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Resilient hosts: The porous coordination solids CUK‐1 (see structure; Co purple, C gray, N blue, O red/pink) and CUK‐2 are synthesized from unsymmetrical ligands and CoII ions. Even after the removal of co‐crystallized guests, the host frameworks are exceptionally stable. CUK‐1 shows a high capacity for H2 adsorption and is one of very few materials capable of separating N2 from O2.

A rare example of a molecular species prepared by solvothermal synthesis is the macrocyclic cobalt phosphonate/carboxylate 1, whose structure is shown schematically. At low temperatures this compound displays spontaneous magnetization due to canted antiferromagnetic ordering, which is very unusual for a discrete molecular material.

As a size‐selective molecular sieve, the coordination polymer formed from cobalt and pyridine‐2,4‐dicarboxylic acid (CUK‐1, see figure) shows unprecedented selectivity for O2 and preferential selectivity for CO2 over CH4. The present sorption results encourage the development of new adsorbent materials that may find use in the production of high‐purity gas products. This work demonstrates that CUK‐1 can be utilized, for the first time, in the separation of light gases via gas chromatography.

The hydrothermal reaction of thiosalicylic acid, (C(6)H(4)(CO(2)H)(SH)-1,2) with manganese(III) acetate leads to formation of the coordination solid [Mn(5)((C(6)H(4)(CO(2))(S)-1,2)(2))(4)(mu3-OH)2] (1) via a redox reaction, where resulting manganese(II) centres are coordinated by oxygen donor atoms and S-S disulfide bridge formation is simultaneously observed. Reaction of the same ligand under similar conditions with zinc(II) chloride yields the layered coordination solid [Zn(C(6)H(4)(CO(2))(S)-1,2)] (2). Hydrothermal treatment of manganese(III) acetate with 2-mercaptonicotinic acid, (NC(5)H(3)(SH)(CO(2)H)-2,3) was found to produce the 1-dimensional chain structure [Mn(2)((NC(5)H(3)(S)(CO(2))-2,3)(2))(2)(OH(2))(4)].4H(2)O (3) which also exhibits disulfide bridge formation and oxygen-only metal interactions. Compound 3 has been studied by thermogravimetric analysis and indicates sequential loss of lattice and coordinated water, prior to more comprehensive ligand fragmentation at elevated temperatures. The magnetic behaviour of 1 and 3 has been investigated and both exhibit antiferromagnetic interactions. The magnetic behaviour of 1 has been modelled as two corner-sharing isosceles triangles whilst 3 has been modelled as a 1-dimensional chain.

Reaction of selenium with (PhP)5, or Li2Se with PhPC12, gives a reactive intermediate (I) which undergoes reaction with acetone or CS2 to give new organo-phosphorus-selenium heterocycles which have been characterised by X-ray crysta I log ra p hy.

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