Cooperative regulation is useful to construct a host responding to external stimuli because dynamic and/or fine regulation of the functions can be achieved due to the synergistic interactions, as seen in allosteric systems.  To design cooperative metallo-systems we have utilized salen, saloph and salamo (1,2-bis(salicylideneaminooxy)ethane) as a strong ligation site to a metal ion.  Here we report linear and macrocyclic ligands containing these ligating units as precursors for multi-metal supramolecular systems. These ligands showed a highly cooperative metal binding behavior to give the corresponding homo- and hetero multi-nuclear metal complexes.  In the cases of the linear ligands the helical sense of such metal complexes can be controlled by introducing a chiral auxiliary.  In addition, we successfully changed the helicity of a multi-metal system that has crown ether moieties when diammonium guests were used as an external stimulus.  Formation and morphology control of molecular assemblies of the macrocyclic multi-metal complexes are also presented.  Other examples of cooperative and functional saloph and salamo metallo-supramolecular systems will also be discussed.

Multimetal supramolecular systems containing C=N ligating units with highly cooperative functions

246th National Meeting (2013)

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