Supporting Information Controlling Growth of Molecular Crystal Aggregates with Distinct Linear and Nonlinear Optical Properties Yusen Luo,,,# Chunqing Yuan,,# Jialiang Xu*, Yongjun Li*, Huibiao Liu, Sergey Semin, & Theo Rasing, & Wensheng Yang *, and Yuliang Li Beijing National Laboratory for Molecular Sciences (BNLMS), CAS Key Laboratory of Organic Solids, Institute of Chemistry, CAS Research/Education Center for Excellence in Molecular Sciences, Chinese Academy of Sciences, Beijing 100190, P. R. China. State Key Laboratory for Supramolecular Structures and Materials, College of Chemistry, Jilin University, Changchun 130012, P. R. China. School of Chemical Engineering and Technology, Tianjin University, Yaguan Road 135, Tianjin 300350, P. R. China. & Radboud University, Institute for Molecules and Materials (IMM), Heyendaalseweg 135, 6525 AJ Nijmegen, The Netherlands. # These authors contribute equally. Corresponding Authors: E-mail: jialiang.xu@tju.edu.cn, liyj@iccas.ac.cn, wsyang@jlu. edu.cn S-1
Materials. All chemical reagents were purchased from Alfa Aesar or Aldrich Chemicals and used without further purification. Column chromatography was performed on silica gel (size 200 300 mesh). Characterizations and Measurements. 1 H NMR spectra were obtained at Bruker ARX400 spectrometer using tetramethylsilane (TMS) as the internal standard. EI mass spectrometric measurements were obtained on the SHIMADZU GCMS-QP2010 pulse spectrometer. Single crystal X-ray diffraction data were collected on a Rigaku Saturn X-ray diffractometer with graphite-monochromator Mo-Kα radiation (λ = 0.71073 Å) at 173 K. Intensities were collected for absorption effects using the multi-scan technique SADABS. The structures were solved by direction methods and refined by a full matrix least squares technique based on F2 using SHELXL 97 program (Sheldrick, 1997). The extended packing plots and data from crystal packing were obtained using the software Mercury 1.4.1. SEM images were taken from Hitachi S-4800 microscopes at an accelerating voltage of 15 kv. TEM images were taken from a JEOL JEM-1011 microscope at an accelerating voltage of 100 kv. The aggregate nanostructures of the DBD and BBD were prepared in silicon slide for SEM and copper grids for TEM. UV-Vis spectra were measured on a Hitachi U-3010 spectrometer. The fluorescence spectra were measured on a Hitachi F-4500 spectrometer. Fluorescence images of the microstructures were taken by using a laser-based fluorescence microscope (Olympus IX81) and an intensified charge-coupled device (CCD, Olympus DP71) detection system. The NLO measurements were studied using a laser scanning microscope with the pump at 800 S-2
nm (Spectra Physics Mai-Tai, pulse width: 100 fs, repetition rate: 82 MHz) in a reflection geometry with incident and detection angles both at 45.The NLO signal was led through a fiber waveguide to a monochromator (Princeton Instruments), and sent to be detected by a charge-coupled device (CCD) or photomultiplier tube (PMT). The polarization state of the incident beam was controlled with a half-wave-plate. Table S1. Crystal data and structure refinement for DBD and BBD. Identification code mx2989 mx3432 Empirical formula C 24 H 12 N 2 O 2 C 26 H 16 N 2 O 4 Formula weight 360.36 420.41 Temperature 173.1500 K 173.1500 K Wavelength 0.71073 Å 0.71073 Å Crystal system, space group Monoclinic, P 1 21/c 1 Monoclinic, C 1 2/c 1 Unit cell dimensions a = 15.039(3) Å α= 90. b = 6.8992(14) Å β= 103.23(3). c = 17.874(4) Å γ = 90. a = 23.162(7) Å α= 90. b = 9.176(3) Å β= 105.992(4). c = 9.967(3) Å γ = 90. Volume 1805.3(7) Å 3 2036.4(10) Å 3 Z, Calculated density 4, 1.326 Mg/m 3 1.371 Mg/m 3 Absorption coefficient 0.086 mm -1 0.094 mm -1 F(000) 744 872 Crystal size 0.35 x 0.31 x 0.07 mm 3 0.13 x 0.12 x 0.05 mm 3 Theta range for data collection 2.434 to 27.498 1.829 to 27.475. Index ranges -19<=h<=15, -8<=k<=8, -19<=l<=23-30<=h<=30, -11<=k<=11, -12<=l<=12 Reflections collected / unique 12342/4120 [R(int) = 0.0591] 7011/2312 [R(int) = 0.0378] S-3
Completeness to theta = 26.000 99.5 % 99.2 % Absorption correction Semi-empirical from equivalents Semi-empirical from equivalents Max. and min. transmission 1.0000 and 0.5547 1.0000 and 0.8088 Refinement method Full-matrix least-squares on F 2 Full-matrix least-squares on F 2 Data / restraints / parameters 4120 / 0 / 253 2312 / 0 / 146 Goodness-of-fit on F^2 1.179 1.154 Final R indices [I>2sigma(I)] R1 = 0.0664, wr2 = 0.1372 R1 = 0.0531, wr2 = 0.1209 R indices (all data) R1 = 0.0772, wr2 = 0.1445 R1 = 0.0593, wr2 = 0.1248 Largest diff. peak and hole 0.215 and -0.191 e.å -3 0.300 and -0.184 e.å -3 S-4
Figure S1. 1 H NMR spectrum of DBD. S-5
Figure S2. 13 C NMR spectrum of DBD. Figure S3. 1 H NMR spectrum of BBD. S-6
Figure S4. TOF MS spectrum and elemental analysis report of BBD. S-7
Figure S5. TOF MS spectrum and elemental analysis report of DBD. S-8
DFT Computations For compounds DBD and BBD, DFT calculations were performed using the Gaussian 09 program. Geometries were optimized in the gas phase using the ωb97xd functional and 6-311g* basis set on all atoms. The geometrical structure and Cartesian coordinates of the compounds DBD and BBD at the ground and excited states are shown in Table S2 and S3, respectively. Table S2. The geometrical structure and Cartesian coordinates of the compound DBD and BBD at the ground states. BBD DBD Row Symbol X Y Z Row Symbol X Y Z 1 C -0.678582 0.005233-0.000093 1 C -0.326565 0.022426-0.701214 2 C -1.368577 1.231018-0.000057 2 C -0.326565 0.022426 0.701214 3 C -0.770195 2.49385-0.00005 3 C 0.913815 0.026082 1.346808 4 C 0.65074 2.54246-0.000087 4 C 2.151621 0.033341 0.703286 5 C 1.33399 1.323535-0.000118 5 C 2.151621 0.033341-0.703286 6 C 0.729171 0.053335-0.000122 6 C 0.913815 0.026082-1.346808 7 C -1.685408-1.005553-0.000138 7 O 0.744313 0.01924-2.683327 8 C -2.894516-0.360652-0.000073 8 O 0.744313 0.01924 2.683327 9 H -1.531388-2.071734-0.000175 9 C -1.300867 0.01156-1.746106 10 O -2.708037 1.010832 0.000027 10 H -2.373671-0.000929-1.634576 S-9
11 C 1.802326-0.886339-0.000218 11 C -1.300867 0.01156 1.746106 12 H 1.72132-1.960486-0.000288 12 H -2.373671-0.000929 1.634576 13 C 2.964726-0.160618-0.00006 13 C -1.01928-0.00838-4.31498 14 O 2.685422 1.194903-0.000051 14 C -2.375113 0.090587-4.646567 15 C -4.26923-0.823821-0.000022 15 C -0.070577-0.128826-5.334992 16 C -5.33865 0.082555 0.000095 16 C -2.771365 0.067384-5.975328 17 C -4.563836-2.20205-0.000091 17 H -3.122833 0.189092-3.866843 18 C -6.658357-0.356293 0.000134 18 C -0.474608-0.15097-6.663308 19 H -5.138084 1.145956 0.000168 19 H 0.982495-0.207422-5.09166 20 C -5.870947-2.646435-0.000051 20 C -1.823222-0.053945-6.987599 21 H -3.762475-2.930956-0.000132 21 H -3.82475 0.146717-6.221671 22 C -6.934615-1.728308 0.000058 22 H 0.269637-0.244719-7.446796 23 H -7.456107 0.373252 0.000253 23 H -2.135638-0.071661-8.026326 24 H -6.100484-3.704917-0.000071 24 C -0.605891 0.009786-2.915362 25 C 4.368183-0.528027 0.000015 25 C -1.01928-0.00838 4.31498 26 C 5.376914 0.454935 0.000042 26 C -0.070577-0.128826 5.334992 27 C 4.755689-1.875998 0.000032 27 C -2.375113 0.090587 4.646567 28 C 6.712591 0.098966 0.000069 28 C -0.474608-0.15097 6.663308 29 H 5.104649 1.502217 0.000079 29 H 0.982495-0.207422 5.09166 30 C 6.095464-2.242792 0.000063 30 C -2.771365 0.067384 5.975328 31 H 4.005486-2.657594 0.000027 31 H -3.122833 0.189092 3.866843 32 C 7.087873-1.253119 0.000071 32 C -1.823222-0.053945 6.987599 33 H 7.490229 0.852898 0.000113 33 H 0.269637-0.244719 7.446796 34 H 6.354222-3.292447 0.000099 34 H -3.82475 0.146717 6.221671 35 C -1.559987 3.674325 0.000053 35 H -2.135638-0.071661 8.026326 S-10
36 N -2.210778 4.629761 0.000108 36 C -0.605891 0.009786 2.915362 37 C 1.3574 3.774543-0.000008 37 C 3.35922 0.037974-1.45806 38 N 1.94032 4.772819 0.000042 38 C 3.35922 0.037974 1.45806 39 C -9.308217-1.389533 0.000157 39 N 4.329604 0.041842-2.077276 40 H -10.181983-2.037362 0.000213 40 N 4.329604 0.041842 2.077276 41 H -9.319754-0.760513 0.894831 42 H -9.320048-0.760378-0.89443 43 C 8.873022-2.854729 0.000193 44 H 8.533437-3.384232 0.894861 45 H 8.533763-3.384505-0.89445 46 H 9.959446-2.801454 0.000338 47 O 8.420466-1.497836-0.000082 48 O -8.177958-2.266491-0.000049 Table S3. The geometrical structure and Cartesian coordinates of the compound DBD and BBD at the excited states. BBD DBD Row Symbol X Y Z Row Symbol X Y Z 1 C 0.679422-0.008613-0.000061 1 C -0.326565-0.022426 0.701214 2 C 1.365876 1.217449-0.00006 2 C -0.326565-0.022426-0.701214 S-11
3 C 0.76795 2.482517-0.000028 3 C 0.913815-0.026082-1.346808 4 C -0.649764 2.530376 0.000018 4 C 2.151621-0.033341-0.703286 5 C -1.331404 1.308406 0.000027 5 C 2.151621-0.033341 0.703286 6 C -0.728568 0.038853-0.000013 6 C 0.913815-0.026082 1.346808 7 C 1.691466-1.016116-0.0001 7 O 0.744313-0.01924 2.683327 8 C 2.898261-0.367539-0.000063 8 O 0.744313-0.01924-2.683327 9 H 1.543095-2.084458-0.000136 9 C -1.300867-0.01156 1.746106 10 O 2.706992 0.999092-0.000079 10 H -2.373671 0.000929 1.634576 11 C -1.805562-0.898381 0.000014 11 C -1.300867-0.01156-1.746106 12 H -1.728315-1.974206 0.000032 12 H -2.373671 0.000929-1.634576 13 C -2.966426-0.170633-0.00002 13 C -1.01928 0.00838 4.31498 14 O -2.684155 1.179977 0.000058 14 C -2.375113-0.090587 4.646567 15 C 4.275647-0.824518-0.000063 15 C -0.070577 0.128826 5.334992 16 C 5.337853 0.088668-0.000065 16 C -2.771365-0.067384 5.975328 17 C 4.58176-2.199211-0.000097 17 H -3.122833-0.189092 3.866843 18 C 6.660453-0.342144-0.000057 18 C -0.474608 0.15097 6.663308 19 H 5.127536 1.151098-0.000082 19 H 0.982495 0.207422 5.09166 20 C 5.891254-2.6355-0.000085 20 C -1.823222 0.053945 6.987599 21 H 3.78415-2.934378-0.000137 21 H -3.82475-0.146717 6.221671 22 C 6.947557-1.710779-0.000027 22 H 0.269637 0.244719 7.446796 23 H 7.452349 0.395681-0.000138 23 H -2.135638 0.071661 8.026326 24 H 6.131877-3.692442-0.00012 24 C -0.605891-0.009786 2.915362 25 C -4.372067-0.532987 0.000009 25 C -1.01928 0.00838-4.31498 26 C -5.374451 0.456167-0.00003 26 C -0.070577 0.128826-5.334992 27 C -4.769811-1.876165 0.000064 27 C -2.375113-0.090587-4.646567 S-12
28 C -6.712081 0.109407 0.000009 28 C -0.474608 0.15097-6.663308 29 H -5.092744 1.50182-0.000114 29 H 0.982495 0.207422-5.09166 30 C -6.112534-2.233918 0.00011 30 C -2.771365-0.067384-5.975328 31 H -4.024137-2.664091 0.000081 31 H -3.122833-0.189092-3.866843 32 C -7.097468-1.238453 0.000109 32 C -1.823222 0.053945-6.987599 33 H -7.486646 0.867652-0.000041 33 H 0.269637 0.244719-7.446796 34 H -6.377973-3.283321 0.000108 34 H -3.82475-0.146717-6.221671 35 C 1.566206 3.659665-0.00004 35 H -2.135638 0.071661-8.026326 36 N 2.234925 4.601809-0.000056 36 C -0.605891-0.009786-2.915362 37 C -1.365584 3.759412 0.000054 37 C 3.35922-0.037974 1.45806 38 N -1.966347 4.746253 0.000068 38 C 3.35922-0.037974-1.45806 39 C 9.313137-1.363044 0.000356 39 N 4.329604-0.041842 2.077276 40 H 10.1922-2.004059 0.000635 40 N 4.329604-0.041842-2.077276 41 H 9.324607-0.731654-0.893829 42 H 9.324062-0.731684 0.894574 43 C -8.894706-2.816809-0.000182 44 H -8.561915-3.353429-0.894623 45 H -8.562438-3.353797 0.894244 46 H -9.980955-2.755854-0.000454 47 O -8.433804-1.47249 0.000201 48 O 8.195555-2.242324-0.000025 S-13
Figure S6. Simulated absorbance spectra of BBD and DBD. S-14