The assembly of monovalent species of [Ni(dmit)2] (dmit2- = 2-thioxo-1,3-dithiole-4,5-dithiolate), which bear S = 1/2 spin on each molecule, was controlled by using crown-ether based supramolecular cations. We could regulate the shape and valence of the supramolecular cations by changing the ring size of the crown ethers as well as the metal cations included. Since the structure of the ionic crystals is mainly determined by the Madelung energy and the Lennard-Jones potential (shape of molecules), a large diversity in crystal structure was observed. A relationship between the overlap of [Ni(dmit)2] frontier orbitals and the magnetism is discussed.
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