SUPPLEMENTARY INFORMATION

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1 SUPPLEMENTARY INFORMATION Synthesis of metl oxide with roomtemperture photoreversile phse trnsition Shin-ichi Ohkoshi 1 *, Yoshihide Tsunouchi, 1 Tomoyuki Mtsud, 1 Kzuhito Hshimoto, 2 Asuk Nmi, 1 Fumiyoshi Hkoe, 1 nd Hiroko Tokoro 1 1 Deprtment of Chemistry, School of Science, The University of Tokyo Hongo, Bunkyo-ku, Tokyo , JAPAN 2 Deprtment of Applied Chemistry, School of Engineering, The University of Tokyo Hongo, Bunkyo-ku, Tokyo , JAPAN Correspondence should e ddressed to S. O. ohkoshi@chem.s.u-tokyo.c.jp Contents 1. Movie 2. Crystllogrphic dt of λ-ti 3 nnocrystl in SiO 2 mtrix 3. Synthesis of flke form λ-ti 3 4. Powder XRD pttern of flke form λ-ti 3. Crystllogrphic dt of flke form λ-ti 3 6. Crystl structure of flke form λ-ti 3 7. Temperture dependence of the crystl structure of flke form Ti 3 8. Mgnetic property of λ-ti 3 nnocrystl in SiO 2 mtrix 9. First principl clcultion for β-ti 3 nd λ-ti 3 1. Clcultion of phse trnsition in conventionl lrge crystl Ti 3 using Slichter-Drickmer model 11. Pressure-induced phse trnsition from λ-ti 3 to β-ti The clculted Gis free energy versus the frction of chrge-deloclized unit for Ti 3 nnocrystl 13. Isoltion of λ-ti 3 nnocrystl from SiO 2 mtrix nd prospect towrd high density opticl memory medi with scnning proe microscope using the isolted λ-ti 3 nnocrystls Movie S1 Tle S1 Figure S1 Figure S2 Tle S2 Figure S3 Figure S4 Figure S Figures S6-S7 Figure S8 Figures S9-S1 Figure S11 Figure S12 Pge S2 S3 S4 S S6 S7 S8 S9 S1-S11 S12 S13-S14 S1 S16 nture chemistry 1

2 1. Movie Movie S1. Reversile photoinduced phse trnsition in λ-ti 3. Movie of flke form λ-ti 3 y irrditing 32 nm nd 41 nm lser light. When the pellet of the flke form λ-ti 3 ws irrdited with the 32 nm ns-pulsed lser light t room temperture, the color of the irrdited re chnged from lck to rown. Successively, y the irrdition of 41 nm lser light, the color of irrdited spot returned to lck. The photoinduced color chnges were repetedly oserved y the lternting irrditions of 32 nm nd 41 nm lser lights. 2 nture chemistry

3 2. Crystllogrphic dt of λ-ti 3 nnocrystl in SiO 2 mtrix Tle S1. Crystllogrphic dt of λ-ti 3 nnocrystl in SiO 2 mtrix. Dt includes the lttice prmeters nd tomic coordintes otined y Rietveld refinement of the powder XRD pttern. Crystl system Monoclinic Spce group C 2/m (No. 12) (Å) (11) (Å) (2) c (Å) (7) β (º) (6) V (Å 3 ) 372. (6) Z 4 R wp (%) 1.7 S 1.47 T (K) 29 x/ y/ z/c Ti(1).6337 ().37 (4).339 (3).244 ().633 ().434 (4) O(1).442 (2).3941 (12) O(2).1842 (14).792 (13) O(3).7177 (9).2472 (13) O(4). (2).866 (11) O().1834 (1).427 (12) nture chemistry 3

Synthetic procedure of flke form λ-ti 3. (middle) SEM imge nd size distriution of flke form λ-ti 3.

4 3. Synthesis of flke form λ-ti 3 TiO 2 ntse (size = 7 nm) Clcintion 12ºC, h H 2 (.3 dm 3 min -1 ) Flke form λ-ti 3 ssemled y nnocrystls SEM imge 4 2 ±. µm TEM imge µm Numer of prticles Dimeter (µm) 3 2 ± 1 nm 1 nm Numer of prticles Dimeter (nm) Figure S1. Synthetic procedure of flke form λ-ti 3. (middle) SEM imge nd size distriution of flke form λ-ti 3. (lower) TEM imge nd size distriution of the nnocrystl in flke form λ-ti 3. 4 nture chemistry

5 4. Powder XRD pttern of flke form λ-ti 3 Figure S2. Powder XRD pttern of the flke form λ-ti 3. Upper nd lower green rs represent the clculted positions of the Brgg reflections of λ- Ti 3 (96%) nd β-ti 3 (4%), respectively. nture chemistry

6 . Crystllogrphic dt of flke form λ-ti 3 Tle S2. Crystllogrphic dt of flke form λ-ti 3. Dt includes the lttice prmeters nd tomic coordintes otined y Rietveld refinement of the powder XRD pttern. Crystl system Monoclinic Spce group C 2/m (No. 12) (Å) () (Å) (11) c (Å) (3) β (º) (3) V (Å 3 ) (4) Z 4 R wp (%) 6.12 S 1.47 T (K) 294 x/ y/ z/c Ti(1).6299 (3).22 (2).3 (2).2462 (3).6347 (3).432 (2) O(1).419 (9).3872 (7) O(2).179 (8).67 (8) O(3).7343 (8).2487 (7) O(4).468 (8).8732 (7) O().193 (8).428 (7) 6 nture chemistry

, Asymmetric unit. Views of the unit cell in the, c-, c, -, nd d, c-plne.

7 6. Crystl structure of flke form λ-ti 3 O(2) O(3) Ti(1) O(1) O(4) O() 91.27(3) c c Ti(1) Ti(1) c d Ti(1) c Figure S3. Crystl structure of λ-ti 3., Asymmetric unit. Views of the unit cell in the, c-, c, -, nd d, c-plne. Red, light red, deep red, nd gry lls represent Ti(1),,, nd O toms, respectively. nture chemistry 7

8 7. Temperture dependence of the crystl structure of flke form Ti 3 1. (Å) Intensity (1 3 counts) α ( 2 3) λ (2-3) λ (2 3) 3K 33K 3K 4K 4K 48K K K 6K 64K (Å) c (Å) θ (degree) β ( ) V (Å 3 ) Temperture (K) Figure S4., Temperture dependence of XRD pttern in region of flke form Ti 3. The diffrction peks of λ-ti 3 (2 3) nd (2 3) continuously chnged to pek of α-ti 3 ( 2 3) with incresing temperture., Temperture dependence of the lttice constnts nd volume of flke form Ti 3. 8 nture chemistry

9 8. Mgnetic property of λ-ti 3 nnocrystl in SiO 2 mtrix 3. χ ( 1-4 emu/mol Ti) Temperture (K) 6 Figure S. χ versus T plot of λ-ti 3 nnocrystl in SiO 2 under externl field of. T. nture chemistry 9

10 9. First principl clcultion for β-ti 3 nd λ-ti 3 DOS plots nd nd structures β-ti 3 Energy (ev) Totl Ti(1) Energy (ev) E F E F -1-1 Energy (ev) DOS (ev -1 cell -1 ) 1 DOS (ev -1 cell -1 ) Totl Ti(1) λ-ti 3 E F Energy (ev) -2 Γ ZM AΓ V Brillouin zone direction -2 Γ ZM AΓ V Brillouin zone direction E F A Figure S6. First principl clcultion for β-ti 3 nd λ-ti 3., The density of sttes (DOS) (left) nd nd structure (right) of the Ti 3d round Fermi level for β-ti 3., The DOS (left) nd nd structure (right) of the Ti 3d round Fermi level for λ-ti 3. The nd A (red line) is locted on Fermi level. In DOS plots, the dotted, roken, nd solid lines represent the contriutions from Ti(1),, nd, respectively. 1 nture chemistry

11 Electron denity mp of the nd for λ-ti3o locted on Fermi level z y x y c x z c Figure S7. Electron density mps of the nd A for λ-ti3o y the clcultion sed on VASP from two different directions. Isosurfce is drwn for n equidensity level of. eå-3. S11 11 nture chemistry

12 1. Clcultion of phse trnsition in conventionl lrge crystl Ti 3 using Slichter-Drickmer model In this clcultion, the first-order phse trnsition etween β-ti 3 nd α-ti 3 on conventionl lrge crystl Ti 3 is regrded s the metl-semiconductor phse trnsition etween the chrge-loclized ( ) nd the chrge-deloclized ( 3 Ti Ti Ti Ti ) 3 systems. The therml hysteresis loop of the metl-semiconductor phse trnsition etween β-ti 3 nd α-ti 3 for conventionl Ti 3 is well reproduced using the oserved vlues of H= 13. kj mol -1 nd S = 29. J K -1 mol -1 in DSC mesurement when γ is set to e 9.3 kj mol -1. χ (1-4 emu/mol Ti) Oservtion c. 1 Clcultion Frction (x) Temperture (K) chrge-loclized phse chrge-deloclized phse Figure S8. Clcultion of phse trnsition in conventionl lrge crystl Ti 3 using Slichter-Drickmer model., The oserved χ versus T plot of conventionl lrge crystl of Ti 3 under externl field of. T., Temperture dependence of clculted frction of chrge-deloclized unit (x) using Slichter-Drickmer model. c, The clculted Gis free energy (G) versus the frction of chrge-deloclized unit (x) for conventionl crystl Ti 3 from 6 K to 16 K with 2 K intervl. Pink nd lue spheres indicte the therml popultions of α-ti 3 nd β-ti 3, respectively. 12 nture chemistry

13 11. Pressure-induced phse trnsition from λ-ti 3 to β-ti 3 Pressure 3. GP XRD mesurement Flke form λ-ti 3 16 c 1. Intensity (Counts) Pressure λ-ti 3 (2 ) β-ti 3 (2 1) Frction of β phse θ (degree) Pressure (GP) 4 Figure S9. The pressure induced phse trnsition of flke form Ti 3., The procedure of pressure-induced phse trnsition mesurement., The chnge of the XRD pttern. Gry nd lck lines represent efore nd fter pplying externl pressure of.3 GP. c, The increse of the frction of β-ti 3 y the externl pressure. nture chemistry 13

14 DSC mesurement for nnocrystl β-ti 3 β-ti 3 α-ti 3 Het flow (mw mg -1 ) H = 4.8 kj mol Temperture (K) 48 Figure S1. DSC chrt of the phse trnsition from β-ti 3 nnocrystl, which is converted from λ-ti 3 y the externl pressure of.3 GP. 14 nture chemistry

12. The clculted Gis free energy versus the frction of chrge-deloclized unit for Ti 3 nnocrystl chrge-loclized phse chrge-deloclized phse Figure S11.

15 12. The clculted Gis free energy versus the frction of chrge-deloclized unit for Ti 3 nnocrystl chrge-loclized phse chrge-deloclized phse Figure S11. The clculted Gis free energy (G) versus the frction of chrgedeloclized unit (x) for Ti 3 nnocrystl from 6 K to 16 K with 2 K intervl. Pink, lue nd red spheres indicte the therml popultions of α-ti 3, β-ti 3 nd λ-ti 3, respectively. As the temperture decreses from the high clcintion temperture, the system does not trnsit to chrge-loclized phse (β-ti 3 ) ut mintins chrgedeloclized phse (α-ti 3 or λ-ti 3 ). nture chemistry 1

13. Isoltion of λ-ti 3 nnocrystl from SiO 2 mtrix nd prospect towrd high density opticl memory medi with scnning proe microscope using the isolted λ-ti 3 nnocrystls.

As prospect, let us consider high density dt storge system with λ-ti 3 nnocrystls using the scnning proe microscope, which is contrived to surpss the wvelength limit of light. As shown in Fig.

16 13. Isoltion of λ-ti 3 nnocrystl from SiO 2 mtrix nd prospect towrd high density opticl memory medi with scnning proe microscope using the isolted λ-ti 3 nnocrystls. An isolted λ-ti 3 nnocrystl cn e otined y SiO 2 etching of the λ-ti 3 nnocrystl in SiO 2 mtrix (Fig. S12). As prospect, let us consider high density dt storge system with λ-ti 3 nnocrystls using the scnning proe microscope, which is contrived to surpss the wvelength limit of light. As shown in Fig. S12, the storge medium composed of the λ-ti 3 nnocrystls (size = 2 nm) cn rech memory density of 1 terit inch -2 using ner-field light, which is 2 times greter thn the memory density of DVD. Furthermore, s for reding method, λ-ti 3 nnocrystl cn e red not only y the difference of reflectnce index etween λ-ti 3 nd β-ti 3 ut lso y the chnge in electronic conductivity or mgnetic susceptiility. λ-ti 3 S io 2 λ-ti 3 nnocrystl in S io 2 mtrix S io 2 etching KOH / EtOH 6ºC, 24 h λ-ti 3 Figure S12., The isoltion of λ-ti 3 nnocrystl from SiO 2 mtrix y KOH etching nd TEM imge of isolted λ-ti 3 nnocrystl., The isolted λ-ti 3 nnocrystls were otined y the etching of SiO 2 mtrix using KOH ethnol solution. Schemtic imge of opticl storge medium with scnning proe microscope using λ-ti 3 nnocrystls. The dt on λ-ti 3 cn e red not only y the reflectnce index ut lso y the chnge in the electronic conductivity or mgnetic susceptiility, ecuse λ-ti 3 shows reversile photoinduced metl-semiconductor phse trnsition. 16 nture chemistry

Supplementary Figure 1 Supplementary Figure 2

Supplementary Figure 1 Supplementary Figure 2 Supplementry Figure 1 Comprtive illustrtion of the steps required to decorte n oxide support AO with ctlyst prticles M through chemicl infiltrtion or in situ redox exsolution. () chemicl infiltrtion usully