In the presence of the Et 4 N + cation the chloranilate dianion (can 2− ) associates with a range of divalent cations, M 2+ , to yield an isomorphous series of crystalline compounds of composition (Et 4 N) 2 [M 2 (can) 3 ] (M = Mg, Mn, Fe, Co, Ni, Cu, and Zn). The fluoranilate dianion (fan 2− ) likewise affords the closely related (Et 4 N) 2 [Zn 2 (fan) 3 ]. The structures of (Et 4 N) 2 [Zn 2 (can) 3 ], (Et 4 N) 2 [Fe 2 (can) 3 ], and (Et 4 N) 2 [Zn 2 (fan) 3 ] were determined by single crystal X-ray diffraction. Powder X-ray diffraction indicates that all the members of the can 2− series are isomorphous. The structure of (Et 4 N) 2 [Zn 2 (fan) 3 ] is very closely related to the structures of the can 2− compounds. The [M 2 (can) 3 2−

Reaction of the chloranilate dianion with Y(NO3)3 in the presence of Et4N+ in the appropriate proportions results in the formation of (Et4N)[Y(can)2], which consists of anionic square‐grid coordination polymer sheets with interleaved layers of counter‐cations. These counter‐cations, which serve as squat pillars between [Y(can)2] sheets, lead to alignment of the square grid sheets and the subsequent generation of square channels running perpendicular to the sheets. The crystals are found to be porous and retain crystallinity following cycles of adsorption and desorption. This compound exhibits a high affinity for volatile guest molecules, which could be identified within the framework by crystallographic methods. In situ neutron powder diffraction indicates a size‐shape complementarity leading to a strong interaction between host and guest for CO2 and CH4. Single‐crystal X‐ray diffraction experiments indicate significant interactions between the host framework and discrete I2 or Br2 molecules. A series of isostructural compounds (cat)[MIII(X‐an)2] with M=Sc, Gd, Tb, Dy, Ho, Er, Yb, Lu, Bi or In, cat=Et4N, Me4N and X‐an=chloranilate, bromanilate or cyanochloranilate bridging ligands have been generated. The magnetic properties of representative examples (Et4N)[Gd(can)2] and (Et4N)[Dy(can)2] are reported with normal DC susceptibility but unusual AC susceptibility data noted for (Et4N)[Gd(can)2].

The need for effective CO capture systems remains high, and due to their tunability, metallosupramolecular architectures are an attractive option for gas sorption. While the use of extended metal organic frameworks for gas adsorption has been extensively explored, the exploitation of discrete metallocage architectures to bind gases remains in its infancy. Herein the solid state gas adsorption properties of a series of [Pd (L) ] lantern shaped coordination cages (L = variants of 2,6-bis(pyridin-3-ylethynyl)pyridine), which had solvent accessible internal cavities suitable for gas binding, have been investigated. The cages showed little interaction with dinitrogen gas but were able to take up CO . The best performing cage reversibly sorbed 1.4 mol CO per mol cage at 298 K, and 2.3 mol CO per mol cage at 258 K (1 bar). The enthalpy of binding was calculated to be 25-35 kJ mol , across the number of equivalents bound, while DFT calculations on the CO binding in the cage gave ΔE for the cage-CO interaction of 23-28 kJ mol , across the same range. DFT modelling suggested that the binding mode is a hydrogen bond between the carbonyl oxygen of CO and the internally directed hydrogen atoms of the cage.

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