Double Cation-π Directed Two-Dimensional Metallacycle-Based Hierarchical Self-Assemblies for Dual-Mode Catalysis.

Hierarchical self-assembly of Pt(II) metallacycles for the construction of functional materials has received considerable research interest, owing to their potential to meet increasing complexity and functionality demands while being based on well-defined scaffolds. However, the fabrication of long-range-ordered Pt(II) metallacycle-based two-dimensional hierarchical self-assemblies (2D HSAs) remains a challenge, primarily because of the limitations of conventional orthogonal noncovalent interaction (NCI) motifs and the intrinsic characteristics of Pt(II) metallacycles, making the delicate self-assembly processes difficult to control. Herein, we prepare well-regulated Pt(II)-metallacycle-based 2D HSAs through a directed strategy involving double cation-π interactions derived from C 3 -symmetric hexagonal Pt(II) metallacycles and C 2 -symmetric sodium phenate monomers. Spatially confined arrays of planar Pt(II) metallacycles and the selective growth of self-assemblies at desired locations are achieved by employing strong cation-π driving forces with well-defined directionality as the second orthogonal NCI, realizing the bottom-up, three-stage construction of Pt(II)-metallacycle-based 2D HSAs. The resultant 2D HSAs are applied as dual-mode catalysis platforms, which are loaded with two different nanocatalysts, one promoting catalytic oxidation and the other promoting photocatalytic reduction.