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.
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