Making 3d–4f hexanuclear clusters from heterotrinuclear cationic building blocks

• Published in: Inorganica Chimica Acta Vol. 360; no. 14; pp. 4044 - 4050
• Main Authors: Gheorghe, Ruxandra, Andruh, Marius, Costes, Jean-Pierre, Donnadieu, Bruno, Schmidtmann, Marc, Müller, Achim
• Format: Journal Article
• Language: English
• Published: Elsevier B.V 01.11.2007
• Subjects: Copper; Hexanuclear clusters; Lanthanides; Magnetic properties; Nickel; X-ray crystal structures; X-ray crystal structures; Nickel; Hexanuclear clusters; Copper; Lanthanides; Magnetic properties
• ISSN: 0020-1693; 1873-3255
• DOI: 10.1016/j.ica.2007.05.018

Two new 3d–4f hexanuclear systems, [{(LCu(ONO 2))(LCu(H 2O))Nd} 2(η 4-C 2O 4)](NO 3) 2 · 6H 2O ( 1), and [{(LNi(H 2O){N(CN) 2}) 2Pr} 2(η 3-NO 3)](OH) · 2H 2O · 3CH 3CN ( 2), were obtained by interconnecting heterotrinuclear cationic complexes [{LM II} 2Ln III] 3+ with oxalato and nitrato linkers, respectively; L is the dianion of the Schiff-base resulted from the 2:1 condensation of 3-methoxysalyciladehyde with 1,3-propanediamine. The syntheses and crystal structures of two new hexanuclear complexes are reported: [{(LCu II(ONO 2))(LCu II(H 2O))Nd III} 2(μ-C 2O 4)](NO 3) 2 · 6H 2O ( 1) and [{(LNi II(H 2O))(N(CN) 2)} 2Pr III} 2(ONO 2)](OH) · 2H 2O · 3CH 3CN ( 2) (L is the dianion of the Schiff-base resulted from the 2:1 condensation of 3-methoxysalyciladehyde with 1,3-propanediamine). Compounds 1 and 2 were obtained by connecting heterotrinuclear cationic complexes [{LM II} 2Ln III] 3+ with oxalato or nitrato linkers. The structure of the complex cation in 1 shows two almost linear trinuclear [Cu 2Nd] moieties which are linked by a bis-chelating oxalato bridge between the neodymium ions. The hexanuclear cationic moiety in 2 is built up of two heterotrinuclear [Ni 2Pr] units that are linked by a nitrato group bridging two praseodymium(III) ions. The spectroscopic (FTIR, UV–Vis) and magnetic properties of 1 and 2 have been investigated.