Abstract
The M(6)L(4) cage, self-assembling from six Pd(II) or Pt(II) 90-degree blocks and four triazine-cored triangular ligands, has an effective hydrophobic cavity of about 450 Å(3) capable of encapsulating one or more small molecules. Here, from the same components, we successfully constructed an M(9)L(6) cage with an internal volume expanded to 1540 Å(3) via the self-assembly of an M(8)L(6) precursor using pillar[5]arene as a template. This cage retains the high molecular recognition ability of the M(6)L(4) cage while recognizing medium-sized guest molecules with molecular weights of up to ∼1600.