Supporting Information

Transcription

1 Supporting Information Two-Dimensional Organic Single Crystals with Scale Regulated, Phase Switchable, Polymorphism-Dependent and Amplified Spontaneous Emission Properties Zhenyu Zhang, Xiaoxian Song, Shipan Wang, Feng Li, Hongyu Zhang, Kaiqi Ye* and Yue Wang* State Key Laboratory of Supramolecular Structure and Materials, College of Chemistry, Jilin University, 2699 Qianjin Avenue, Changchun , P. R. China S1

2 Table of Contents 1. Experimental Section (Page S2 - Page S4) 2. Figures and Tables (Page S5 - Page S16) S2

3 1. Experimental Section General Information. All starting materials and solvents were purchased from commercial sources. 1 H NMR, 13 C NMR were measured on Bruker Avance 500 MHz spectrometer with tetramethylsilane (TMS) as internal standard. Mass spectra were recorded on GC/MS mass spectrometer. Elemental analyses were performed on a Vario Micro (Elementar) spectrometer. UV-vis absorption spectra were recorded by a Shimadzu UV-2550 spectrophotometer. The emission spectra were recorded by a Shimadzu RF-5301 PC spectrometer. Fluorescence lifetime and quantum efficiency were carried out with Edinburgh fluorescence spectrometer (FLS980) with an integrating sphere. Differential scanning calorimetric (DSC) measurements were performed on a NETZSCH DSC204 instrument at a heating rate of 10 C min 1 under nitrogen. The structural optimization and calculation of relative energies for the potential energy surfaces of S 0 and S 1 states were performed by the CAM-B3LYP functional combined with 6-31G+(d) basis set using Gaussian09 package, D01 version. Single Crystal Structure. Single crystal X-ray diffraction data were collected on a Rigaku R-AXIS RAPID diffractometer using the ω-scan mode with graphitemonochromator Mo Kα radiation. The structures were solved with direct methods using the SHELXTL programs and refined with full-matrix least-squares on F 2. Nonhydrogen atoms were refined anisotropically. The positions of hydrogen atoms were calculated and refined isotropically. The crystallographic information has been deposited with Cambridge Crystallographic Data Centre, and signed to CCDC code for the red polymorph and for the yellow polymorph. ASE measurements. The single crystal was irradiated by the third harmonic (355 nm) of a Nd:YAG (yttrium-aluminum-garnet) laser at a repetition rate of 5 Hz and pulse S3

4 duration of about 10 ns. The energy of the pumping laser was adjusted by using the calibrated neutral density filters. The beam was focused into a stripe whose shape was adjusted to mm 2 by using a cynlindrical lens and a slit. The edge emission and PL spectra of the crystals was detected using a Maya2000 Pro CCD spectrometer. The polarization of light emitted from the edge of the crystal was measured by rotating a polarizer. The gain coefficients are measured by adjusting a slit. All the measurements were carried out at room temperature under ambient conditions. Synthesis. The synthesis of salicylidene(4-dimethylamino)aniline (SADA) was followed the procedure described in previous report. Scheme S1. The synthetic procedure of the SADA. Salicylaldehyde (1.22 g, 10 mmol) and N,N-dimethyl-benzene-1,4-diamine (1.36 g, 10 mmol) was heated in ethanol at 80 C for 4 hours. After cooling to room temperature, the resulting mixture was purified by column chromatography using a mixture of petroleum ether/dichloromethane as the eluent column and then by vacuum sublimation to afford orange solid in 75% yield (1.80 g). 1 H NMR (500 MHz, CDCl 3 ): δ (br, 1H), 8.61 (s, 1H), (m, 4H), 6.99 (d, J = 5 Hz, 1H), 6.91 (t, J = 7.5 Hz, 1H), 6.77 (m, 2H), 3.00 (s, 6H). 13 C NMR (CDCl 3, 500 MHz, ppm): δ 161.0, 157.7, 149.9, 137.2, 132.0, 131.5, 122.2, 119.8, 118.8, 117.0, 112.8, 77.3, 77.0, 76.8, Elemental analysis: found C, 74.92%; H, 6.79%; N, 11.71%; calc. for C 15 H 16 N 2 O: C, 74.97%; H, 6.71%; N, 11.66%. MS m/z: [M + ] (calcd: 240.3). S4

5 2. Figures and Tables Figure S1. The UV-vis absorption and fluorescence emission spectra in CH 2 Cl 2 solution of the compound SADA. Inset: Photographic image of the solution under UV-lighting (λ max = 365 nm) irradiation. Figure S2. The plate-like crystals of the SADA analogues (diameter of the quartz plate: 2 cm). S5

6 Normalized Intensity/ a.u. Normalized Intensity/ a.u Red Polymorph Yellow Polymorph Wavelength/ nm Figure S3. The emission spectra of two polymorphs at 77 K. Red polymorph Yellow polymorph Time/ ns Figure S4. Nanosecond time-resolved photoluminescent dynamic of the two polymorphs. S6

7 Normalized Intensity/ a.u Toluene Solution Yellow Polymorph Wavelength/ nm Figure S5. The emission spectra of the yellow polymorph and in toluene solution at 77 K. S7

8 Figure S6. Crystal structure of the red polymorph. Figure S7. Crystal structure of the yellow polymorph. S8

9 Figure S8. The predicted growth morphology of the compound SADA (a: the red polymorph; b: the yellow polymorph). Table S1. Calculated Attachment Energies for Different Crystal Faces of the red polymoph. hkl d hkl /Å E att (Total)/kcal mol -1 % Total facet area (0 0 2) (1 0 2) (1 1 1) Table S2. Calculated Attachment Energies for Different Crystal Faces of the yellow polymorph. hkl d hkl /Å E att (Total)/kcal mol -1 % Total facet area (0 0 2) (0 1 1) (1 0 1) (1 1 0) The growth morphology method was applied to investigate the shapes of organic molecular crystals in this study. In general, the growth rate of one crystal face is assumed to be proportional to its attachment energy (E att ), that is, the face with lower S9

10 attachment energy is slower growing and hence has more morphological importance. The attachment energy can be calculated by: Where E lattice is the lattice energy of the crystal and E slice is the energy for a growth slice of thickness d hkl, respectively. S10

11 Intensity/ a.u. Red Crystal Simulated Red Crystal Experiment Red Solid Experiment Yellow Crystal Simulated Yellow Crystal Experiment Yellow Solid Experiment theta/ deg Figure S9. XRD patterns of different phase states. Figure S10. The emission spectra of different phase states. S11

12 Normalized Intensity/ a.u. Endothermic red crystal yellow crystal T =105 o C Temperature / o C Figure S11. DSC curves of the two polymorphs microcrystal normal-sized crystal nm 610 nm Wavelength/ nm Figure S12. Absorption spectra of the different sizes crystals of the red polymorph measured by diffuse reflectance spectroscopy. S12

13 Figure S13. The XRD patterns of the red crystals with different sizes and the XRD pattern simulated from single crystal X-ray diffraction data of red emissive crystal. Figure S14. The red polymorph: a) Peak intensity of PL spectra as a function of the pump stripe length at different pump energies; b) The net gain coefficient as a function of wavelength at different pump energies. S13

14 PL intensity/ a.u Theta/ deg Figure S15. Dependence of the intensity of polarized light from the red crystal on the relative polarization angle. S14

15 Figure S16. The yellow polymorph: a) PL spectra as the function of the pump laser energy; b) Dependence of the peak intensity and FWHM of the emission spectra on the pump laser energy; c) Peak intensity of PL spectra as a function of the pump stripe length at different pump energies; d) The net gain coefficient as a function of wavelength at different pump energies. S15

16 Normalized Intensity/ a.u normal-sized crystal microcrystal nm Wavelength/ nm Figure S17. The absorption spectra of the different sizes crystals of the yellow polymorph measured by diffuse reflectance spectroscopy. Figure S18. The ASE performance of red crystals originated from the heat-treated method: a) PL spectra as the function of the pump laser energy; b) Dependence of the peak intensity and FWHM of the emission spectra on the pump laser energy; c) Peak intensity of PL spectra as a function of the pump stripe length at different pump energies; d) The net gain coefficient as a function of wavelength at different pump energies. S16