A μ-oxo-dinuclear iron complex of a supramolecular porphyrin-phthalocyanine conjugate was synthesized and its catalytic electrochemical oxygen reduction properties were investigated. In the conjugate, porphyrin and phthalocyanine units were connected to form a cofacial dimeric structure through a flexible fourfold rotaxane linkage, which was advantageous for accommodating small substrates between the iron centers. The conjugate showed efficient catalytic properties, at more positive potentials than those of other reported dinuclear porphyrinoid iron complexes, to selectively afford water through a four-electron reduction process.

Catalytic CH4 oxidation using a μ-nitrido-bridged iron porphyrinoid dimer was successfully activated by supramolecular complexation.

We report the preparation and crystal structure of a triply stacked metal complex array in which a Cu-phthalocyanine is sandwiched between different Cu-porphyrins. The discrete heterogeneous assembly was prepared through formation of a fourfold rotaxane from a tetradactyl porphyrin with alkylammonium moieties and a phthalocyanine bearing four crown ethers and the subsequent formation of an ionic complex between the fourfold rotaxane and a tetraanionic porphyrin. The tetraanionic porphyrin, Cu-TPPS(4-), is selectively bound to the fourfold rotaxane through cooperative π-π and ionic interactions. The crystal structure revealed the columnar stacked array of the three planar building components in a precise order and spatial arrangement that promote intermolecular electronic communication.

Development of supramolecular methods to further activate ah ighly reactive intermediate is af ascinating strategyt oc reate novel potent catalysts for activation of inert chemicals. Herein, as upramolecular approacht oe nhance the oxidizing ability of ah igh-valent oxo species of a nitrido-bridged iron porphyrinoid dimer that is ak nown potent molecular catalyst for light alkane oxidation is reported. For this purpose, an itrido-bridgedd inucleari ron complex of porphyrin-phthalocyanine heterodimer 3 5 + ,w hich is connected through af ourfold rotaxane, was prepared.H eterodimer 3 5 + catalyzed ethane oxidation in the presenceo f H 2 O 2 at ar elativelyl ow temperature. The site-selectivec om-plexation of 3 5 + with an additional anionic porphyrin (TPPS 4À )t hrough p-p stackinga nd electrostatic interactions afforded as table 1:1c omplex. It was demonstrated that the supramolecular post-synthetic modification of 3 5 + enhances its catalytic activity efficiently.Moreover,supramolecular conjugates achieved higherc atalytic ethane oxidation activity than nitrido-bridgedi ron phthalocyanine dimer,w hich is the most potent iron-oxo-based molecular catalystf or lightalkaneo xidation reported so far.E lectrochemical measurementsp rovedt hat the electronic perturbation from TPPS 4À to 3 5 + enhancedt he catalytic activity.[a] Dr.Supporting Information and the ORCID identification number(s) for the author(s) of this articlecan be found under: https://doi.

Controlled directional transport of molecules is essential to complex natural systems, from cellular transport up to organismal circulatory systems. In contrast to these natural systems, synthetic systems that enable transport of molecules between several spatial locations on the macroscopic scale, when external stimuli are applied, remain to be explored. Now, the transfer of a supramolecular cage is reported with controlled directionality between three phases, based on a cage that responds reversibly in two distinct ways to different anions. Notably, circulatory phase transfer of the cage was demonstrated based on a system where the three layers of solvent are arranged within a circular track. The direction of circulation between solvent phases depended upon the order of addition of anions.