A Single-Crystal to Single-Crystal Conversion Scheme for a Two-Dimensional Metal–Organic Framework Bearing Linear Cd₃ Secondary Building Units

Abstract

The single-crystal to single-crystal (SCSC) conversion of metal–organic frameworks (MOFs) represents a facile route to new MOFs with structures and functionalities that are challenging to obtain by direct synthesis. However, conversion products are often structurally limited for a given precursor. We herein report that a two-dimensional (2D) MOF featuring a linear Cd3 cluster secondary building unit (SBU) converts into one type of three-dimensional (3D) interpenetrated and two types of 3D non-interpenetrated MOFs upon reaction with dipyridyl ligands. One of the interpenetrated 3D MOFs, in turn, undergoes either ligand substitution to give isoreticular interpenetrated MOFs, or ligand addition to give a self-penetrated 3D MOF. This rich SCSC conversion library is made possible by the inclined nature of the Cd3 SBU with respect to the 2D plane of the starting material to create an anisotropic environment around the SBU.