Template and Solid-State-Assisted\nAssembly of an M<sub>9</sub>L<sub>6</sub> Expanded Coordination Cage\nfor Medium-Sized\nMolecule Encapsulation

The M<sub>6</sub>L<sub>4</sub> cage, self-assembling\nfrom six Pd(II)\nor Pt(II) 90-degree blocks and four triazine-cored triangular ligands,\nhas an effective hydrophobic cavity of about 450 Å<sup>3</sup> capable of encapsulating one or more small molecules. Here, from\nthe same components, we successfully constructed an M<sub>9</sub>L<sub>6</sub> cage with an internal volume expanded to 1540 Å<sup>3</sup> via the self-assembly of an M<sub>8</sub>L<sub>6</sub> precursor\nusing pillar[5]arene as a template. This cage retains the high molecular\nrecognition ability of the M<sub>6</sub>L<sub>4</sub> cage while recognizing\nmedium-sized guest molecules with molecular weights of up to ∼1600.