, 1H), 7.53 (d, J = 8.8 Hz, 2H), (m, 5H), 7.3 (d, J = 7.8 Hz, 2H), 7.4 (d, J = 8.8 Hz, 2H), 7.2 (d, J = 8.8 H, 2Hz), 6.95 (t, J = 6. Hz, 2H), 6.9 (d, J = 8.8 Hz, 1H), 2.7 (dq, J 1 = 13.6, J 2 = 6.8 Hz, 2H), 1.14 (d J = 6.8 Hz, 12H,); 13 C NMR (151 MHz, CDCl3): δ 162.9, 155.4, 155.2, 155.1, 155.4, 152.4, 151.7, 145.6, 133.2, 133.2, 133.2, 131.6, 13.6, 13.5, 129.8, 129.8, 129.6, 128.2, 128.1, 127.4, 126.4, 126., 125.6, 125.5, 124.5, 124.3, 124., 122.4, 122., 121.9, 121.1, 12., 119.9, , 116.7, 116.6, 112.3, 29.1, 24.; MALDI-TOF-MS (m/z): [M+1] + Calcd. for C 52 H 36 Br 3 NO 5, ; found, HPLC purity: 99.5%, eluting with DCM : hexane = 3 : 7. N-(2,6-diisopropylphenyl)-1,6,9-tris[4-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)-phenyl]- perylene-3,4-dicarboximide compound (9). Compound 8 (.2 g,.2 mmol) and bis(pinacolato)diboron (.31 g, 1.2 mmol) were mixed together with potassium acetate (.15 g, 1.5 mmol) in dioxane (2 ml) under a light stream of nitrogen. Finally, PdCl 2 (dppf) catalyst (22 mg,.3 mmol) was added, and the reaction mixture was stirred under nitrogen atmosphere for 16 h at 9 C. After cooling down, the reaction mixture was extracted with DCM, washed with water three times, dried over with MgSO 4, concentrated under reduced pressure. The crude product was chromatographed on silica gel eluting with DCM/hexane 8:2 and recrystallized in DCM/Hexane binary solvents to yield a red solid (.12 g, 54%). 1 H NMR (4 MHz, CDCl 3 ): δ 9.33 (d, J = 7.8 Hz, 1H), 9.15 (d, J = 8.8 Hz, 1H), 8.38 (d, J = 8.2 Hz, 1H), 8.33 (s, 1H), 8.31 (s, 1H), 7.83 (t, J = 8.9 Hz, 4H), 7.79 (d, J = 8.5 Hz, 2H), 7.59 (t, J = 8.1 Hz, 1H), 7.43 (t, J = 7.8 Hz, 1H), 7.28 (d, J = 7.8 Hz, 2H), (m, 4H), 7.5 (d, J = 8.5 Hz, 2H), 6.92 (d, J = 8.8 Hz, 1H), 2.71 (dq, J 1 = 13.7, J 2 = 6.8 Hz, 2H), (m, 33H), 1.14 (d, J = 6.8 Hz, 12H); 13 C NMR (151 MHz, CDCl 3 ): δ 163., 159., 158.7, 155.2, 152.3, 151.5, 145.7, 137.1, 137.1, 136.9, 131.7, 13.7, 129.8, 129.8, 129.4, 128.5, 128.4, 127.5, 126.8, 126.2, 126.1, 126., 124.5, 124.4, 124., 122.5, 121.8, 121., 119.1, 117.4, 117.2, 113.1, 83.9, 83.9, 83.8, 29.1, 24.9, 24.; HRMS (APCI) (m/z): [M+1] + calcd. for C 7 H 72 B 3 NO 11, ; found, PMI-2DTE-Br (1). N-(2,6-diisopropylphenyl)-1,6,9-tribromo-perylene-3,4-dicarboximide (7,.237 g,.331 mmol), compound 6 (.55 g,.83 mmol) and potassium carbonate (.17 g, 1.23 mmol) were stirred in NMP (1 ml) at 7 C for 1 h. After cooling down to room temperature, the reaction mixture was poured into hydrochloric acid aqueous(1 M,1 ml). The resulting precipitate was washed with water and dried. The crude product was purified by column

33 chromatography on silica gel using 4 % dichloromethane in hexane as eluent, and the fraction of first ribbon was collected to get.135 g red solid (yield: 22 %). 1 H NMR (6 MHz, CDCl 3 ): δ 9.32 (d, J = 7.8 Hz, 1H), 9.9 (d, J = 8.5 Hz, 1H), (m, 3H), 7.9 (d, J = 8.5 Hz, 1H), 7.71 (t, J = 8.1 Hz, 1H), 7.54 (d, J = 8.4 Hz, 4H), 7.45 (t, J = 8.6 Hz, 5H), 7.3 (d, J = 7.8 Hz, 2H), 7.22 (s, 2H), (m, 6H), 6.89 (d, J = 8.6 Hz, 4H), 3.97 (t, J = 6.6 Hz, 4H), 2.71 (m, 2H), 1.95 (s, 6H), 1.93 (s, 6H), (m, 4H), (m, 4H), (m, 16H), 1.15 (d, J = 6.7 Hz, 12H),.89 (t, J = 6.5 Hz, 6H); 13 C NMR (151 MHz, CDCl3): δ 162.9, 159.1, 155.4, 155.3, 153., 152.9, 145.6, 142.3, 141.3, 141.1, 14.2, 132.1, 131.6, 131.1, 13.7, 13.5, 129.8, 129.7, 129.6, 129.5, 1288, 128., 127.6, 127.4, 127.3, 127.1, 126.9, 126., 125.9, 125.9, 125.6, 125.2, 125.1, 124., 123.7, 122.4, 122.1, 122.1, 121.1, 119., 119., 114.9, 68.2, 31.8, 29.4, 29.2, 29.2, 29.1, 26., 24., 22.7, 14.6, 14.5, 14.1; MALDI-TOF-MS (m/z): [M+1] + calcd. for C 14 H 9 BrF 12 NO 6 S 4, ; found, ; HPLC purity: 99.7%, eluting with DCM : hexane = 2 : 8. PMI-1DTE (11). To a 1 ml two-neck round flask, compound 4 (.85 g,.12 mmol), compound 3 (.12 g,.18 mmol), Na 2 CO 3 (.64 g, 6. mmol), water (1.25 ml) and dimethoxyethane (5 ml) were added under N 2 atmosphere, then the catalyst Pd(PPh 3 ) 4 (6.9 mg,.6 mmol) was added under N tream. The reaction mixture was refluxed at 9 C for 18 hours. After cooling down, Water (5 ml) and ethyl ether (5 ml) were added and the organic layer was washed with water (5 ml 3), dried over Na 2 SO 4 and concentrated under reduced pressure. The crude product was purified by gravity silica-gel column chromatography (silica gel) eluting with hexane DCM: hexane (1 : 1) to yield a red solid (.1g, 73 %). 1 H NMR (6 MHz, CDCl 3 ): δ 8.65 (d, J = 8. Hz, 1H), 8.62 (d, J = 8. Hz, 1H), 8.51 (d, J = 7.5 Hz, 1H), 8.43 (d, J = 8.1 Hz, 1H), 8.37 (d, J = 8.3 Hz, 1H), 8.34 (d, J = 8.5 Hz, 1H), 8.3 (d, J = 8.1 Hz, 1H), 7.66 (t, J = 7.9 Hz, 1H), 7.61 (d, J = 8.6 Hz, 2H), 7.48 (d, J = 7.8 Hz, 1H), 7.45 (d, J = 8.8 Hz, 2H), 7.34 (d, J = 7.8 Hz, 2H), 7.27 (s, 1H), 7.21 (d, J = 8.6 Hz, 2H), 7.16 (s, 1H), 7.2 (d, J = 8.3 Hz, 1H), 6.9 (d, J = 8.7 Hz, 2H), 3.97 (t, J = 6.6 Hz, 2H), (m, 2H), 1.99 (s, 3H), 1.98 (s, 3H), (m, 2H), (m, 2H), (m, 8H), 1.18 (d, J = 6.8 Hz, 12H),.89 (t, J = 6.9 Hz, 3H); 13 C NMR (151 MHz, CDCl 3 ): δ 164., 159.1, 155.9, 155.9, 145.7, 142.4, 141.4, 141.2, 14.2, 137.5, 132.1, 132., 131.1, 13.7, 13., 129.4, 129.3, 129.3, 127.4, 127.1, 126.9, 126.7, 126.1, 125.9, 125.7, 124.9, 124.7, 124.6, 124.4, 124., 122.5, 121.1, 121.1, 12.4, 12.3, 12.1, 119.5, 115., 113., 68.2,

34 31.8, 29.7, 29.4, 29.2, 29.1, 26., 24., 22.7, 14.6, 14.5, 14.1; HRMS (APCI) (m/z): [M+1] + calcd. for C 69 H 59 F 6 NO 4 S 2, ; found, HPLC purity: 98.5 %, eluting with DCM : hexane = 3 : 7. PMI-2DTE (12). To a 1 ml two-neck round flask, PMI-2DTE-Br (.5 g,.27 mmol), Na 2 CO 3 (.14 g,.13 mmol), water (1 ml) and dimethoxyethane (4 ml) were added under N 2 atmosphere, then the catalyst Pd(PPh 3 ) 4 (1.5 mg, 13 mmol) was added under N tream. The reaction mixture was refluxed at 9 C for 24 hours. After cooling down, Water (2 ml) and ethyl ether (2 ml) were added and the organic layer was washed with water (2 ml 3), dried over Na 2 SO 4 and concentrated under reduced pressure. The crude product was purified by gravity silica-gel column chromatography (silica gel) eluting with hexane DCM: hexane (2:3) to yield a red solid (.3 g, 63%). 1 H NMR (4 MHz, CDCl 3 ): δ = 9.29 (d, J = 7.5 Hz, 2H), 8.36 (s, 2H), 7.93 (d, J = 7.7 Hz, 2H), 7.61 (t, J = 8. Hz, 2H), 7.53 (t, J = 6.2 Hz, 4H), 7.44 (d, J = 8.7 Hz, 4H), 7.3 (d, J = 7.8 Hz, 2H), 7.21 (s, 2H), 7.13 (d, J = 8.9 Hz, 6H), 6.89 (d, J = 8.8 Hz, 4H), 3.97 (t, J = 6.6 Hz, 4H), 2.71 (dt, J = 13.6, 6.8 Hz, 2H), 1.95 (s, 6H), 1.93 (s, 6H), 1.78 (dt, J 1 = 14.6, J 2 = 6.6 Hz, 4H), 1.46 (tt, J = 14.6, 7.7 Hz, 4H), (m, 16H), 1.15 (d, J = 6.8 Hz, 12H),.89 (t, J = 6.7 Hz, 6H); 13 C NMR (151 MHz, CDCl 3 ): δ 164., 159.1, 156., 155.9, 145.7, 142.4, 141.4, 141.2, 14.2, 137.5, 132.1, 132., 131.1, 13.7, 13., 129.4, 129.3, 129.3, 127.4, 127.1, 126.9, 126.7, 126.1, 125.9, 125.7, 124.9, 124.7, 124.6, 124.4, 124., 122.5, 121.1, 121.1, 12.4, 12.3, 12.1, 119.5, 115., 113., 68.2, 31.8, 29.7, 29.4, 29.2, 29.2, 29.2, 26., 24.2, 22.7, 14.6, 14.5, 14.1; HRMS (APCI) (m/z): [M+1] + calcd. for C 14 H 91 F 12 NO 6 S 4, , found; ; HPLC purity: 99.2 %, eluting with DCM : hexane = 2 : 8. PMI-3DTE (13). To a 1 ml two-neck round flask, compound 4 (.39 g,.65 mmol), compound 9 (.11 g,.11 mmol), Na 2 CO 3 (.17 g, 1.62 mmol), water (2.5 ml) and dimethoxyethane (1 ml) were added under N 2 atmosphere, then the catalyst Pd(PPh 3 ) 4 (19 mg,.16 mmol) was added under N tream. The reaction mixture was refluxed at 9 C for 24 hours. After cooling down, Water (5 ml) and ethyl ether (5 ml) were added and the organic layer was washed with water (5 ml 3), dried over Na 2 SO 4 and concentrated under reduced pressure. The crude product was purified by gravity silica-gel column chromatography (silica gel) eluting with hexane DCM: hexane (3:2) to yield a red solid (.9 g, 37 %). 1 H NMR (6 MHz, CDCl 3 ): δ 9.39 (d, J = 7.7 Hz, 1H), 9.2 (d, J = 8.8 Hz, 1H), 8.46 (d, J = 8.2 Hz, 1H), 8.37 (s, 1H), 8.34 (s, 1H), 7.67 (t, J =

35 8.1 Hz, 1H), 7.58 (d, J = 8.6 Hz, 2H), 7.55 (d, J = 8.7 Hz, 2H), 7.52 (d, J = 8.7 Hz, 2H), (m, 7H), 7.3 (d, J = 7.8 Hz, 2H), (overlap with CDCl 3, 2H), 7.21 (d, J = 11.1 Hz, 2H), (m, 6H), 7.9 (d, J = 8.7 Hz, 2H), 6.97 (d, J = 8.8 Hz, 1H), (m, 6H), (m, 6H), 2.72 (dt, J 1 = 13.6, J 1 = 6.8 Hz, 2H), (m, 18H), (m, 6H), (m, 6H), (m, 24H), (m, 12H),.89 (t, J = 6.8 Hz, 9H); 13 C NMR (151 MHz, CDCl 3 ): δ 163.1, 159.1, 159.1, 155.8, 155.6, 155.5, 152.6, 151.9, 145.6, 142.4, 142.3, 141.3, 141.2, 14.3, 14.1, 131.7, 13.7, 13.6, 13., 129.8, 129.8, 129.6, 129.5, 129.5, 129.4, 128.2, 128.1, 127.6, 127.6, 127.5, 127.4, 126.9, 126.1, 126., 126., 125.9, 125.9, 125.9, 125.7, 125.7, 125.6, 125.4, 124.5, 124.2, 124., 122.5, 122.4, 122.3, 122.3, 121.9, 121.1, 121.1, 121., 12.6, 12.4, 118.9, 118.8, 115., 114.5, 112.5, 67.9, 31.8, 29.4, 29.3, 29.2, 29.1, 26.1, 26., 24., 22.7, 14.6, 14.1; MALDI-TOF-MS (m/z): [M] +. HRMS (APCI) (m/z): [M+1] + calcd. for C 139 H 123 F 18 NO 8 S 6, , found; ; HPLC purity: 99.1%, eluting with DCM : hexane = 2 : 8. Supplementary References 1. Gillanders, F., Giordano, L., Díaz, S. A., Jovin, T. M. & Jares-Erijman, E. A. Photoswitchable fluorescent diheteroarylethenes: substituent effects on photochromic and solvatochromic properties. Photochem. Photobiol. Sci. 13, (214). 2. Giordano, L., Jovin, T. M., Irie, M., & Jares-Erijman, E. A. Diheteroarylethenes as thermally stable photoswitchable acceptors in photochromic fluorescence resonance energy transfer (pcfret). J. Am. Chem. Soc. 124, (22). 3. Sauer, M., Hafkens J. & Enderlein, J. Handbook of Fluorescence Spectroscopy and Imaging. Wiley-VCH (211). 4. Geerts, Y. et al. Quaterrylenebis(dicarboximide)s: near infrared absorbing and emitting dyes. J. Mater. Chem. 8, (1998). 5. Li, C. et al. Photocontrolled intramolecular charge/energy transfer and fluorescence switching of tetraphenylethene-dithienylethene-perylenemonoimide triad with donor bridge acceptor structure. Chem-Asian J. 9, (214). 6. Williams, A. B. & Hanson, R. N. Synthesis of substituted asymmetrical biphenyl amino esters as alpha helix mimetics. Tetrahedron 68, (212).