Morphological Evolution of Metal‐Organic Frameworks into Hedrite, Sheaf and Spherulite Superstructures with Localized Different Coloration

Abstract

The branched metal‐organic frameworks (MOFs) are the first superstructures of this kind, and the growth mechanism may explain crystal shapes of other materials. The mechanism of the formation of fascinating structures having a hedrite, sheaf or spherulite appearance are detailed. The branching can be controlled, resulting in crystals that either exhibit multiple generations of branching or a single generation. These structures might result from an increasing number of defects on fast‐grown rods. As the basal facets become less reactive, material is added to the prism facets, leading to secondary nucleation and triangular branches. These triangular structures are connected to the rod surface, growing longer than the central rod. Electron diffraction analyses show that the sheafs are polycrystalline structures with their fantails consisting of single‐crystalline nanorods deviating gradually from each‐other in their orientation. The crystallographic structure formed from achiral components consists of helical channels with opposite handedness. The accessibility of the nanochannels and the porosity of the superstructures are demonstrated by chromophore diffusion into the channels. The confinement and alignment of the chromophores inside the channels resulted in polarized‐light dependent coloration of the crystals; the polycrystallinity generated areas having different optical properties.