Supporting Information. for. Angew. Chem. Int. Ed. Z Wiley-VCH 2004

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1 Supporting Information for Angew. Chem. Int. Ed. Z Wiley-VCH Weinheim, Germany

2 Angew. Chem. Int. Ed., Z. Y. Tian Z54131 Supporting Info Page 1 Supplementary Materials: Material A providing the synthesis and characterization of the model compounds. Material B showing the low and high magnification SEM images of the nanospheres formed by compound 2. Material C showing the steady-state excitation and emission fluorescence spectra of the nanospheres of compound 2 with different sizes. Material D showing the XRD patterns of the bulk crystal sample and the nanorods sample of compound 1. Material E showing the comparison of the calculated results of the absorption spectrum according to the proposed aggregation models with the experimental results. Material F showing computer-generated molecular orbitals of HOMO and LUMO+1, through which intermolecular charge transfer (Inter-CT) process occurring between the neighboring molecules in the nanorods of compound 1 is confirmed. Material G showing the SEM image and the absorption spectra of the nanorods formed by compound 3. 1

3 Angew. Chem. Int. Ed., Z. Y. Tian Z54131 Supporting Info Page 2 A. Synthesis and characterization of the model compounds: Model compound 1 was synthesized according to the literature (Zhan, C. L., Wang, D. Y., J. Photochem. & Photobiology A: Chem. 2002, 147, 93.) IR (KBr)/cm -1 : pyridinio: (w); N-methylpyrrole: (m), (s, s), (m); CH=CH: (m); N-methylpyrrole: (m), (s), (s); pyridinio: (s), (m). UV/vis (ethanol): λ max (log ε = 446 nm (6.56). 1 H-NMR (d, ppm, DMSO-d 6 ): 3.65 (s, 3H, CH 3 -N), 4.20 (s, 3H, CH 3 ) (m, 1H, pyrrole-h), 6.89 (d, 1H, pyrrole-h), 7.08 (m, 1H, pyrrole-h), 7.01(m, 1H, CH=CH), 7.89 (d, 1H, CH=CH), 8.08 (m, 2H, pyridinio-h), 8.70 (m, 2H, pyridinio-h). MALDI-TOF MS: m/z = (M + -I). Elemental analysis: Calculated for C 13 H 15 N 2 I ( ): C, 47.87; H, 4.64; N, 8.59; I, Found: C, 47.96; H, 4.54; N, Model compound 2 was synthesized as follows: g (3 mmol) 4-hexadecyloxybenzaldehyde and g (1.5 mmol) N, 2, 6-trimethylpyridimium Iodide were stirred in 20 ml ethanol. Several drops of piperidine were added into the mixture as catalyst. The reactants were refluxed overnight. The product was filtered and washed with water and ethanol for several times to afford compound 2 (1.057 g, 79%) as a yellow powder. IR (KBr)/cm -1 : pyridinio: 1647 (m); phenyl: 1624 (w), 1601 (m), (m); CH=CH: 972 (m); phenyl: 884 (m); pyridinio: 831 (s), (m). UV/vis (ethanol): λ max (log ε = 409 nm (4.39). 1 H-NMR (d, ppm, CDCl 3 ): 0.83 (t, 6H, CH 3 ); 1.24 (m, 56H, (CH 2 ) 14 ); 3.98 (t, 4H, -OCH 2 -); 4.38 (s, 3H, -N-CH 3 ); 7.05 (d, 4H, -Ar-H); 7.74 (d, 4H, -Ar-H); 8.17 (t, 1H, pyridinio); 8.79 (d, 2H, pyridinio); 7.41 (d, 2H, CH=CH); 7.92 (d, 2H, CH=CH). MALDI-TOF MS: m/z = 778 (M + -I-1). Elemental analysis: Calculated for C 54 H 84 O 2 NI ( ): C, 71.57; H, 9.34; N, Found: C, 70.83; H, 9.29; N,

4 Angew. Chem. Int. Ed., Z. Y. Tian Z54131 Supporting Info Page 3 By replacing N, 2, 6-trimethylpyridimium Iodide with N, 4-dimethylpyridimium Iodide, the synthetic procedure of compound 2 was employed to synthesize model compound 3. IR (KBr)/cm -1 : pyridinio: 1643 (m); phenyl: 1622 (w), 1601 (m), 1564 (m); CH=CH: 985 (m); phenyl: (m); pyridinio: (s), 537 (m). UV/vis (ethanol): λ max (log ε = 392 nm (5.02). 1 H-NMR (d, ppm, DMSO-d 6 ): 0.89 (t, 3H, CH 3 ); 1.22 (m, 28H, (CH 2 ) 14 ); 3.82 (t, 2H, -OCH 2 -); 4.23 (s, 3H, -NCH 3 ); 7.05 (d, 2H, pyridinio-h); 7.72 (d, 2H, Ar-H); 8.16 (d, 2H, pyridinio-h); 8.81 (d, 2H, pyridinio-h); 7.37 (d, 1H, CH=CH); 7.98 (d, 1H, CH=CH). MALDI-TOF MS: m/z = (M + -I). Elemental analysis: Calculated for C 30 H 46 NOI ( ). C, 63.93; H, 8.23; N, Found: C, 63.57; H, 8.13; N,

5 Angew. Chem. Int. Ed., Z. Y. Tian Z54131 Supporting Info Page 4 B. a) Low magnification SEM images to show large quantity of the nanospheres from 2. b) High magnification SEM image of the nanospheres formed by compound 2 clearly show that highly monodisperse nanospheres assemble into regular hexagonal array in small domain. a) b) 4

6 Angew. Chem. Int. Ed., Z. Y. Tian Z54131 Supporting Info Page 5 C. Steady-state excitation and emission fluorescence spectra of the nanospheres of compound 2 with different sizes in water. Line (m), the spectra of dilute solution of compound 2 in ethanol; (a) 30 nm; (b) 60 nm; (c) 100 nm; (d) 130 nm. For excitation spectrum a), the emission wavelength is at 550 nm; for emission spectrum b), the excitation wavelength is at 400 nm. With increasing the particle sizes, both the excitation and emission spectra of the nanospheres show similar trend of hypsochromic shift as that in the absorption spectra, indicating the formation of the H-type aggregates of molecule 2 in the nanospheres (I = intensity, arbitrary units). a) 160 I Emission Wavelength: 550nm (m) (a) (b) (c) (d) λ / nm b) 150 Excitation Wavelength: 400nm 120 I (a) (b) (c) (d) (m) l / nm 5

7 Angew. Chem. Int. Ed., Z. Y. Tian Z54131 Supporting Info Page 6 D. XRD experimental results of the bulk crystal sample of compound 1 and the nanorods sample that was collected on porous alumina membrane filters (Whatman Ltd., Anodisc 13, Quoted diameters of 20 nm) after filtration. The results of these two samples confirmed that, upon forming nanorods under the condition described in the text, the nanorods grown preferentially along the crystallographic [011] direction, eventually leading to the formation of the ordered 1D nanostructures.(i = relative intensity) a) Bulk crystal sample I q b) Nanorod sample 250 I q 6

8 Angew. Chem. Int. Ed., Z. Y. Tian Z54131 Supporting Info Page 7 Zhiyuan Tian, Yu Chen, Wensheng Yang, Jiannian Yao* Lingyun Zhu, Zhigang Shuai E. Comparison of the calculated results of the absorption spectrum according to the proposed aggregation models in Fig. 4 in the text with the experimental results (Fig. 3 in the text). The slightly red-shifted π-π* band and the additional intermolecular charge transfer band of 1 and the blue-shifted π-π* transition of 2 upon aggregation are consistent with the corresponding experimental results. Compound 1 Compound 2 Exp. results Cal. results Exp. results Cal. results Monomers 2.77 ev 2.68 ev 3.03 ev 2.78 ev 2.75 ev 2.60 ev 3.10 ev 2.91 ev Nanostructures 2.52 ev 2.35 ev 7

9 Angew. Chem. Int. Ed., Z. Y. Tian Z54131 Supporting Info Page 8 Zhiyuan Tian, Yu Chen, Wensheng Yang, Jiannian Yao* Lingyun Zhu, Zhigang Shuai F. Computer-generated molecular orbitals of HOMO and LUMO+1. Apparent change of the charge density unambiguously indicates that intermolecular charge transfer (Inter-CT) process occurs between the neighboring molecules in the nanorods of compound 1, which is well consistent with the Inter-CT absorption band (Fig. 3a) proposed in the text. Intermolecular CT Molecular orbital of HOMO Molecular orbital of LUMO+1 8

10 Angew. Chem. Int. Ed., Z. Y. Tian Z54131 Supporting Info Page 9 Zhiyuan Tian, Yu Chen, Wensheng Yang, Jiannian Yao* Lingyun Zhu, Zhigang Shua G. a): SEM image of the nanorods of compound 3; b): The absorption spectra of the dispersions of the nanorods with different diameters: (a) 35 nm; (b) 75 nm; (c) 100 nm; (d) 140 nm; line (m), the spectrum of the monomer. The aggregates formed from molecule 3 are rod-like but rather undefined when compared to the nanorods of 1 and the nanospheres of 2. Neither apparent Inter-CT as that in the nanorods nor blue-shifted spectral feature as that in the nanospheres is observed for the rod-like nanostructures. Both the morphological and spectral features of the nanostructures of 3 are expected to be a result of the competition between the two relatively weaker intermolecular D-A and solvophobic interactions. (A = absorbance, arbitrary units) a) b) 0.4 A (a) (b) (c) (d) (m) l / nm 9