Iron-Directed Thermolysis of Pyridine-N-Oxide in Layered Metal Cyanides

Precision chemical synthetic methodologies are urgently required to address challenges in the energy-intensive and difficult-to-control synthesis and modification of solid-state compounds, as well as the development of emergent molecular-scale reactivity. Here, we install potentially reactive pyridine-N-oxide (pyO) molecules within layered metal cyanides known as Hofmann clathrates and demonstrate control of heat-induced pyO reactivity through framework tuning. A suite of spectroscopic and diffraction-based analyses suggests that Fe(pyO)2Ni(CN)4 transforms to Fe(py)2Ni(CN)4 while evolving O2(g) and oxidized aromatic products upon heating─behavior that is not observed for Ni(L)2Ni(CN)4 (L = py, pyO) or Fe(py)2Ni(CN)4─suggesting promising distinct molecular reactivity in the solid state.