Ultrafine Sub-1 nm One-Dimensional Coordination Polymer Nanowires for Boosting Photocatalytic Functionalization of Inert C( sp 3 )–H Bonds

The heterogenization of molecular catalysts to be compatible with industrialization demands still faces great challenges. In this work, we demonstrate for the first time that the activity of a molecular catalyst is unrestricted when installed in nanostructured coordination polymers (CPs). CPs that can be used to obtain ultrafine nanowires by ultrasound exfoliation are extremely limited. We illustrate that chain-like CPs can be designed using electrostatic ligand-capped low-coordination-number metal ions and electropositive ligands as building blocks. This guides the preparation of the three-dimensional (3D) chain-like CPs from chloride ion-capped Cu-based chromophores and 1,1’-(1,4-phenylenebis(methylene))bis(3-carboxy quinolin-1-ium) chloride; subsequently, ultrafine sub-1 nm nanowires were obtained via ultrasound exfoliation. The formed ultrafine sub-1 nm CP nanowires demonstrate high activity enhancement for functionalization of C( sp 3 ) − H bonds with conversion being significantly increased for alkylation, thiolation, and oxidation of C( sp 3 ) − H bonds after exposure to external surfaces of the flexible nanowires. Therefore, the observed activity increases in the order CuCl 2 < bulk CP crystals < CP nanowires in functionalization of C( sp 3 ) − H bonds. This work not only provides a strategy for constructing chain-like CPs and their ultrafine nanowires but also paves the way for expanding the diversity of the ultrafine 1D CP nanowires.