Rational Design of Homo and Hetero Hexanuclear Coordination Compounds: Syntheses and Magnetic Properties of [Cu2IIM4II] (M= Cu, Ni) Species and the Crystal Structure of {[Cu(tmen)(H2O)]2[Cu(tmen)]2[CuL](H2O)}(ClO4)4.2H2O

[EN] New homo¿ and heterometallic hexanuclear complexes of formula {[Cu(tmen)(H2O)]2[Cu(tmen)]2[Cu2L](H2O)}(ClO4)4 · 2 H2O [Cu6¿tmen] {[Cu(pmdien)]4[Cu2L]}(ClO4)4 · 4 H2O [Cu6¿pmdien] and {[Ni(cyclam)]4[Cu2L]}(ClO4)4 · 4 H2O [Cu2Ni4¿cyclam] [H8L = tetrakis(aminomethylene)methanetetrakis(oxamic acid), tmen = N,N,N¿,N¿¿tetramethylethylenediamine, pmdien = N,N,N¿,N¿,N¿¿pentamethyldiethylenetriamine, and cyclam = 1,4,8,11¿tetraazacyclotetradecane] have been synthesized. The crystal structure of [Cu6¿tmen] has been determined by single¿crystal X¿ray diffraction. The structure consists of cationic {[Cu(tmen)(H2O)]2[Cu(tmen)]2[Cu2L](H2O)}4+ hexanuclear units. The hexanuclear cation is made up of two symmetry¿related oxamato¿bridged trinuclear units connected through the central carbon atom C(6) of the L8¿ ligand. Variable¿temperature magnetic susceptibility measurements (1.8¿300K) have been performed for these series of complexes including the dinuclear precursors of formula Na4[Cu2L] · 10.5 H2O [Cu2¿Na], (NMe4)4[Cu2L] · 4 H2O [Cu2¿NMe4] and (PPh4)4[Cu2L] · 6 H2O [Cu2¿PPh4]. The magnetic data have been interpreted. Evidence of a weak intramolecular ferromagnetic interaction between the two CuII ions in [Cu2L]4¿ has been observed. For the hexanuclear species, the interaction through the oxamato bridge was found to be equal to ¿6790, ¿2650, and ¿1643 yJ (¿342, ¿133, and ¿82cm¿1) for [Cu6¿tmen], [Cu6¿pmdien], and [Cu2Ni4¿cyclam], respectively. 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