Abstract
The one-pot synthesis of a Cu(II) complex with partially oxidized tetrathiafulvalene (TTF) moieties in its capping MT-Hsae-TTF ligands, [CuII(MT-sae-TTF)2] [CuICl2] was realized by the simultaneous occurrence of Cu(II) complexation and CuIICl2 mediated oxidation of TTF moieties. The crystal structure was composed of one-dimensional columns formed by partially oxidized TTF moieties and thus the cation radical salt showed relatively high electrical conductivity. Tight binding band structure calculations indicated the existence of a Peierls gap due to the tetramerization of the TTF moieties in the one-dimensional stacking column at room temperature, which is consistent with the semiconducting behavior of this salt.
Highlights
The interplay between electrical conductivity and magnetism provides a number of interesting physical phenomena such as colossal magneto-resistance and the Kondo effect, which have been widely investigated in inorganic compounds
[Cu(DCNQI)] has a band structure based on the hybridization of the d-orbitals of Cu and the π-orbitals of DCNQI [5,6], the paramagnetic Fe(III) complex of Phthalocyanine (Pc), TPP[Fe(Pc)(CN)2]2 (TPP = tetraphenylphosphonium) exhibits a giant negative magnetoresistance [7,8], and the single-component molecular metal based on TTF-dithiolato ligand, [Au(tmdt)2], undergoes an antiferromagnetic transition [9,10,11,12]
The Cu(II) complex of the MT-Hsae-TTF ligand was synthesized by the addition of a methanolic solution of CuIICl2·2H2O to a CH2Cl2 solution of MT-Hsae-TTF in the presence of triethylamine (Scheme 1)
Summary
The interplay between electrical conductivity and magnetism provides a number of interesting physical phenomena such as colossal magneto-resistance and the Kondo effect, which have been widely investigated in inorganic compounds. In order to enhance the π-d interaction in molecular based materials, paramagnetic metal complexes with TTF moiety-incorporating ligands have been widely prepared [13]. The TTF moieties in metal complexes are in their neutral state, resulting in electrical insulators with the exception of a few examples in which the TTF moieties are in their complete or partial oxidation states; a Mo(0) carbonyl complex with a TTF-phosphine ligand [14] and a Ni(II) dinuclear complex with TTF-pyridine ligands [15] were reported to afford cation radical salts with completely oxidized. The TTF-based metal complexes are expected to be stable upon oxidation of the TTF moieties in the ligands because of the chelating coordination site of the Schiff base moieties.
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