Bio-inspired stabilization of sulfenyl iodide RS-I in a Zr()-based metal-organic framework

A Zr( iv )-based metal-organic framework (MOF) appended with free-standing thiol (-SH) groups was found to react readily with I 2 molecules to form sulfenyl iodide (S-I) units. In contrast to its solution chemistry of facile disproportionation into disulfide and I 2 , the sulfenyl iodide (SI) function, anchored onto the rigid MOF grid and thus prevented from approaching one another to undergo the dismutation reaction, exhibits distinct stability even at elevated temperatures ( e.g. , 90 °C). On a conceptual plane, this simple and effective solid host also captures the spatial confinement observed for the complex biomacromolecular scaffolds involved in iodine thyroid chemistry, wherein the spatial isolation and consequent stabilization of sulfenyl/selenenyl iodides are exerted by means of the protein scaffolds. Distance lends stability: a solid framework constrains S-I groups from approaching each other, emulating protein scaffolds in iodine thyroid chemistry.