Post-synthetic atomically precise single-CuII sites in a thiacalix[4]arene-supported octahedral Na@Co24 cluster: the Cu–Co synergistic effect for selective photocatalytic conversion of CO2 to CO

Abstract

A thiacalix[4]arene-supported octahedral Na@Co₂₄ cluster has been fabricated by the modular assembly of six Co₄-(TC4A) polynuclear secondary building units (PSBUs) and eight 2,4,6-PTC linkers. The post-modification of Na@Co₂₄ by ion exchange of Na⁺ with Cu²⁺ on the surface of the octahedron afforded a structurally well-defined Cu@Co₂₄ cluster. The obtained Cu@Co₂₄ cluster achieved improved visible-light absorption and selective photoreduction of CO₂ to CO due to the Cu–Co synergistic effect.