When we started this study, there were no reported structures of either TPyP or TBAP in their native uncoordinated states, even though these molecules have been used as struts in metal-organic frameworks (MOFs). A crystal structure of TBAP was subsequently published while this study was in progress. Molecular crystals are not subject to the same intuitive design rules associated with materials such as MOFs and COFs, because the crystallization of organic molecules is governed by an interplay of many weak intra-and intermolecular interactions. It therefore remains a significant challenge to design from first principles new organic molecular crystals that feature porosity and/or extended π-conjugation. Porosity is also much less common in organic crystals because of their strong preference for close packing. At the atomistic level, discovering a new material involves substantiating a stable minimum on the free energy surface defined by chemical composition and the relative positions of atoms within an extended solid. Traditionally, the search for new functional molecular crystals materials has been led by knowledge-guided experiment. However, the role of computation in materials discovery has evolved rapidly in the past few years, from explanatory post-analysis of new materials to genuinely predictive methods that can be applied in advance of, or in tandem with, experiment. Such computationally-led approaches promise to accelerate experimental searches and to unearth materials that might otherwise have remained undiscovered. One area where this applies is the design of porous materials, which have applications in gas storage, separation, and organic catalysis, as well as photocatalytic water splitting. For example, we have developed computational methods for crystal structure prediction (CSP) to generate energy-structure-function (ESF) maps, that have been used to target the discovery of highly porous hydrogen-bonded-frameworks (HOFs) and organic semiconductors. These ESF maps summarize the energetic distribution of stable crystal structures available to a given molecule, along with simulated properties relevant to the desired function.