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Crystal engineering is an emerging area of research in material, biological, and pharma‐ ceutical chemistry that involves synthesis of new materials, analysis of its structure including intermolecular interactions using X‐ray crystallography as well as computa‐ tional methods. It has been shown that the intermolecular interactions involving organic fluorine such as C−F∙∙∙H, F∙∙∙F, and C−F∙∙∙π play an important role in stabilizing the supramolecular assemblies, especially in the absence of strong intermolecular forces. Recently, non‐covalent interactions involving conjugated aromatic system such as porphyrins have been studied intensively. The synthetic porphyrins are of widespread attention because of their close resemblance to naturally occurring tetrapyrrolic pigments and they find various materials and biological applications. In this book chapter, we disclose our recent findings on detailed crystal structure analysis of a few series of fluorinated porphyrins using single‐crystal XRD as well as computational Hirshfeld surface analysis to understand the role of close contacts involving fluorine in the molecular crystal packing.

Fluorinated Porphyrinic Crystalline Solids: Structural Elucidation and Study of Intermolecular Interactions