The infrared spectra of complexes with planar dithiooxamides X. The Cu(LH2)2X1 complexes

In this article, the preparation, X-ray powder results and vibrational properties of a new type of complex with planar dithiooxamides are discussed. In acetonitrile, Cu(I) can form complexes with the formula Cu(LH₂)₂X₁ (X = Cl, Br) where LH₂ is an N,N'-disubstituted dithiooxamide. Complexes with N,N'-dimethyldithiooxamide and N,N'-diethyldithiooxamide have been prepared. A thorough vibrational analysis with infrared and Raman techniques was performed, assisted by H/D and ⁶³Cu/⁶⁵Cu isotope substitution. The vibrational study indicates the presence of an inversion centre in the structure. This leads to the proposal of a very unusual six-coordinate structure for these compounds, with the two dithiooxamide ligands, having S-cis conformation, coordinated to the same copper and with the halogens bridged between two different copper atoms. Confirmation of this result was attempted by X-ray analysis, but although several methods were tried to obtain crystals, only powder X-ray data could be obtained, which could not give a definitive answer. Since such six-coordinate Cu(I) has never been described before, a less rigourous interpretation of the vibrational data was followed, leading to a square-pyramidal five-coordinate structure, with a rather weak bond between Cu(I) and a terminal halogen. The latter structure, with the data available up to now, seems a bit more likely, since five-coordination for Cu(I) has already been described.     

Disorder effects in Mn12–acetate at 83 K

The structure of hexadeca‐μ‐acetato‐tetra­aqua­dodeca‐μ₃‐oxo‐dodecamanganese bis(acetic acid) tetrahydrate, [Mn₁₂O₁₂(CH₃COO)₁₆(H₂O)₄]·2CH₃COOH·4H₂O, known as Mn₁₂–acetate, has been determined at 83 (2) K by X‐ray diffraction methods. The fourfold (S₄) molecular symmetry is disrupted by a strong hydrogen‐bonding interaction with the disordered acetic acid mol­ecule of solvation, which displaces one of the acetate ligands in the cluster. Up to six Mn₁₂ isomers are potentially present in the crystal lattice, which differ in the number and arrangement of hydrogen‐bonded acetic acid mol­ecules. These results considerably improve the structural information available on this molecular nanomagnet, which was first synthesized and characterized by Lis [Acta Cryst. (1980), B 36 , 2042–2046].     

Site-specific ligation of anthracene-1,8-dicarboxylates to an Mn12 core: a route to the controlled functionalisation of single-molecule magnets

A novel single-molecule magnet of the Mn12 family, [Mn12O12(O2CC6H5)8(L)4(H2O)4].8CH2Cl2, has been synthesised by site-specific ligand exchange using a tailor-made dicarboxylate (L2-), which leads to selective occupation of axial binding sites.