Porphyrin-Based Thin-Film Molecular Materials with Highly Adjustable Nanoscale Porosity and Permeability Characteristics.

Mesoporous thin films based on neutral, porphyrin-bridged, tetrarhenium "square" compounds (metallacycles) display permeability to molecules smaller than the dimensions of an individual square cavity, but blocking behavior toward larger species (see schematic representation). The characteristic permeant size cutoff can be systematically and predictably manipulated by decorating the walls of the porphyrin square with axially bound, mono-, bi-, and tetradentate ligands.