Three-Dimensional Polyoxometalate Organic Frameworks with One-Dimensional Channels Constructed by Multiple Helical Chains Based on 22-Core Ln/Mn/Mo Clusters for Proton Conduction.

Two unique 22-core sandwich {[Mn 6 Mo 6 O 37 ]Ln 3 [MnMo 6 O 24 ]} (Ln = La or Pr) units have been assembled, featuring an undisclosed {Mn 6 Mo 6 } cluster. This assembly is subsequently integrated into two three-dimensional polyoxometalate organic frameworks, which exhibit one-dimensional hydrophilic hexagonal channels formed by six intertwined 6 3 helical chains, leading to effective proton conduction primarily facilitated by an abundance of water molecules within the channels.