Uncaging carbon disulfide. Delivery platforms for potential pharmacological applications: a mechanistic approach† †Electronic supplementary information (ESI) available: Additional documentation (10 tables, and 14 figures) including crystallographic parameters, modifications of published synthetic procedures and development of models to fit the kinetics effects of varying buffer concentration. (50 pages total, PDF). Separate Supporting Information files are the X-ray crystallographic data in CIF format. CCDC 1557060–1557062. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c7sc02727c Click here for additional data file. Click here for additional data file.

Figures Figure S1. X-ray structure packing diagram (top) and asymmetric unit (bottom) of K[DIDTC] Figure S2. X-ray structure packing diagram (top) and asymmetric unit (bottom) of K[ImDTC] Figure S3. X-ray structure packing diagram (top) and asymmetric unit (bottom) of K[PyrDTC] Figure S4. Optimized geometries of the DTC anions at a PCM/B3LYP/6-31+G(d,p) theory level. Figure S5. TD-DFT calculated spectrum for DIDTCin a PCM model solvent (water) Figure S6. TD-DFT calculated spectrum for the ImDTCin a PCM model solvent (water). Figure S7 Plot of log kobs versus pH for decay of K[ImDTC] in aqueous solution Figure S8. Plot of kobs–1 vs [H+]–1 for DIDTC– decay in phosphate buffer. pH 6.5-7.8 at 37 °C Figure S9. Temporal spectra of the DIDTC– anion in acidic media Figure S10. kobs as a function of phosphate buffer concentration for the decay of K[DIDTC] Figure S11. Ionic strength effects on DIDTC– decay. Figure S12. Eyring plots (ln( kobs/T) vs. 1/T) for the decay of DIDTC– at pH7.4 and pH 2.0. Figure S13. Eyring plot (ln( kobs/T) vs. 1/T) for the decay of ImDTC– at pH7.4 Figure S14. Optimized geometries of DTCH species at a PCM/B3LYP/6-31+G(d,p) theory level. Figure S15. DFT calculated rotation around the N-CS2 bond of dimethyl DTC–