Three‐dimensional organotin–hexacyanoferrate polymers as effective oxidizing reagents towards phenols

Three‐dimensional organotin–hexacyanoferrate polymers of the type _∞³[(R₃Sn)₃Fe^III(CN)₆] where R = Me (I), n‐butyl (II) and phenyl (III), represent members of the family of supramolecular coordination polymers (SCPs) which have zeolitic‐like structure containing micropores. The structures of I–III contain wide channels capable of encapsulating resorcinol, which undergoes in situ oxidation to 1,3,4‐trihydroxy benzene (THB) or p‐nitrophenol (PNP), which converts to 1,4‐benzoquinone (BQ) and 2‐hydroxybenzoquinone (2‐HBQ). The oxidation products were investigated by spectroscopic methods and by HPLC. The SCP III was found to be a more effective oxidizing reagent than I and II due to the presence of terminal Sn‐OH₂ groups hydrogen bonded to one‐sixth of the terminal CN groups, causing more wide expandable channels. In addition, mechanisms of the oxidation processes of resorcinol and PNP have been proposed. Copyright © 2010 John Wiley & Sons, Ltd.