Double and triple calix[4]arenis connected via the oxygen functions

New macrocyclic molecules are described containing two or three p-tert-butylcalix[4]arene subunits connected via their oxygen atoms. These macrocycles are available by two general methods which are capable of producing assemblies with bridges of varying rigidity and length.

A New Type of Double Calix[4]arenes by Linkage via the Phenolic Hydroxy Groups

Metal ion complexation by tetraester derivatives of bridged calix [4] arenes

A series of bridged calix [4] arenes (5–10 methylene groups in the bridge) were synthesized and transformed into their tetraester derivatives by reaction with ethyl bromoacetate. The stability constants for complexes of the tetraester derivatives with sodium, potassium and silver cations, determined in methanol by spectroscopic or potentiometric techniques, show a drastic decrease (more than 105 for Na +) for the shorter methylene chains. 1H NMR studies demonstrate a conformational rearrangement of the calixarene part to fourfold symmetry to be necessary for the complexation of a cation, which is prevented by the shorter chains. This is further confirmed by the X-ray structure of a tetraest…