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When bound to residues which can work as particularly strong electron withdrawing groups, fluorine can display a region of positive electrostatic potential (positive σ-hole). Fluorine can thus function as a halogen bond donor and form complexes with lone-pair-containing neutral atoms and anions. Examples in the gas, liquid, and solid phases are discussed.

Graphical abstract: The fluorine atom as a halogen bond donor, viz. a positive site

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