The halogen bond is a non-covalent interaction between the electrophilic σ-hole of a halogen atom and the nucleophilic region of a second molecule (Figure ) . The inclusion of halogen bonds within a molecule often introduces specific and interesting properties associated with their directional 2 and hydrophobic nature 3 . For this reason, their routine exploitation has been used to drive the development of new modalities with exciting applications in many important research areas. A non-comprehensive but indictative list of examples includes crystal engineering 4 , supramolecular chemistry , biomolecular systems 6 , as well as the design of new drugs and catalysis 8 . Similarly, the use of haloorganic motifs as halogen bond catalysts also shows significant potential as an effective route to new catalyst exemplars that in many cases are capable of activating an array of diverse and important organic processes; examples include Diels-Alder reaction 9 , N-heteroarene reduction , Michael addition reaction 11 , and imine activation 12 . It is also noteworthy that the vast majority of halogen-bond catalysts incorporate either iodo (I), bromo (Br), or chloro (Cl) groups. A fact that contrasts sharply with the limited number of reactions catalyzed via F-halogen bonding interactions, which, to date, have received scant attention 8 . The existence of F-halogen bonding has been deliberated for some time. This stems from the fact that the strength of a halogen bond is closely related to the polarizability and electronegativity of the halogen atom employed , as well as the strength of the halogen bond it forms, which follows the order: I > Br > Cl 7a, 14 . For this reason, convention dictates that the most electronegative and least polarizable fluorine atom is not ordinarily expected to generate the essential σ-hole associated with efficient halogen bonding . Interestingly however, Politzer et al. and others 17 have demonstrated through computer simulations and crystallography that fluorine can form halogen bond interactions in both the gaseous and solid states (Figure ). Additionally, Baxter et al. reported experimental and computational evidence of nitrogenfluorine halogen bonding in Ag(I)-initiated radical C-H fluorinations (Figure ) . Most recently, Scheiner proposed conditions for fluorine-centered halogen bonding , and Lectka, Dudding and coworkers computationally designed systems demonstrating strong halogen bonding which included motifs using fluorine atoms and bicyclic diamine derivatives (Figure ) . Collectively, these findings indicate the possibility that fluorine-centred halogen bonding can occur under specific conditions . Given this under explored potential, their exploitation could open the door to innovative applications in many different and important research areas, such as synthetic and materials chemistry, catalysis, and supramolecular complex formation.