A surprising substitution of Cu by Li has been observed during the intercalation reaction of Cu3N with n‐butyllithium, besides an expected incorporation of Li. The twofold coordinated Cu+ ions are shifted into cuboctahedral cavities along with a reduction to Cu0 (see picture). The chemical bonding of the compounds LixCu3N is analyzed in comparison to Cu4N on the basis of band‐structure calculations.

The new compounds Ca6Pt8Cd16 (I), SrPt2Cd4 (II), and BaPt2Cd4 (III) are identified in the title systems.

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International audienceThe influences of an oxygen ligand on the structural, magnetic and electronic properties of octahedral niobium cluster-based oxides and oxychlorides are reported. The Nb6 metal cluster is edge-bridged by twelve inner ligands and additionally bonded to six apical ligands to form Nb6Li12La6 units (L = Cl, O) wherein oxygen and chlorine are perfectly ordered. Oxygen favours the interconnection of clusters via double Oi-a/Oa-i bridges in a similar way to the double Si-a/Sa-i bridges found in Chevrel phases based on face capped Mo6Li8La6 units. Periodic density functional theory (DFT) calculations confirm that increasing the number of inner oxygen ligands at the expense of chlorine atoms favours the 14 metal-electron (ME) count per octahedral cluster unit. It is also shown that weak interactions occur between neighbouring clusters. Indeed, magnetic measurements performed on AxNb6Cl12O2 (A = Rb, x = 0.816(8); A = Cs, x = 1) series containing 15-ME species evidence antiferromagnetic interactions at low temperatures. Broken-symmetry DFT calculations of exchange parameters within spin dimer analysis confirm the experimental results