The structure and topology of an amorphous metal-organic framework

TL;DR

This study employs a data-driven approach combining experimental scattering data and machine learning to elucidate the structure of amorphous metal-organic frameworks, revealing key differences from crystalline counterparts and challenging previous assumptions.

Contribution

It introduces a systematic topology notation for amorphous solids and applies it to characterize the structure of an amorphous MOF, advancing understanding of amorphous framework materials.

Findings

Revealed structural differences between a-ZIF and other amorphous tetrahedral networks.

Invalidated the assumption that inorganic and hybrid glasses are topologically equivalent.

Developed a new topology notation for amorphous solids.

Abstract

Amorphous metal-organic frameworks are an important emerging materials class that combine the attractive physical properties of the amorphous state with the versatility of metal-organic framework (MOF) chemistry. The structures of amorphous MOFs have largely been inferred by drawing analogies to crystalline polymorphs and inorganic glasses, but ultimately the validity of such structural models has been challenging to establish either experimentally or computationally. Here we use a unified data-driven approach, combining experimental scattering data and active machine learning for interatomic potentials, to determine the structure of an amorphous zeolitic imidazolate framework (a-ZIF) -- the canonical amorphous MOF. Our results reveal clear differences between the structure of a-ZIF and that of other amorphous tetrahedral networks, allowing us to invalidate the long-standing assumption that these inorganic and hybrid glasses are topologically equivalent. To this end, we introduce a systematic notation for the network topology of amorphous solids, building a bridge to the successful use of topology analysis in crystalline MOFs and to materials informatics. Our work provides insights into the structure and topology of the archetypal amorphous MOF and opens up new avenues for modelling and understanding amorphous framework materials more generally.