Topology-Guided Construction of Three-Dimensional, π-d Conjugated Metal–Organic Frameworks

π-d conjugated metal-organic frameworks (MOFs) are a unique class of materials that combine permanent porosity with electrical conductivity, making them ideal candidate materials for various electrochemical applications. To date, however, majority of the π-d conjugated MOFs are two-dimensional, and their three-dimensional (3D) counterparts, which are more advantageous in achieving well-defined porosity and structural diversity, remain scarce. In this work, we present π-d PORMAKE, a software that enables the topology-guided construction of new 3D π–d conjugated MOFs. The software accurately accounts for the distinct coordination environments of π-d conjugated MOFs, particularly those that give rise to non-planar 3D structures. Leveraging π–d PORMAKE, we explore various combinations of redox-active MOF components in different topologies to construct 171 MOFs, each exhibiting significant porosity and π-d conjugated CT pathways for conductivity. By analyzing these MOFs, we derive essential design principles that can expedite the discovery of new 3D π-d conjugated MOFs better tailored for the electrochemical applications of interest.