Cyclobis(paraquat-4,4′-biphenylene) - An organic molecular square

Template-directed syntheses of cyclobis(paraquat-4,4′-biphenylene) (1) - a molecular square - have been achieved by use of π-electron-rich macrocyclic hydroquinone-based and acyclic ferrocenebased templates. In particular, the use of a polyether-disubstituted ferrocene derivative as a template permits synthesis of 1 (which is accessible only in very low yields without templates) on a preparative scale. Furthermore, the use of a macrocyclic hydroquinone-based polyether template incorporating an ester function in one polyether chain - an "oriented" macrocycle - affords a 1:1 mixture of two topologically stereoisomeric [3]catenanes. Ester hydrolysis of the π-electron-rich macrocyclic components mechanically interlocked with 1 within the catenated structures releases the tetracationic cyclophane in quantitative yield as a result of the degradation of the [3]catenanes. The molecular square has been characterized by X-ray crystallography, FAB mass spectrometry, ¹H NMR and ¹³C NMR spectroscopies, and elemental analysis. The binding properties of 1 and of the smaller cyclophane cyclobis(paraquat-p- phenylene) toward a series of π-electron-rich guests have also been investigated with the above techniques and UV/VIS spectroscopy. The self-assembly of the resulting supramolecular complexes in solution and in the solid state is driven mainly by π-π stacking interactions and hydrogen-bonding interactions, as well as by edge-to-face T-type interactions. In particular, the complexation of ferrocene or a ferrocene-based derivative within the cavity of 1 suggests the possibility of constructing functioning ferrocene-based molecular and supramolecular devices that can be controlled electrochemically in the form of catenanes, rotaxanes, and pseudorotaxanes.