Supplementary Figure 1. Mass spectrum (top) and 1 H NMR spectrum (bottom, in CDCl 3 ) of [ppy 2 IrNH] + PF 6 -.

Transcription

1 Supplementary Figure 1. Mass spectrum (top) and 1 H NMR spectrum (bottom, in CDCl 3 ) of [ppy 2 IrNH] + PF

2 Supplementary Figure 2. Mass spectrum (top) and 1 H NMR spectrum (bottom, in CDCl 3 ) of [ppy 2 IrNH] + BF

3 Supplementary Figure 3. Mass spectrum (top) and 1 H NMR spectrum (bottom, in CDCl 3 ) of [ppy 2 IrNH] + I -. 3

4 Supplementary Figure 4. Mass spectrum (top) and 1 H NMR spectrum (bottom, in CDCl 3 ) of [ppy 2 IrNH] + Br -. 4

5 Supplementary Figure 5. Mass spectrum (top) and 1 H NMR spectrum (bottom, in CDCl 3 ) of [ppy 2 IrNH] + Cl -. 5

6 Supplementary Figure 6. Mass spectrum (top) and 1 H NMR spectrum (bottom, in CDCl 3 ) of [pq 2 IrNH] + PF

7 Supplementary Figure 7. Mass spectrum (top) and 1 H NMR spectrum (bottom, in CDCl 3 ) of [pq 2 IrNH] + I -. 7

8 Supplementary Figure 8. Mass spectrum (top) and 1 H NMR spectrum (bottom, in CDCl 3 ) of [pq 2 IrNH] + Br -. 8

9 Supplementary Figure 9. Mass spectrum (top) and 1 H NMR spectrum (bottom, in CDCl 3 ) of [pq 2 IrNH] + Cl -. 9

10 Supplementary Figure 10. Mass spectrum (top) and 1 H NMR spectrum (bottom, in CDCl 3 ) of [ppy 2 IrNEt] + PF

11 Supplementary Figure 11. Mass spectrum (top) and 1 H NMR spectrum (bottom, in CDCl 3 ) of [ppy 2 IrNEt] + Br -. 11

12 Supplementary Figure 12. FTIR spectra of [ppy 2 IrNH] + A -. The FTIR spectrum of [ppy 2 IrNH] + PF 6 - shows sharp N-H stretching at 3357 cm -1, whereas, for other complexes, the N-H stretching peak is broad and red-shifted due to the stronger hydrogen bond. 12

13 Supplementary Figure 13. X-ray crystallographic analysis of [ppy 2 IrNH] + PF 6 - at 296 K (CCDC ). a) ORTEP structure of a 1D chain of the tetrameric [ppy 2 IrNH] + PF 6 - along the a axis. b) Molecular packing viewed along the a axis. c) Molecular packing viewed along the c axis. 13

14 Supplementary Figure 14. X-ray crystallographic analysis of [ppy 2 IrNH] + PF 6 - at 120 K (CCDC ). a) ORTEP structure of a 1D chain of the tetrameric [ppy 2 IrNH] + PF 6 - along the a axis. b) Molecular packing viewed along the a axis. c) Molecular packing viewed along the c axis. 14

15 Supplementary Figure 15. X-ray crystallographic analysis of [ppy 2 IrNH] + BF 4 - at 296 K (CCDC ). a) ORTEP structure of a 1D chain of the tetrameric [ppy 2 IrNH] + BF 4 - along the c axis. b) Molecular packing viewed along the a axis. c) Molecular packing viewed along the c axis. 15

16 Supplementary Figure 16. X-ray crystallographic analysis of [ppy 2 IrNH] + Br - at 296 K (CCDC ). a) ORTEP structure of the dimeric [ppy 2 IrNH] + Br -. b) Molecular packing viewed along the a axis. c) Molecular packing viewed along the b axis. d) Molecular packing viewed along the c axis. 16

17 Supplementary Figure 17. Emission lifetime decay profiles of [ppy 2 IrNH] + A - (10 μm) monitored at emission maxima (λ ex = 379 nm, in deaerated CH 2 Cl 2 at 296 K). 17

18 Supplementary Figure 18. Absorption spectra of [ppy 2 IrNH] + A - (10 μm) in air-equilibrated CH 2 Cl 2 at 296 K. 18

19 Supplementary Figure 19. Molecular orbitals (iso-surface plots) of [ppy 2 IrNH] + and [pq 2 IrNH] +. 19

20 Supplementary Figure 20. Cyclic voltammograms of [ppy 2 IrNH] + A - and [ppy 2 IrNEt] + PF 6 - (scan rate = 100 mv s -1 ). 20

21 Supplementary Figure 21. Photographs of [ppy 2 IrNH] + PF 6 - before and after exerting a pressure of 20 MPa in an IR pellet press under excitaiton by UV lamp. 21

22 Supplementary Figure H NMR spectra of [ppy 2 IrNH] + PF 6 - -G, [ppy 2 IrNH] + PF 6 - -Y and [ppy 2 IrNH] + PF 6 - -Y-CH 2 Cl 2. 22

23 Supplementary Figure 23. Mass spectrum of [ppy 2 IrNH] + PF 6 - -Y. 23

24 Supplementary Figure 24. The photographs of [ppy 2 IrNH] + PF 6 - in CH 3 CN (200 μm) upon applying a voltage of 15 V for 0-6 min under excitaiton by a UV lamp. 24

25 Supplementary Figure H NMR spectra of [ppy 2 IrNH] + PF 6 - in CD 3 CN during the electrochromic phosphorescence experiment. 25

26 Supplementary Figure 26. Mass spectrum of [ppy 2 IrNH] + PF 6 - near cathode after the treatment of a voltage of 15 V for 3 min. 26

27 Supplementary Figure F NMR spectra of [ppy 2 IrNH] + PF 6 - in CD 3 CN during electrochromic phosphorescence experiment. 27

28 Supplementary Figure 28. The photographs of [ppy 2 IrNEt] + PF 6 - in CH 3 CN (200 μm) before and after applying a voltage of 20 V for 10 min under excitaiton by a UV lamp. 28

29 Supplementary Figure 29. Photographs of the BMIM + PF 6 - ionic liquid with different contents (0, 4, 8 and 10 wt%) of silica nanoparticles. 29

30 Supplementary Figure 30. The emission spectra of [ppy 2 IrNH] + PF 6 - (10 μm) in CH 2 Cl 2, CH 3 CN, and BMIM + PF 6 - without and with silica nanoparticles (λ ex = 365 nm) at 296 K. 30

31 Supplementary Figure 31. Emission spectra of [ppy 2 IrNH] + PF 6 - in BMIM + PF 6 - without (a) and with (b) silica nanoparticles before (1) and after (2) applying a voltage. Inset: photographs under excitaion by a UV lamp. 31

32 Supplementary Figure 32. Chemical structure of the BODIPY dye used in this work. 32

33 Supplementary Figure 33. a) Normalized UV/Vis absorption spectrum of the BODIPY dye and emission spectrum of [ppy 2 IrNH] + PF 6 - in ionic liquids. b) Normalized UV/Vis absorption spectrum of [ppy 2 IrNH] + PF 6 - and emission spectrum of the BODIPY dye in ionic liquids. c) Emission lifetime decay profiles of the mixture of the BODIPY dye and [ppy 2 IrNH] + PF 6 - in ionic liquids with different concentrations of the BODIPY dye (λ ex = 379 nm, air-equilibrated). d) Emission spectra of the mixture of the BODIPY dye (100 μm) and [ppy 2 IrNH] + PF 6 - (10 μm) in air-equilibrated ionic liquids: black line, no delay; red line, delay time = 100 ns, λ ex = 379 nm. 33

34 Supplementary Figure 34. Excitation spectra of the BODIPY dye (100 M) and [ppy 2 IrNH] + PF 6 - (10 M) in ionic liquids monitored at their emission maxima, respectively. 34

35 Supplementary Figure 35. Fabrication of the quasi-solid data encryption device (left) and the probe station (right) used for electrochromic phosphorescence experiments: (i) [ppy 2 IrNH] + - PF 6 in BMIM + PF - 6 ; (ii) the BODIPY dye in BMIM + PF - 6 ; (iii) [ppy 2 IrNH] + - PF 6 and the BODIPY dye in BMIM + PF - 6 ; (iv) [ppy 2 IrNH] + - PF 6 and the BODIPY dye in BMIM + PF - 6 containing silica nanoparticles; (v) film coated on ITO glass. 35

36 Supplementary Table 1. Summary of X-ray Crystallographic Data for [ppy 2 IrNH] + PF 6 -, [ppy 2 IrNH] + BF 4 - and [ppy 2 IrNH] + Br -. Complex [ppy 2 IrNH] + PF 6 - [ppy 2 IrNH] + PF 6 - [ppy 2 IrNH] + BF 4 - [ppy 2 IrNH] + Br - Empirical Formula C 34 H 25 F 6 IrN 5 P C 34 H 25 F 6 IrN 5 P C 34 H 25 F 4 IrN 5 B C 34 H 25 BrIrN 5 Formula Weight Crystal System orthorhombic orthorhombic monoclinic triclinic Space Group Pbca Pbca P21/c P1 a (Å) (11) (18) 8.716(16) (3) b (Å) (17) (3) (6) (4) c (Å) (3) (5) (2) (4) α ( o ) (5) β ( o ) (3) (4) γ ( o ) (4) V (Å 3 ) (10) (17) (10) (9) Z value D(calcd) (g cm -3 ) Temperature (K) μ (mm -1 ) F(000) Scan Type ω-2θ ω-2θ ω-2θ ω-2θ R 1, wr , , , , Goodness of fit

37 Supplementary Table 2. Selected Bond Lengths and Hydrogen Bonding Distances in Single Crystal Structrues of [ppy 2 IrNH] + PF 6 - at 296 K and 120 K, [ppy 2 IrNH] + BF 4 - and [ppy 2 IrNH] + Br - at 296 K. [ppy 2 IrNH] + PF - 6 (296 K) Bond lengths (Å) Ir1 C (5) Ir1 N (5) Ir1 C (5) Ir1 N (4) Ir1 N (5) Ir1 N (5) Hydrogen bonding distance (Å) N2 F4 3.08(1) [ppy 2 IrNH] + PF - 6 (120 K) Bond lengths (Å) Ir1 C (7) Ir1 N (7) Ir1 C (9) Ir1 N (7) Ir1 N (7) Ir1 N (7) Hydrogen bonding distance (Å) N3 F4 3.01(1) [ppy 2 IrNH] + BF - 4 (296 K) Bond lengths (Å) Ir1 C (7) Ir1 N (4) Ir1 C (6) Ir1 N (5) Ir1 N (4) Ir1 N (6) Hydrogen bonding distance (Å) N11 F (9) [ppy 2 IrNH] + Br - (296 K) Bond lengths (Å) Ir1 C (2) Ir1 N4 2.06(1) Ir1 C1 2.00(1) Ir1 N2 2.13(1) Ir1 N3 2.06(2) Ir1 N1 2.28(2) Hydrogen bonding distance (Å) N5 Br1 3.24(2) 37

38 Supplementary Table 3. Electrochemical Data for [ppy 2 IrNH] + A - and [ppy 2 IrNEt] + PF 6 - at 296 K. a E re onset (V) E ox onset (V) [ppy 2 IrNH] + - PF b 0.87 c [ppy 2 IrNH] + - BF b 0.87 c [ppy 2 IrNH] + I b 0.88 c [ppy 2 IrNH] + Br b 0.87 c [ppy 2 IrNH] + Cl b 0.87 c [ppy 2 IrNEt] + - PF c 0.87 c a Electrochemical data were obtained in a typical three-electrode cell with a working electrode (glassy carbon electrode), a reference electrode [Ag/Ag + ], referenced against ferrocene/ferrocenium (FOC), and a counter electrode (Pt wire) under a nitrogen atmosphere at a sweeping rate of 100 mv s -1 in a solution of 0.1 M tetra-n-butyl-ammounium hexafluorophosphate ( t Bu 4 NPF 6 ) in acetonitrile. b Irreversible wave. c Reversible couple. 38