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.     

<Emphasis Type="Italic">In situ</Emphasis> Oxidation of phenol and <Emphasis Type="Italic">o</Emphasis>-aminophenol in the channels of 3d-supramolecular coordination polymers

The host attractive properties of supramolecular coordination polymers of the type _￥³ _\infty^3 [(R₃Sn)₃FeIII(CN)₆], where R = methyl (I), n-butyl (II), and phenyl (III), afford the ability to be used as effective oxidizing reagents for phenol and o-aminophenol forming new host-guest supramolecular coordination polymers. Phenol was oxidized to 1,4-benzoquinone while o-aminophenol was oxidized to poly-o-aminophenol by the polymers I and II and to 2-aminophenoxazin-3-one by the polymer III. The oxidation products were investigated by methods of spectroscopy and high-performance liquid chromatography. The redox reactions were characterized by first-order kinetics. Moreover, mechanisms of the oxidation processes of phenol and o-aminophenol have been proposed.     

Paramagnetic charge-transfer guest–host coordination polymers. Thiophene compounds encapsulated within the channels of the three-dimensional coordination polymers [(R3Sn)3Fe(CN)6] n,R = Me,n-Bu or Ph

Various thiophene compounds have been shown to be encapsulated and partly oxidized within the channels of the three-dimensional (3D) host coordination polymers [(R₃Sn)₃Fe(CN)₆] _n (R = Me, n-Bu or Ph) to give guest–host encapsulated systems. The structure and physical properties of these systems were studied by X-ray powder diffraction, i.r., u.v.–vis., e.p.r. spectra and magnetic measurements. Thiophene compounds do not polymerize within the channels of the host, but rather give paramagnetic charge-transfer guest–host systems.     

NOVEL SUPRAMOLECULAR DERIVATIVES CONTAINING TWO R3Sn+ (R = Me,n-Bu,or Ph) CONNECTING UNITS: THE FORMATION OF NOVEL HOST–GUEST SYSTEMS BY THE FACILE ENCAPSULATION OF GUEST THIOPHENE COMPOUNDS

New supramolecular complexes [(Me ₃ Sn)(Ph ₃ Sn) ₂ Fe(CN) ₆ ] (I) and [(n-Bu ₃ Sn)(Ph ₃ Sn) ₂ Fe(CN) ₆ ] (II) are readily accessible by straightforward self-assembly of [Fe(CN) ₆ ] ^3? and hydrated R ₃ Sn⁺/R′ ₃ Sn ⁺ ions (R = Ph, and R′ = Me or n-Bu). The structural characterization of (I) and (II) is compared with well-documented supramolecular complex containing only Ph ₃ Sn ⁺ unit, [(Ph ₃ Sn) ₃ Fe(CN) ₆ ]. These novel compounds have wide internal cavities capable of encapsulating voluminous organic compounds, and they behave as host acceptors forming charge transfer complexes (CTC). Thiophene compounds acting as guest donor species are encapsulated within the cavities of the three-dimensional (3D) supramolecular hosts. The structure and physical properties of these hosts and host–guest systems were studied by X-ray powder diffraction, IR, UV/Vis., and magnetic measurements.