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1 Electronic Supplementary Material (ESI) for Green hemistry This journal is The Royal Society of hemistry 2012 Supplementary information Preparation of electrochromic Prussian blue nanoparticles dispersible into various solvents for realisation of printed electronics Manabu Ishizaki, a Katsuhiko Kanaizuka, a Makiko Abe, a Yuji Hoshi, a Masatomi Sakamoto, a,b Tohru Kawamoto, b Hisashi Tanaka, b and Masato Kurihara *a,b An insoluble solid of historic Prussian blue (PB) has been transformed into dispersible PB nanoparticles in water and various hydrophilic and hydrophobic organic solvents. Via hybrid surface modification using a 4 [Fe II () 6 ] and short-chain alkylamines, the insoluble PB was successfully dispersed in hydrophilic-and-hydrophobic boundary alcohols, such as n-butanol. The n-butanol-dispersible PB nanoparticles afforded homogeneous spin-coated thin films on various substrates. The chemisorbed shorter-chain alkylamines, n-propylamines, of the PB nanoparticles were thermally released at 100 from their surfaces to present stubborn electrochromic PB thin films adhering to the substrate via mutual coordination-bonding networks. (2 0 0) Scherrer s particle size : 10.5 nm 10.2 nm Intensity / a.u. (2 2 0) (4 0 0) (4 2 0) (4 2 2) (4 4 0) (6 0 0) (6 2 0) θ / degree Fig. S1. XRD patterns of the original PB (insoluble PB P solid), the water-dispersible PB P solid using a 4 [Fe() 6 ].

2 Electronic Supplementary Material (ESI) for Green hemistry This journal is The Royal Society of hemistry 2012 H2O H2O H2O H2 H3 H2 + H3 OH OH + Fe H 3 FeII FeIII OH III H2 + FeII FeIII FeII Fig. S2. Two types of surface modification using Fe(III)-OH2 sites with alkylamines (R-H2). absorbanc Wavelength / nm Fig S3. UV-Vis-near IR absorption spectrum of the n-dodecylamine (12-amine)-modified PB Ps almost independently dispersed in n-butanol (78 μg / ml), and a photograph of the blue dispersion solution with high transparency. 200 nm 200 nm Fig. S4. AFM images of the spin-coated thin film using dilute and dense n-dodecylamine (12-amine)-modified PB P inks.

3 Electronic Supplementary Material (ESI) for Green hemistry This journal is The Royal Society of hemistry 2012 Alkylamine-modified PB Ps (i) Scherrer s particle size; 10.2 nm (h) 9.6 nm (g) 9.3 nm (f) (e) (d) 10.6 nm 9.9 nm 11.1 nm (c) 10.5 nm 10.0 nm 10.5 nm θ / degree Fig. S5. Powder X-ray diffraction (XRD) patterns of the original PB (insoluble PB P solid), n-propylamine-modified, (c) n-butylamine-modified, (d) n-hexylamine-modified, (e) n-octylamine-modified, (f) n-dodecylamine-modified, (g) n-hexadecylamine-modified, (h) n-octadecylamine-modified, (i) oleylamine-modified PB P solids. The XRD patterns were recorded on Rigaku MiniFlex II desktop X-ray diffractometer (u Kα 1 radiation ( Å)). The single-crystalline particle diameter (D) was calculated by the Scherrer s equation: D = Kλ/βcosθ, where K = 0.9 (Scherrer s constant), λ = wavelength of X-ray, β = half band width, and θ = peak angle.

4 Electronic Supplementary Material (ESI) for Green hemistry This journal is The Royal Society of hemistry 2012 Alkylamine-modified PB Ps H stretching bands O 2 stretching band (h) (g) (f) (e) (d) (c) Wavenumber / cm Fig. S6. FT-IR spectra of n-propylamine-modified, n-butylamine-modified, (c) n-hexylamine-modified, (d) n-octylamine-modified, (e) n-dodecylamine-modified, (f) n-hexadecylamine-modified, (g) n-octadecylamine-modified, (h) oleylamine-modified PB P solids.

5 Electronic Supplementary Material (ESI) for Green hemistry This journal is The Royal Society of hemistry 2012 Hybrid surface-modified PB Ps (i) Scherrer s particle size; 10.8 nm (h) (g) (f) (e) (d) (c) 10.6 nm 10.3 nm 9.7 nm 10.4 nm 10.6 nm 10.7 nm 10.4 nm 10.5 nm θ / degree Fig. S7. Powder X-ray diffraction (XRD) patterns of the original PB (insoluble PB P solid), n-propylamine-modified, (c) n-butylamine-modified, (d) n-hexylamine-modified, (e) n-octylamine-modified, (f) n-dodecylamine-modified, (g) n-hexadecylamine-modified, (h) n-octadecylamine-modified, (i) oleylamine-modified PB P solids. The XRD patterns were recorded on Rigaku MiniFlex II desktop X-ray diffractometer (u Kα 1 radiation ( Å)). The single-crystalline particle diameter (D) was calculated by the Scherrer s equation: D = Kλ/βcosθ, where K = 0.9 (Scherrer s constant), λ = wavelength of X-ray, β = half band width, and θ = peak angle.

6 Electronic Supplementary Material (ESI) for Green hemistry This journal is The Royal Society of hemistry 2012 Hybrid surface-modified PB Ps H stretching bands O 2 stretching band (h) (g) (f) (e) (d) (c) Wavenumber / cm -1 Fig. S8. FT-IR spectra of n-propylamine-modified, n-butylamine-modified, (c) n-hexylamine-modified, (d) n-octylamine-modified, (e) n-dodecylamine-modified, (f) n-hexadecylamine-modified, (g) n-octadecylamine-modified, (h) oleylamine-modified PB P solids.

7 Electronic Supplementary Material (ESI) for Green hemistry This journal is The Royal Society of hemistry 2012 Eluted Apparently not eluted Apparently not eluted (c) water n-butanol Propylene carbonate Fig. S9. Photographs of the PB P thin film after drying at room temperature in water, n-butanol, and (c) propylene carbonate. Eluted Eluted Eluted Apparently not eluted (c) (d) water water water water Fig. S10. Photographs of the PB P thin film in water after heating at 50 for 10 min, at 80 for 10 min, (c) at 100 for 10 min, and (d) at 100 for 20 min.

8 Electronic Supplementary Material (ESI) for Green hemistry This journal is The Royal Society of hemistry Absorbance Wavelength / nm Absorbance Wavelength / nm Fig. S10. Time-course change in the UV-vis absorption spectra of the PB P film at -0.8 V and 0.5 V vs. Ag/Ag +.