Supplementary Materials for

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1 Supplementary Materials for A design strategy for the hierarchical fabrication of colloidal hybrid mesostructures Lin Jia, Guangyao Zhao, Weiqing Shi, Neil Coombs, Ilya Gourevich, Gilbert C. Walker, Gerald Guerin*, Ian Manners* and Mitchell A. Winnik* *To whom correspondence should be addressed. mwinnik@chem.utoronto.ca (M. A. W); ian.manners@bristol.ac.uk (I. M.), gguerin@chem.utoronto.ca (G. G.) This file includes: 1. Supplementary Figures 2. Supplementary Table S1

2 List of Acronyms and Abbreviations 2-PrOH = 2-propanol AFM = atomic force microscopy Au = gold AuCl 3 = gold(iii) chloride BCP = block copolymer CDSA = crystallization-driven self-assembly DDAB = didodecyldimethylammonium bromide d n = number average diameter d w = weight average diameter EDX = energy dispersive X-Ray L n = number average contour length of the PFS 30 -b-p2vp 300 micelles L n,rod = number average contour length of the silica coated nanorods L w = weighted average contour length of the PFS 30 -b-p2vp 300 micelles L w,rod = weighted average contour length of the silica coated nanorods micelles@sio 2 = silica nanoparticles coated with PFS-b-P2VP micelles Me 4 N + [OH] - = tetramethylammonium hydroxide M n = number average molecular weight M w = weight average molecular weight NiCl 2 = nickel dichloride NP = nanoparticle NR = nanorod PDI = polydispersity index (ratio of M w /M n for polymer, L w /L n for micelle contour lengths and d w /d n for silica nanoparticles) PFS = poly(ferrocenyldimethylsilane) P2VP = poly(2-vinylpyridine) PFS-P2VP@SiO 2 = silica nanoparticles coated with PFS-b-P2VP unimers R h = hydrodynamic radius seeds@sio 2 = silica nanoparticles coated with PFS-b-P2VP seeds SiO 2 = silica SiO = silica-coated nanorods of a nickel-hydrazine complex TBAB = tetra-n-butylammonium bromide TEM = transmission electron microscopy TEOS = tetraethyl orthosilicate THF = tetrahydrofuran TiO 2 = titanium oxide T n = number average thickness of the silica layer deposited on the nickel-hydrazine nanorods T w = weight average thickness of the silica layer deposited on the nickel-hydrazine nanorods W n,rod = number average width of the silica coated nanorods W w,rod = weight average width of the silica coated nanorods S2

3 1. Supplementary Figures Supplementary Figure 1 Silica nanoparticles (SiO 2 NPs). (a) TEM image and (b) SEM image of the silica nanoparticles (SiO 2 NPs) with d n = 246 nm (PDI TEM = 1.01). Supplementary Figure 2 Preparation of PFS 30 -b-p2vp 300 seed crystallites. (a) TEM images of elongated micelles formed by adding an aliquot of PFS 30 -b-p2vp 300 in THF (100 μl, 10 mg/ml) to 2-PrOH (2 ml) and aging for 24 h. (b) TEM image of seed crystallites of PFS 30 -b-p2vp 300 (L n = 60 nm, PDI TEM =1.09) obtained by sonication (3 10 min, 70 watt bath sonicator) at room temperature of long PFS 30 -b-p2vp 300 micelles (a) in 2-PrOH. S3

4 Supplementary Figure 3 SiO 2 NPs mixed with PFS 30 -b-p2vp 300 seeds. A 2-PrOH solution (1 ml) of SiO 2 NPs (1 mg) was treated with excess PFS 30 -b-p2vp 300 seeds (0.5 mg, L n = 60 nm) in 2-PrOH (1 ml) and aged for 24 h. (a), (b) Additional TEM images (see Fig. 1a, main text) from different positions of the same TEM grid at different magnifications. Supplementary Figure 4 PFS 30 -b-p2vp 300 seed-coated SiO 2 NPs. The excess of PFS 30 -b-p2vp 300 seeds was removed from the seed-coated SiO 2 NPs by sedimentation-resuspension with 2-PrOH. (a), (b) Additional TEM images (see Fig. 1b, main text) from different positions of the same grid at different magnifications. S4

5 PFS-b-P2VP seed-coated SiO 2 NPs Nitrogen Iron 1 µm Oxygen Silicon Carbon Supplementary Figure 5 SiO 2 NPs coated with PFS 30 -b-p2vp 300 seeds in 2-PrOH. EDX Line scan analysis. Supplementary Figure 6 Sunflower-like assemblies prepared by seeded growth. The sunflower hybrid assemblies were prepared by adding an aliquot of PFS 30 -b-p2vp 300 in THF (15 μl, 10 mg/ml) to a 2-propanol solution (1 ml) containing seed-coated SiO 2 NPs (0.5 mg/ml) and aging for 24 h. (a), (b) Additional TEM images (see Fig. 1c, main text) from different positions of the same TEM grid at different magnifications. S5

6 Supplementary Figure 7 Sunflower-like assemblies prepared by self-seeding. (a), (b) TEM images of the sunflower-like assemblies after a 2-PrOH solution (2 ml) containing a mixture of SiO 2 NPs (1 mg) and PFS 30 -b-p2vp 300 seeds (0.8 mg) was heated at 90 o C for 30 minutes, then cooled to room temperature and aged 24 h. (c), (d) Additional TEM images (see Fig. 1d, main text) of the sunflower hybrid micelles after the solution was heated at 90 o C for another 90 minutes, then cooled down to room temperature and aged 24 h. S6

7 Supplementary Figure 8 Nickel-hydrazine nanorods with PFS 30 -b-p2vp 300 seeds. (a) TEM image of silica-coated nickel-hydrazine nanorods (SiO with L n = 375 nm (PDI TEM = 1.01) and W n,rod = 93 nm (PDI TEM = 1.06). The uniform silica shell is characterized by T n = 30 nm (PDI TEM = 1.03). The inset shows a single SiO at higher magnification. (b) TEM image of a mixture of SiO + excess PFS 30 -b-p2vp 300 seed crystallites (L n = 60 nm) after stirring 24 h in 2-PrOH. S7

8 Supplementary Figure 9 Sunflower-like assemblies 4a. The sunflower-like assemblies were prepared by seeded growth, by adding an aliquot of PFS 30 -b-p2vp 300 in THF (10 µl, 10 mg/ml) to a 2-PrOH stock solution (1 ml) containing PFS 30 -b-p2vp 300 seed-coated SiO 2 NPs (0.25 mg) and then aging for 24 h at room temperature. (a), (b), (c), (d) Additional TEM images (see Fig. 4a, main text) from different positions of the same grid at different magnifications. S8

9 a b c d g (2) (τ)-1 ff(rh) e Lag time (ms) Rh (nm) Supplementary Figure 10 Sunflower-like assemblies 4b. The sunflower-like assemblies were prepared by seeded growth, by adding an aliquot of PFS 30 -b-p2vp 300 in THF (20 µl, 10 mg/ml) to a 2-PrOH stock solution (1 ml) containing PFS 30 -b-p2vp 300 seed-coated SiO 2 NPs (0.25 mg). The solution was aged 24 h at room temperature before performing right angle DLS measurements. (a), (b), (c), (d) Additional TEM images (see Fig. 4b, main text) from different positions of the same grid. (e) Autocorrelation plot of the sunflower hybrids 4b in 2-PrOH. (f) CONTIN plot of the sunflower hybrid assemblies 4b evaluated from the autocorrelation plot. A second order cumulant analysis gives: R h = 496 nm and PDI = 0.1. Some dimers with their cores in contact can be seen in Supplementary Fig. 14a and c. We assume that the core-dimers were formed during coating of the SiO 2 NPs with micelle seeds. The DLS results in (e) and (f) show that these dimers do not make a significant contribution to the measured size distribution of the system in solution. S9

10 Supplementary Figure 11 Sunflower-like assemblies 4c. The sunflower-like assemblies were prepared by petal elongation of sunflower-like assemblies 4a. (a), (b) Additional TEM images (see Fig. 4c, main text) from different positions on the same grid at different magnification. Supplementary Figure 12 Sunflower-like assemblies 4d. The sunflower-like assemblies were obtained by petal elongation of sunflower-like assemblies 4b. (a), (b) Additional TEM images (see Fig. 4d, main text) from different positions on the same grid at different magnification. S10

11 SiO 2 NPs Iron 1 µm Oxygen Silicon Carbon Supplementary Figure 13 Uncoated SiO 2 NPs. EDX Line scan analysis. SiO 2 NP + PFS-b-P2VP Nitrogen Iron 1 µm Oxygen Silicon Carbon Supplementary Figure 14 SiO 2 NPs coated with PFS 30 -b-p2vp 300 unimers in THF. EDX Line scan analysis. S11

12 Supplementary Figure 15 Mixture of elongated PFS 30 -b-p2vp 300 micelles and SiO 2 NPs coated with PFS 30 -b-p2vp 300 unimers. The sample was prepared by the following protocol: SiO 2 NPs (1 mg) coated in THF with PFS 30 -b-p2vp 300 unimers were first redispersed in 2-PrOH (2 ml), and treated with an aliquot of PFS 30 -b-p2vp 300 in THF (80 μl, 10 mg/ml). The solution was aged for 24 h at room temperature. (a), (b) TEM images from different positions of the same grid. Supplementary Figure 16 Bundled sunflower-like assemblies. The sunflower micelles were prepared with different petal lengths (a shorter, b longer) on a particularly humid summer day. Humidity appeared to induce bundling of the micelle petals during the deposition of the samples on the TEM grids. This problem was avoided if the TEM grids were prepared in a glove bag in a nitrogen atmosphere. S12

13 2. Supplementary Table Supplementary Table 1. Hydrodynamic diameters of SiO 2 NPs before and after treatment with PFS 30 -b-p2vp 300 unimers or seeds Sample Polymer or seeds Solvent Hydrodynamic Diameter (nm) a PDI a SiO 2 NPs None THF SiO 2 NPs None 2-PrOH SiO 2 NPs PFS-b-P2VP b (unimers) THF SiO 2 NPs PFS-b-P2VP c (seeds) 2-PrOH a The hydrodynamic diameters and polydispersity indices (PDI) of these samples were determined with a BI-90 particle sizer. b SiO 2 NPs (1 mg) dispersed in THF (1.5 ml) were treated with a solution of PFS 30 -b-p2vp 300 (1 mg) in THF (1 ml) and aged 24 h. c SiO 2 NPs (1 mg) dispersed in 2-PrOH (1.5 ml) were treated with a suspension of PFS 30 -b-p2vp 300 seeds (0.5 mg) in 2-PrOH (1.0 ml) and stirred gently for 24 h. Excess seeds were removed by sedimentation-resuspension before the DLS measurement. S13