Adsorption of I2 by Macrocyclic Polyazadithiophenolato Complexes Mediated by Charge‐Transfer Interactions

The macrocyclic complex [Ni₂(L)(OAc)]ClO₄ ( 1 ) adsorbs up to 17 molar equivalents (>270 wt %) of iodine, although it does not exhibit permanent porosity. Vibrational spectroscopic and crystallographic studies reveal that two I₂ molecules are captured by means of thiophenolate→I₂ charge‐transfer interactions, which enable the diffusion and sorption of further I₂ molecules in a polyiodide‐like network. The efficient sorption and desorption characteristics make this material suitable for accommodation, sensing, and slow release of I₂.