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Microporous networks based on boronate ester-capped iron(ii) clathrochelate complexes are described. The networks were obtained by covalent cross-linking of tetrabrominated clathrochelate complexes via Suzuki–Miyaura polycross-coupling reactions with diboronic acids, or by Sonogashira–Hagihara polycross-coupling of clathrochelate complexes with terminal alkyne functions and 1,3,5-tribromobenzene. The networks display permanent porosity with apparent Brunauer–Emmett–Teller surface areas of up to SABET = 593 m2 g−1. A clathrochelate complex based on an enantiopure dioximato ligand was used to prepare chiral networks. One of these networks was shown to preferentially absorb d-tryptophan over l-tryptophan. [ABSTRACT FROM AUTHOR]