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1 Supporting nformation Chromism Based on Supramolecular H-bonds Xiaowei Yu,, Chuanlang Zhan, *, Xunlei Ding, Shanlin Zhang, Xin Zhang, Huiying Liu, Lili Chen, Yishi Wu, Hongbing Fu, Shenggui He, *, Yan Huang, *, and Jiannian Yao, * Beijing National Laboratory for Molecular Sciences, CS Key Laboratory of Photochemistry, nstitute of Chemistry, Chinese cademy of Sciences, Beijing 18, P. R. China. Tel/Fax: / , (C.Z.) clzhan@iccas.ac.cn, (J.Y.) jnyao@iccas.ac.cn. State Key Laboratory of Materials-Oriented Chemical Engineering, College of Chemistry and Chemical Engineering, Nanjing University of Technology, Nanjing 219, PR China. huangy@njut.edu.cn. Beijing National Laboratory for Molecular Sciences, State Key Laboratory for Structural Chemistry of Unstable and Stable Species, nstitute of Chemistry, Chinese cademy of Sciences, Beijing 18, P. R. China. shengguihe@iccas.ac.cn. Contents 1. nstruments and methods.7 2. DFT calculations Supporting figures...7 Fig. S1..7 Fig. S2..7 Fig. S3..8 Fig. S4..9 Fig. S5..1 Fig. S6..12 Fig. S7..14 Fig. S8..16 Fig. S9..16 Fig. S1 17 Fig. S11 18 Fig. S12 19 Fig. S Supporting tables.2 Table S1 2 Table S2...2 Table S3...2 Table S4...2 Table S Table S Table S References. 21

2 1. nstruments and methods The UV-visible absorption spectra were measured with a Shimadzu UV-161PC double-beam spectrophotometer. ll spectroscopic measurements were carried out at room temperature. Fluorescence spectra were measured using F-45 (Hitachi). For the measurements of absorption spectra, we used a quartz cell with a typical optical length of 1 cm. nd the fluorescence spectra were measured using a quartz cell with an optical length of 1 cm and a reflection measurement along the 45 direction relative to the excitation light direction was used to eliminate re-absorbing phenomena from high concentrations. Fluorescence kinetics were measured using a picosecond timeresolved fluorescence apparatus. 1 1 H NMR and 13 C NMR spectra were recorded on a Bruker VNCE 4 or VNCE spectrometer and referenced to solvent signals. COSY, NOESY, HSQC and HMBC spectra were recorded on a Brucker VNCE spectrometer and referenced to solvent signals. For NMR experiments, the d 1 -TF instead of the normal TF was used, mixing with 1ml of d 2 -. The electrochemical cyclic voltammetry (CV) was performed using a Zahner M6e electrochemical workstation in a.1 mol/l tetrabutylammonium hexafluorophosphate (Bu 4 NPF 6 ) dichloromethane () solution with a scan speed at.1 V/s. Pt wire and g/gcl were used as the counter and reference electrodes, respectively. 2. DFT calculations Computational details are presented as follows: Density functional theory (DFT) calculations were performed using the Gaussian 3 program 2 with the B3LYP exchange-correlation functional. 3 ll-electron triple-ξ valence basis sets with polarization functions (6-311G**) 4 are used for all atoms. Geometry optimizations were performed with full relaxation of all atoms. Calculations were performed in gas phase without solvent effects. Charge distribution of the molecules was calculated by natural population analysis Supporting figures Fig. S1. bsorption spectra of the M solution of PDs 1 (a), 2 (b) and 3 (c) upon titration of TF. (c) (a).8 PD 1 [TF] (b) 1. PD 2 n TF /n 1 = 1, (c) 1.5 PD 3.6 [TF] 1. n TF /n 1 = 1, [TF].4 n TF /n 1 = 1, n TF /n 1 =5, n TF /n 1 =5, 4 5. n TF /n 1 =5, 4 5 Fig. S2. Fluorescence spectra of the M solution of PDs 1 (a), 2 (b) and 3 (c) upon titration of TF. (a) 9 PD 1 3 [TF] Fluorescence quench: 86/13.4=6.1 n TF /n 1 = 1, n TF /n 1 =5, (b) 9 3 [TF] PD 2 Fluorescence quench: 72/23.5=3.6 n TF /n 1 = 1, n TF /n 1 =5, (c) [TF] PD 3 Fluorescence quench: 722/378=1.9 n TF /n 1 = 1, n TF /n 1 =5,

3 Fig. S3. 1 H NMR spectra of the -d 2 solution of TF (green line, [TF]=1 1-3 M) and PDs 1 (a and b), 2 (c-f) and 3 (g and h) ([PD]=1 1-3 M) as (black line), 1 (red line), 1 (blue line) and 1 (pink line) equivalences of TF was added, respectively. ssignments of the perylene-hs are supported by the COSY, H-H NOE, HSQC and HMBC spectra of PD 1 (Figure S5), 2 (Figure S6) and 3 (Figure S7) in d 2 -. PD 1 PD 2: The set of the weak signals are originated from the 1,6-4-tert-butylphenoxyl PD derivatives.

4 PD 3 Fig. S4. 13 C NMR spectra of the -d 2 solution of TF (green line, [TF]=1 1-3 M) and PDs 1 (a), 2 (b), and 3 (c) ([PD]=1 1-3 M) as (black line), 1 (red line), 1 (blue line) and 1 (pink line) equivalence of TF is added, respectively. ssignments of the perylene carbons are supported by the COSY, H-H NOE, HSQC and HMBC spectra of PD 1 (Figure S5), 2 (Figure S6) and 3 (Figure S7) in d 2 -. PD 1 PD 2 PD 3

5 Fig. S5. COSY, H-H NOESY, HSQC and HMBC spectra of the -d 2 solution of PD 1 ([1]=1 1-3 M). COSY NOE

6 HSQC HMBC

7 Fig. S6. COSY, H-H NOESY, HSQC and HMBC spectra of the -d 2 solution of PD 2 ([2]=1 1-3 M). COSY NOE

8 HSQC HMBC

9 Fig. S7. COSY, H-H NOESY, HSQC and HMBC spectra of the -d 2 solution of PD 3 ([3]=1 1-3 M). COSY NOE

10 HSQC HMBC

11 Fig. S8. The static potential out of the PD 1 molecule: More red means more easily H-bonding with the TF molecule. This figure shows that the imide C=O is more red than the bridged O- atom, indicating that the imide C=O is more easily H-bonded with the TF molecule. Fig. S9. Cyclic voltammetry of PDs 1, 2, and 3 after addition of, 1, and 1 equivalence of TF into the M solution in with.1 M Bu 4 NPF 6 and a scanning rate of.1 V/s. 1 µ PD equiv. TF PD equiv. TF PD 1 + equiv. TF 2 µ PD equiv. TF PD equiv. TF PD 2 + equiv. TF Current /µ Current /µ Ptential (V) Potential/V µ 2 PD equiv. TF PD equiv. TF PD 3 + equiv. TF 2 µ PD 1 + equiv. TF PD 2 + equiv. TF PD 3 + equiv. TF Current /µ 1.63 V Current /µ Potential/V Ptential (V)

12 Fig. S1. bsorption spectra of the M solution of PD 1 (a), PD 2 (b), and PD 3 (c) without or with addition of 5, equivalence of TF, TCl,, TFOH, and EtOTF, respectively. (a).5.4 TCl TF (a).5 +EtOTF +TFEtOH.4 +TF (b) TCl +TF (b).6.45 EtOTF TFEtOH TF (c) TCl +TF (c) 1. EtOTF.8 TFEtOH TF

13 Fig. S11. Fluorescence spectra of the M solution of PD 1 (a and b), PD 2 (c and d), and PD 3 (e and f) without or with addition of 5, equivalence of TF, TCl,, TFOH, and EtOTF, respectively. (a) f (/ acid / f f ) 47.1 (1.) 37.6 (.8) 13.8 (.29).19 (.4) + + TCl + TF (b) f ( acid / f f ) 47.1 (1.) 37.5 (.8) 23.1 (.49).19 (.4) +EtOTF +TFEtOH +TF x x (c) f ( acid / f f ) 62.1 (1.) 45.6 (.73) 21.4 (.34).8 (.13) + + TCl + TF (d) f ( acid / f f ) 62.1 (1.) 45. (.72) 31. (.5).8 (.13) +EtOTF +TFEtOH +TF x x (e) 15 1 f ( acid / f f ) (1.) 13.6 (.92) 74.2 (.66) 62.1 (.55) + + TCl + TF (f) 15 1 f ( acid / f f ) (1.) 19. (.97) 18. (.96) 62.1 (.55) +EtOTF +TFEtOH +TF

14 Fig. S12. Fluorescence decay curves measured from the M solution of PDs 1 (a), 2 (b) and 3 (c) upon addition of, 1,, 5, and 5, equiv. of TF inside, respectively. (a) 4 PD 1 Pure solution + 1, equiv. TF + 5, equiv. TF + 5, equiv. TF (b) 9 PD 2 Pure solution + 1, equiv. TF + 5, equiv. TF + 5, equiv. TF Time /ns Time /ns (c) PD 3 Pure solution + 1, equiv. TF + 5, equiv. TF + 5, equiv. TF Time /ns Fig. S13. Fluorescence decay curves measured from the M solution of PD 1 after addition of 5, equiv. of TF (a), TCl (b), (c), TFEtOH (d) and EtOTF (e) inside, respectively. (a) TF 1+TF-Fit τ f =1.2 ns (b) 1 8 τ f =2.5 ns 1+TCl 1+TCl-Fit (c) Fit τ f =6.57 ns Time /ns Time /ns Time /ns (d) 9 1+TFEtOH 1+TFEtOH-Fit (e) 9 1+EtOTF 1+EtOTF-Fit τ f =6.71 ns τ f =6.62 ns Time /ns Time /ns

15 4. Supporting tables Table S1. Calculated H-bonding energy (ev) of one or two TF molecules onto the H-bonding sites of the imide C=O, imide N atom, and the bridged O- atom of PD 1, respectively. TF molecules H-bonding site mide C=O Bridged O- mide N One TF molecule Energy (ev) Two TF molecule H-bonding site mide C=O + C=O mide C=O + Bridged O- / Energy (ev) *.6 1. = / Table S2. Electrochemical data of PDs 1, 2, and 3 after addition of, 1, and 1 equivalences of TF, respectively. n TF/n PD PD 1 PD 2 PD 3 E Red (V) E Ox (V) E Red (V) E Ox (V) E Red (V) E Ox (V) 1.22, , 1.36, , , ,.69 /, /, 1.86 (1.63 [a] ) 1.98, , 1.58, , , ,.69 /, /, 1.86 (1.63) ,.76,.46 [b] 1.25, 1.58, ,.71,.46 [b] 1.47, ,.68,.45 [b] /, /, 1.86 (1.63) [a] This value was estimated from the on-set of the oxidation potential (Figure S9) and was used to calculated the energy gap of PD 3 because the calculated energy gap (2.32 ev/534 nm ) was consistent well with the experimental data from the absorption maximum (2.36 ev/525 nm without addition of any TF inside, Figure S1c and Table 1). [b] this potential is originated from the added TF. Table S3. Calculated HOMO and LUMO energy levels (ev), energy gap (ev), absorption maximum (λ a max, nm) and absorption red-shifting ( λ a max, nm) after H-bonding one or two TF molecules onto the imide C=O functions of PD 1. DFT First excited state calculated by time-dependent DFT [c] HOMO (ev) LUMO (ev) E g (ev) λ a max (nm) λ a max (nm) E g (ev) λ a max (nm) λ a max (nm) PD TF-Ot [a] TF-Ot-Ot [b] TF-Ot-Ob [d] Note: [a] one TF molecule H-bonds onto the imide C=O; [b] Two TF molecules with one H-bonded onto one C=O of the imide and the other H-bonded onto another C=O of the imide. H-bonding of the second TF molecule onto the imide C=O accumulates (1) the reduction of the energy gap and further the red-shifting of the absorption, as revealed from the time-dependnet DFT calculation results and (2) the depressions of the HOMOs and LUMOs energy levels, as revealed from the DFT calculation results; [c] Time-dependent DFT (TD-DFT) calculations support the observations of red-shifting for absorption spectra when TF is H-bonded, and the red-shifting degree agrees well with the data calculated from the HOMO and LUMO values (and also the experimental values). The values and nm by TD-DFT is more consistent with the experimental values than and nm that are calculated from the HOMO and LUMO values. [d] lthough H-bonding and the second TF molecule onto the bridged O atom enlarges the energy gap, E g, yielding the blue-shifting of the absorption, sum of the effects

16 from the H-bonding of the TF molecules onto the imide C=O and onto the bridged O atom both reduce the energy gap, resulting in the red-shifting. Table S4. Fluorescent lifetime (τ f ) of PD 1 after addition of 5, equivalences of TF, TCl,, TFEtOH, and EtOTF, respectively. n pure +TF +TCl + +TFEtOH +EtOTF τ f (ns) 6.62± ±.1 2.5± ± ± ±.11 6,62/τ f acid f/ f References 1. Liu, H. Y.; Jia, H.; Wang, L. F.; Wu, Y. S.; Zhan, C. L.; Fu, H. B.; Yao, J. N. Phys. Chem. Chem. Phys. 212, DO: 1.139/c2cp41288h. 2. Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M..; Cheeseman, J. R.; Montgomery Jr., J..; Vreven, T.; Kudin, K. N.; Burant, J. C.; Millam, J. M.; yengar, S. S.; Tomasi, J.; Barone, V.; Mennucci, B.; Cossi, M.; Scalmani, G.; Rega, N.; Petersson, G..; Nakatsuji, H.; Hada, M.; Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.; shida, M.; Nakajima, T.; Honda, Y.; Kitao, O.; Nakai, H.; Klene, M.; Li, X.; Knox, J. E.; Hratchian, H. P.; Cross, J. B.; Bakken, V.; damo, C.; Jaramillo, J.; Gomperts, R.; Stratmann, R. E.; Yazyev, O.; ustin,. J.; Cammi, R.; Pomelli, C.; Ochterski, J. W.; yala, P. Y.; Morokuma, K.; Voth, G..; Salvador, P.; Dannenberg, J. J.; Zakrzewski, V. G.; Dapprich, S.; Daniels,. D.; Strain, M. C.; Farkas, O.; Malick, D. K.; Rabuck,. D.; Raghavachari, K.; Foresman, J. B.; Ortiz, J. V.; Cui, Q.; Baboul,. G.; Clifford, S.; Cioslowski, J.; Stefanov, B. B.; Liu, G.; Liashenko,.; Piskorz, P.; Komaromi,.; Martin, R. L.; Fox, D. J.; Keith, T.; l-laham, M..; Peng, C. Y.; Nanayakkara,.; Challacombe, M.; Gill, P. M. W.; Johnson, B.; Chen,W.; Wong, M. W.; Gonzalez, C.; Pople, J..; Gaussian 3, Revision C.2, Gaussian, nc., Wallingford CT, a) Lee, C. T.; Yang, W. T.; Parr, R. G. Phys. Rev. B 1988, 37, ; b) Becke,. D. J. Chem. Phys. 1993, 98, Krishnan, R.; Binkley, J. S.; Seeger, R.; Pople, J.. J. Chem. Phys. 198, 72, Glendening, E. D.; Reed,. E.; Carpenter, J. E.; Weinhold, F. NBO Version 3.1, 1995.