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Container molecules such as carcerand, hemicarcerand, and self-assembled molecular capsule have been characterized as molecular scavengers, molecular storages, molecular reactors and controlled-releasing systems. Various heterobridged hemicarceplexes in which the fourth bridging unit differs from the other three bridging units were reported by Cram et al. and the fourth bridging unit has been used to adopt an additional binding site or to connect with another hemicarcerand to obtain covalently linked dimeric hemicarceplexes. The characteristics of container molecules can be accumulated when they are assembled to highly ordered supramolecular systems. Dimeric container system could duplex the functions of monomeric container molecule and a wellordered multiple container system would result in a new high density information storage system. Metal coordination has become an important synthetic strategy for the self-assembly of high-ordered and welldefined supramolecular architectures because it allows well defined geometry, coordination number, and a range of binding strengths. Recently the interesting guest’s size and shape selectivities of cyanohemicarcerand 1 was reported. 8 But the stability of Pd(II) or Pt(II)-coordinated dimeric assembly 1-ML2-1 was too weak to be observed by H NMR spectrometry. Here we report on the synthesis of hemicarcerand 4 which has a metal coordinating p-pyridylphenyl unit on a pillar and its formation of dimeric self-assemblies 5a and 5b by Pd(II) and Pt(II)-coordination, respectively.

Molecular Engineering. Part 13. Formation of Hemicarcerand Dimer by Metal Coordination