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1 Electronic Supplementary Material (ESI) for ChemComm. This journal is The Royal Society of Chemistry 214 Supplementary Information for Phosphorescent organoplatinum(ii) complexes with a lipophilic anion: Supramolecular soft nanomaterials through ionic self-assembly and metallophilicity Yong Chen, a,b Chi-Ming Che* a and Wei Lu* c a State Key Laboratory of Synthetic Chemistry, HKU-CAS Joint Laboratory on ew Materials, and Department of Chemistry, The University of Hong Kong, Pokfulam Road, Hong Kong, P. R. China. cmche@hku.hk b Key Laboratory of Photochemical Conversion and Optoelectronic Materials, Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, Beijing 119, P. R. China. c Department of Chemistry, South University of Science and Technology of China, Shenzhen, Guangdong 51855, P. R. China. luw@sustc.edu.cn Characterization data and supplementary photophysical data, diffractograms, and thermograms.

2 Experimental Section: All starting materials were purchased from commercial sources and used as received. The solvents used for synthesis were of analytical grade unless stated otherwise. The solvents used for nanostructure preparations and photophysical measurements were of HPLC grade. The compounds 1 Cl 3 Cl, 1 4 Cl 2 and a A 3 were prepared according to literature methods. Electron-spray ionization (ESI) mass spectra were obtained on a Finnigan MAT 95 mass spectrometer. 1 H MR spectra were recorded with Bruker DRX 3 or Avance 4 FT-MR spectrometers. Elemental analyses were performed by Beijing Institute of Chemistry, Chinese Academy of Sciences. Infrared spectra were recorded on a Bio-Rad FT-IR spectrometer. UV-vis absorption spectra were recorded on a Perkin-Elmer Lambda 19 UV/vis spectrophotometer. Steady-state emission spectra were obtained on a SPEX 1681 Fluorolog-2 series F111AI fluorescence spectrophotometer. Emission lifetime measurements were performed with a Quanta Ray DCR-3 pulsed d:yag laser system (pulse output 355 nm, 8 ns). Luminescent quantum yields were referenced to degassed [Ru(bpy) 3](ClO 4) 2 in acetonitrile ( r =.62) with estimated error of ±15%. TEM and SAED were performed on a Philips Tecnai G2 2 S-TWI transmission electron microscope with an accelerating voltage of 2 kv. The TEM micrographs were taken by Gatan MultiScan Camera Model 794. TEM samples were prepared by depositing a few drops of dispersion on the formvar-coated copper grids and the excess solvent was removed by a piece of filter paper. The SEM images were taken on a Hitachi S-48 field emission scanning electron microscope operating at 3. kv. SEM samples were prepared by drop-casting suspensions onto silicon wafers. o gold or platinum sputtering was applied before SEM observations. The powder XRD patterns were recorded on a Bruker D8 Powder X-ray Diffractometer operating with graphite monochromatized CuKα radiation (λ = Å) and a nickel filter. (1) W. Lu, Y. Chen, V. A. L. Roy, S. S. Y. Chui and C. M. Che, Angew. Chem. Int. Ed., 29, 48, (2). A. Larew, A. R. Van Wassen, K. E. Wetzel, M. M. Machala and S. D. Cummings, Inorg. Chim. Acta, 21, 363, (3) U. Beginn, L. L. Yan, S.. Chvalun, M. A. Shcherbina, A. Bakirov and M. Moller, Liq. Cryst., 28, 35,

3 Pt O 3 S C 12 H 25 O 1 A: MS (ESI): m/z [M + ]; 79.9 [M ]. 1 H MR (4 MHz, CDCl3): δ 9.18 (d, 1H, J = 8.1 Hz), 8.84 (d, 1H, J = 7.9 Hz), 8.66 (d, 1H, J = 5.3 Hz), 8.4 (t, 1H, J = 7.9 Hz), 8.14 (t, 1H, J = 8.1 Hz), (m, 2H), 7.65 (d, 1H, J = 7.9 Hz), (m, 3H), (d, 2H, J = 7.8 Hz), (m, 2H), 6.55 (d, 1H, J = 8.8 Hz), 4.23 (t, 2H, J = 7.2 Hz), 3.96 (t, 4H, J = 6.5 Hz), 2.57 (s, 6H), (m, 6H), (m, 54H),.9.83 (m, 9H). Elemental analysis Calcd for C 67H 97 3O 6PtS: C, 63.48; H, 7.71;, Found: C, 63.2; H, 7.76;, medium (T / K) abs / nm em / nm ( / s) ϕ ( / mol 1 dm 3 cm 1 ) CH 2Cl 2 (298) 24 (286) 53 (1.6).3 27 (sh, 2267) 334 (139) 35 (sh, 933) 4 (sh, 49) Cyclohexane (298) 267 (sh, 2326) 673(.9) (986) 431 (22) 2-MeTHF (77) 715(3.4) Solid (298) 678(.5) Solid (77) 758(1.6)

4 dichloromethane cyclohexane.6 Absorbance.4 Pt O 3 S C 12 H 25 O OC 12H Fig. S1 UV-vis absorption spectra of 1 A in dichloromethane (black line) and cyclohexane (red line). Absorbance Cyclohexane/dichloromethane :1 1:9 2:8 3:7 4:6 5:5 6:4 7:3 8:2 9:1 1: Fig. S2 UV-vis absorption spectra of 1 A in cyclohexane/dichloromethane with v/v from :1 to 1: (concentration ~ mol dm 3 ).

5 Absorbance degree 3 degree 4 degree 5 degree 6 degree 7 degree 8 degree /nm Fig. S3 UV-vis absorption traces of 1 A in decalin (concentration ~ mol dm 3 ) when temperature increases from 2 to 8 o C..5.4 Absorbance nm Fig. S4 UV-vis absorption spectra of 1 A in decalin at 2 o C before (black line) and after (red line) variable temperature experiments.

6 8 6 emission in cyclohexane e x = 43 nm excitation in cyclohexane e m = 673 nm emission in dichloromethane e x = 35 nm excitation in dichloromethane e m = 53 nm Waveleng /nm Fig. S5 Emission and excitation spectra of 1 A in dichloromethane and cyclohexane solution (concentration ~ mol dm 3 ). 4 3 CHX solution 43ex dgs CHX slt DCM solution 35ex dgs DCM slt TOL solution 35ex dgs TOL slt Fig. S6 Emission spectra of 1 A in varying solvent systems.

7 Cyclohexane/dichloromethane :1 1:9 2:8 3:7 4:6 5:5 6:4 7:3 8:2 9:1 1: Fig. S7 Spectroscopic trances for 1 A in cyclohexane/dichloromethane with v/v from :1 to 1: (concentration ~ mol dm 3 ) (λex = 378nm) deg 3 deg 4 deg 5 deg 6 deg 7 deg 8 deg 9 deg back to 2 deg nm Fig. S8 Emission spectral traces of 1 A in decalin (concentration ~ mol dm 3 ) when temperature increases from 2 to 9 o C.

8 cyclohexane, 298 K, e x = 43 nm dichloromethane, 298 K, e x = 35 nm MeTHF, 77 K, ex = 365 nm solid-state, 298 K, ex = 365 nm solid-state, 77 K, ex = 365 nm ormalized Fig. S9 ormalized emission spectra of 1 A in solution and solid state.

9 CL79 Pt O 3 S C 12 H 25 O 2 A: MS (ESI): m/z [M + ]; 79.6 [M ]. 1 H MR (4 MHz, CDCl 3): δ 8.4 (d, 2H, J = 5.6 Hz), 8.14 (t, 2H, 7.8 Hz), 7.81 (d, 2H, J = 8. Hz), 7.68 (d, 1H, J = 8.7 Hz), 7.47 (t, 2H, J = 7.3 Hz), 7.42 (d, 2H, J = 7.7 Hz), 7.36 (t, 1H, J = 7.6 Hz), 7.2 (d, 2H, J = 7.6 Hz), 7.9 (t, 1H, J = 7.7 Hz), 6.54 (d, 1H, J = 8.8 Hz), 4.24 (t, 2H, J = 7.1 Hz), (q, 4H), 2.5 (s, 6H), (m, 6H), (m, 54H),.9.87 (m, 9H). Elemental analysis Calcd for C67H973O6PtS H2O: C, 62.59; H, 7.76;, Found: C, 62.4; H, 7.56;, medium (T / K) abs / nm ( / mol 1 dm 3 cm 1 ) em / nm ( / s) CH2Cl2 (298) 253 (3186) 49 (6.) 277 (2296) 523 (5.8) 288 (2712) 317 (872) 332 (153) 351 (564) 4 (sh, 66) Cyclohexane (298) 357 (435) 493 (4.4) 383 (42) 525 (4.2) 483 (371) 532 (237) 2-MeTHF (77) 486 (7.5) 52 (7.) 72 (5.5) Solid (298) 628 (.8) Solid (77) 657 (2.) ϕ.43.36

10 .6 dichloromethane toluene/dichloromethane = 9:1 toluene Absorbance.4 Pt O 3 S C 12 H 25 O Fig. S1 UV-vis absorption spectra of 2 A in dichloromethane (black line), 9% toluene (red line) and pure toluene (green line). Absorbance Toluene/dichloromethane :1 1:9 2:8 3:7 4:6 5:5 6:4 7:3 8:2 9:1 1: Fig. S11 UV-vis absorption spectra of 2 A in toluene/dichloromethane with v/v from :1 to 1: (concentration ~ mol dm 3 ).

11 dichloromethane, 298 K, ex = 4 nm MeTHF, 77 K, e x = 365 nm MeTHF, 77 K, e x = 575 nm solid-state, 298 K, ex = 365 nm solid-state, 77 K, e x = 365 nm Fig. S12 Emission spectra of 2 A in solution and solid state Toluene/dichloromethane :1 1:9 2:8 3:7 4:6 5:5 6:4 7:3 8:2 9:1 1: Fig. S13 Spectroscopic trances for 2 A in toluene/dichloromethane with v/v from :1 to 1: (concentration ~ mol dm 3 ) (λ ex = 37nm).

12 emission, e x = 35 nm emission, e x = 375 nm emission, e x = 4 nm excitation, em = 482 nm excitation, em = 49 nm Fig. S14 Emission spectra of 2 A in degassed dichloromethane solution with varying excitation wavelength. 2 emission, aerated, ex = 4 nm excitation, e m = 525 nm emission, degassed, e x = 4 nm Fig. S15 Emission and excitation spectra of 2 A in toluene solution.

13 emission, ex = 35 nm emission, ex = 4 nm emission, ex = 51 nm excitation, em = 525 nm excitation, em = 65 nm Fig. S16 Emission spectra of 2 A in an aerated toluene solution with varying excitation wavelength.

14 CL78 Pt O 3 S C 12 H 25 O 3 A: MS (ESI): m/z [M + ]; 79.6 [M ]. 1 H MR (4 MHz, CDCl 3): δ 8.88 (d, 2H, J = 4.8 Hz), (m, 4H), (m, 3H), 7.78 (d, 1H, J = 8.7 Hz), 7.53 (t, 2H, J = 6.3 Hz), (d, 2H, J = 7.6 Hz), (m, 3H), 6.67 (d, 1H, J = 8.8 Hz), 4.28 (t, 2H, J = 7. Hz), (q, 4H), (m, 6H), (m, 54H), (m, 9H). Elemental analysis Calcd for C65H933O6PtS H2O CH2Cl2: C, 59.4; H, 7.28;, Found: C, 58.84; H, 7.16;, medium (T / K) abs / nm em / nm ( / s) ϕ ( / mol 1 dm 3 cm 1 ) CH2Cl2 (298) 242 (2211) 69 (1.) (sh, 1217) 316 (673) 332 (617) 346 (637) 46 (177) Cyclohexane (298) 238 (361) on-emissive 267 (sh, 2665) 331 (777) 48 (358) 2-MeTHF (77) 694 (.9) Solid (298) 688 (.2) Solid (77) 71 (1.1)

15 .8 dichloromethane cyclohexane.6 Absorbance.4 Pt O 3 S C 12 H 25 O Fig. S17 UV-vis absorption spectra of 3 A in dichloromethane (black line) and cyclohexane (red line). Absorbance Cyclohexane/dichloromethane :1 1:9 2:8 3:7 4:6 5:5 6:4 7:3 8:2 9:1 1: Fig. S18 UV-vis absorption spectra of 3 A in cyclohexane/dichloromethane with v/v from :1 to 1: (concentration ~ mol dm 3 ).

16 75 6 emission, dichloromethane, 298 K, ex = 445 nm excitation, dichloromethane, 298 K, e m = 69 nm emission, MeTHF, 77 K, e x = 47 nm emission, solid-state, 298 K, ex = 42 nm emission, solid-state, 77 K, ex = 42 nm Fig. S19 Emission and excitation spectra of 3 A in solution and solid state Cyclohexane/dichloromethane :1 1:9 2:8 3:7 4:6 5:5 6:4 7:3 8:2 9:1 1: Fig. S2 Spectroscopic trances for 3 A in cyclohexane/dichloromethane with v/v from :1 to 1: (concentration ~ mol dm 3 ) (λ ex = 445nm).

17 CL8 Pt Cl O 3 S C 12 H 25 O 4 A: MS (ESI): m/z [M + ]; 71. [M ]. 1 H MR (4 MHz, CDCl 3): δ 8.9 (d, 2H, J = 8.2 Hz), 8.84 (d, 4H, J = 7.5 Hz), 8.34 (t, 1H, J = 8.1 Hz), 8.19 (t, 2H, J = 8. Hz), (d, 1H, J = 8.7 Hz), 7.68 (t, 2H, J = 6.9 Hz), 6.66 (d, 1H, J = 8.8 Hz), 4.26 (t, 2H, J = 7. Hz), (q, 4H), (m, 6H), (m, 54H),.9.83 (m, 9H). Elemental analysis Calcd for C57H88Cl3O6PtS 2H2O: C, 56.58; H, 7.66;, Found: C, 56.84; H, 7.5;, medium (T / K) abs / nm ( / mol 1 dm 3 cm 1 ) em / nm ( / s) CH2Cl2 (298) 258 (1963) on-emissive 284 (1918) 38 (1125) 321 (785) 335 (745) 352 (529) 383 (168) 4 (155) Cyclohexane (298) 256 (2385) 63 (.5) 282 (sh, 1838) 66 (.5) 333 (13) 487 (168) 2-MeTHF (77) 628 (4.) Solid (298) 64 (.3) 66 (.3) Solid (77) 642 (2.5) ϕ.4

18 .8 dichloromethane cyclohexane Absorbance.6.4 Pt Cl O 3 S C 12 H 25 O Fig. S21 UV-vis absorption spectra of 4 A in dichloromethane (black line) and cyclohexane (red line). Absorbance Cyclohexane/dichloromethane :1 1:9 2:8 3:7 4:6 5:5 6:4 7:3 8:2 9:1 1: Fig. S22 UV-vis absorption spectra of 4 A in cyclohexane/dichloromethane with v/v from :1 to 1: (concentration ~ mol dm 3 ).

19 5 4 emission, cyclohexane, 298 K, ex = 36 nm excitation, cyclohexane, 298 K, em = 66 nm emission, MeTHF, 77 K, ex = 365 nm emission, solid-state, 298 K, ex = 365 nm emission, solid-state, 77 K, e x = 365 nm Fig. S23 Emission and excitation spectra of 4 A in solution and solid state Cyclohexane/dichloromethane :1 1:9 2:8 3:7 4:6 5:5 6:4 7:3 8:2 9:1 1: Fig. S24 Spectroscopic trances for 4 A in cyclohexane/dichloromethane with v/v from :1 to 1: (concentration ~ mol dm 3 ) (λ ex = 358 nm).

20 Fig. S25 DSC thermograms of 2 A and optical textures of 2 A between two crossed polarizers. Fig. S26 DSC thermograms of 3 A and optical textures of 3 A between two crossed polarizers. Fig. S27 DSC thermograms of 4 A and optical textures of 4 A between two crossed polarizers.

21 l 4.87 Å Diffraction / A. U Å l/ Å 6.1 Å l/ Å l/ Å l/ Å l/6 6.8 Å l/ Å 3.42 Å x / degree Fig. S28 XRD diffraction pattern of 2 A at 25 o C. Diffraction / A. U. % (3 o ) % (18 o ) % (19 o ) % (2 o ) % (21 o ) % (2 o ) % (19 o ) % (18 o ) % (3 o ) % (1 o ) % (18 o ) % (19 o ) % (2 o ) % (21 o ) % (2 o ) % (19 o ) % (18 o ) % (3 o ) / degree Fig. S29 Variable-temperature XRD diffraction pattern of 2 A in the low-angle region.

22 l 4.7 Å Diffraction / A. U l/ Å l/ Å l/ Å l/ Å l/ Å l/7 5.6 Å x / degree Fig. S3 XRD diffraction pattern of 3 A at 25 o C. Diffraction / A. U. % (3 o ) % (9 o ) % (15 o ) % (18 o ) % (19 o ) % (18 o ) % (15 o ) % (9 o ) % (3 o ) % (9 o ) % (15 o ) % (18 o ) % (19 o ) % (18 o ) % (15 o ) % (9 o ) % (3 o ) / degree Fig. S31 Variable-temperature XRD diffraction pattern of 3 A in the low-angle region.

23 l Å Diffraction / A. U Å l/ Å l/ Å l/4 l/ Å 7.3 Å x S32 XRD diffraction pattern of 4 A at 25 o C. 2 / degree Fig. Diffraction / A. U / degree 3 o 16 o 17 o 175 o 18 o 17 o 3 o 7 o 9 o 16 o 17 o 175 o 18 o 17 o 13 o 12 o 11 o 9 o 6 o 3 o Fig. S33 Variable-temperature XRD diffraction pattern of 4 A in the low-angle region.