# Fileset

[Tethering Organic Disulfides_ESI.pdf](https://mdr.nims.go.jp/filesets/931ff84d-ed16-46a3-9de9-bd7757481a09/download)

## Creator

[Jonathon Tanks](https://orcid.org/0000-0002-0232-8240), [Takashi Hiroi](https://orcid.org/0000-0001-6881-1334), [Kenji Tamura](https://orcid.org/0000-0001-6578-0923), [Kimiyoshi Naito](https://orcid.org/0000-0002-3334-4876)

## Rights

©2022 The Chemical Society of Japan[In Copyright](http://rightsstatements.org/vocab/InC/1.0/)

## Other metadata

[Tethering Organic Disulfides to Layered Silicates: A Versatile Strategy for Photo-Controllable Dynamic Chemistry and Functionalization](https://mdr.nims.go.jp/datasets/8d4df259-baab-4e1f-b47e-a589909f0572)

## Fulltext

Tethering Organic Disulfides to Layered Silicates:A Versatile Strategy for Photo-Controllable Dynamic Chemistry and FunctionalizationJonathon Tanks,* Takashi Hiroi, Kenji Tamura, and Kimiyoshi Naito© 2023 The Chemical Society of JapanElectronic Supporting Information for Bulletin of the Chemical Society of Japan © 2021 The Chemical Society of Japan Supporting Information for Tethering Organic Disulfides to Layered Silicates: A Versatile Strategy for Photo-controllable Dynamic Chemistry and Functionalization Jonathon Tanks,*1 Takashi Hiroi,2 Kenji Tamura,3 and Kimiyoshi Naito1,4 1Research Center for Structural Materials, National Institute for Materials Science (NIMS) 2International Center for Young Scientists, National Institute for Materials Science (NIMS) 3Research Center for Functional Materials, National Institute for Materials Science (NIMS) 4Department of Aerospace Engineering, Tohoku University   Disulfide Intercalation  Figure S1. Crystal structures of gauche conformers (a) Cyst and (b) APDS; yellow = S, grey = C, blue = N, white = H, green = Cl. (c) Calculated diffraction patterns (black dotted lines) compared to experimental measurements. Significant deviation of Cyst patterns suggests the ideal gauche structure may not be dominant in the as-received powder.    In principle, the organo-modifier intercalates via electrostatic interactions with the negative layer charge in the silicate. The cation exchange capacity (CEC) of Na-TSM is about 120 meq/g, equating to 0.6 mmol/g of diamine-type intercalating agent. Disulfide contents of 0.58 mmol/g and 0.68 mmol/g were calculated from TGA for Cyst-TSM and APDS-TSM, respectively (Fig. S2a). FTIR spectra show appearance of the benzene (APDS) and ethylene (Cyst) peaks compared to Na-TSM, and the decreased -OH peak (3200-3600 cm-1) confirms that the disulfides intercalate via cation exchange (Fig. S2b). 5 10 15 20 25 30 35 40 45Intensity (a.u.)2 (deg)APDSCyst(c)(a)(b)Electronic Supporting Information for Bulletin of the Chemical Society of Japan © 2021 The Chemical Society of Japan  Figure S2. (a) TGA mass-loss curves and (b) ATR-FTIR spectra of disulfide-intercalated silicates.  Disulfide Exchange Reactions  Figure S3. Calibration curves of (a) disulfide reagents and (b) intercalated silicates; peak absorbance taken at 311 nm (APDS), 322 nm (NPDS), and 281 nm (Cyst).  Our objective in the current study was not to efficiently exfoliate the layered silicates, but rather to investigate the disulfide-based reactions inside the interlayer. However, to emphasize the swelling effect of DMSO, we captured AFM images of APDS-TSM in DMSO and water (for comparison). No statistical data is available, but a cursory observation showed that particles in DMSO had smaller thickness, possibly between 4-10 layers (compared to 8-15). Furthermore, the nanosheets collected from dispersion in DMSO showed negligible change from the initial material, strongly indicating that neither APDS nor Cyst undergo permanent scission (e.g., reduction) in solvent. These functional nanosheets can be dispersed, recovered and reused for a variety of applications. 808590951000 200 400 600Residual mass (%)Temperature (C)Intercalated disulfideNa-TSMAPDS-TSMCyst-TSM500150025003500Absorbance (a.u.)Wavenumber (cm-1)PhSi-OCH2Na-TSMAPDS-TSMCyst-TSMOH(b)(a)y = 0.0281x + 0.3612y = 2.8783x + 0.5552y = 4.2306x + 0.140401234560 0.5 1 1.5 2AbsorbanceConcentration (M)CystamineAPDSNPDS(a)y = 0.0055x + 0.1402y = 0.0015x + 0.238300.511.50 100 200 300 400 500AbsorbanceConcentration (g/mL)APDS-10Cyst-20APDS-TSMCyst-TSM(b)Electronic Supporting Information for Bulletin of the Chemical Society of Japan © 2021 The Chemical Society of Japan  Figure S4. AFM height profiles and photos of the Tyndall effect for (a) water and (b) DMSO dispersions of APDS-TSM. While there were many large agglomerates in both solvents, DMSO showed smaller particle heights overall, suggesting more exfoliation than water. XRD patterns of (c) APDS-TSM and (d) Cyst-TSM before, during, and after swelling in DMSO.    Figure S5. (a) UV-vis spectra of PER3 reaction mixture, (b) change in NPDS concentration and reaction intermediate (496 nm) during irradiation in PER3, and (c) UV-vis spectra taken after 20 min of UV radiation and then again 24 h later.   2 3 4 5 6 7 8 9 10Intensity (a.u.)2 (deg)Cyst-TSM17.8 Åx5Recovered from DMSOSwollen in DMSO2 3 4 5 6 7 8 9 10Intensity (a.u.)2 (deg)PER2x20Recovered from DMSOSwollen in DMSOAPDS-TSMx526.1 Å26.4 Å(d)(c)34210102005100 0.5 1 1.5010200 1 2 3 4 50510Position (m)Position (m)Height (nm)34215 m015300 1 2 3015300153001530Position (m)Height (nm)34214 m1234(b)(a)250 300 350 400 450 500Absorbance (a.u.)Wavelength (nm)450 500 550(b)(a)250 300 350 400 450 500Absorbance (a.u.)Wavelength (nm)450 500 550UV 20min UV 20min + 24h(c)00.10.20.30.40.50 10 20 30 40 50 60A496nm(a.u.)CNPDS(M)Irradiation Time (min)t1/2SSNPDSSilicate+CystElectronic Supporting Information for Bulletin of the Chemical Society of Japan © 2021 The Chemical Society of Japan  Figure S6. (a) “Indiscriminate” disulfide exchange between APDS/NPDS in DMSO and no UV light. (b) UV-vis spectra of PER2 using APDS-TSM that was recovered from DMSO, showing no significant change from the original disulfide-intercalated silicate. (c) UV-vis spectra of PER4, showing the apparent disulfide-thiol exchange between APDS-TSM and -ME.   Disulfide-Initiated in-situ Polymerization We stopped the curing when the films felt solid without tack, which tended to be around 15% conversion by FTIR. We expect a large quantity of unreacted monomer to be immobilized as the film cures. However, our objective was not to fabricate a “perfect” film with unique properties, but rather to simply demonstrate the versatility of disulfide-functionalized nanosheets.  Figure S7. ATR-FTIR spectra of acrylate films (a) F1, (b) F2, (c) F3, and (d) F5. The conversion was calculated by the area under the peak at 807 cm-1 (C=CH2). 250 300 350 400 450 500Absorbance (a.u.)Wavelength (nm)0 min60min450 500 550250 350 450 550Absorbance (a.u.)Wavelength (nm)450 500 5500 h24 h(b)(a) (c)250 300 350 400 450 500 550Absorbance (a.u.)Wavelength (nm)450 500 5500 min40min00.517009001100130015001700Absorbane (norm.)Wavenumber (cm-1)F1C=CH20 min5 min00.517009001100130015001700Absorbance (norm.)Wavenumber (cm-1)F2C=CH20 min5 min00.517009001100130015001700Absorbance (norm.)Wavenumber (cm-1)F5C=CH20 min7 min00.517009001100130015001700Absorbance (norm.)Wavenumber (cm-1)F3C=CH20 min12 min(b)(a)(c) (d)Electronic Supporting Information for Bulletin of the Chemical Society of Japan © 2021 The Chemical Society of Japan  Figure S8. (a) Curing rates and (b) XRD patterns of films F1-3 and F5, and (c) Raman spectra of films F3-F5. (d) UV-vis spectra of the F3 mixture dispersed in DMSO and irradiated with UV, showing a decrease in the APDS peak with no intermediate. (e) The same mixture that was irradiated with visible light (490 nm cut-off filter) then left for 24 h showed no significant changes, indicating the thiyl radical-mediated in-situ polymerization can be controlled by wavelength. (f) PETA/TSM films fabricated by UV radiation and filtration, showing that S-S scission generates radicals for polymerization rather than C-S scission.  250 300 350 400 450Absorbance (a.u.)Wavelength (nm)450 500 5500 min20min (d) (f)01250 300 350 400 450Absorbance (a.u.)Wavelength (nm)Before visvis 5 min + 24 hSPhSPhR'hvSPhR'SPhSPhPhhvR'SRSRR'hvSRR'SRNo reactionn n1 2 3 4 5 6 7 8Intensity (a.u.)2 (deg)F1F5F4F3Dashed lines: x5(b)0510150 2 4 6 8 10 12Conversion (%)Irradiation time (min)F1 F5F2F30480 1 2 3 4F1F5F3(a) (c)(e)-500500150040080012001600IntensityRaman shift (cm-1)400500600700F5F3F4C-S S-SNorm.