Supramolecular stabilization host molecules

The photolyses of 2-aziadamantane (16) within CyD hosts give product distributions that largely depend on the type of CyD and thus the supramolecular structure. The formation of 2,4-didehydroadamantane (22) is essentially precluded when other inter- and innermolecular reaction channels are available. However, the formation of 22 is greatly enhanced within supramolecular coniines. The amount of reduction to hydrocarbon 2, the share of azine 19 and 2-adamantanone, the formation of CyD ethers 25a and 25b, and the insertion into solvent molecules yielding 25c-e can widely be controlled by geometry and composition of the ICs. This very interesting influence of the host as mediator can be observed especially well for the photolyses of 16, which primarily yield carbene 21—a species that has no intramolecular pathways to stabilization. 

Ferrocene has been by far the most used redox-active group in a supramolecular sensor due its stability, its ease of functionalization and its well-understood and reversible redox chemistry. A host of feiTOcene-contain-ing compounds are now known that bind cations anions, and neutral molecules. It can be argued that the first examples of redox-active receptors, for which the complexation of other species was demonstrated, were ferrocenyl crown ether compounds, as reported in the late 1970s and in 1980. " However, it was not until... 

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