f,f Homodinuclear and d,f or f,f′ Heterodinuclear Complexes with a [2+2] Macrocyclic Compartmental Schiff Base

• Published in: European Journal of Inorganic Chemistry 2010-04, Vol.2010 (12), p.1853-1864
• Main Authors: Tamburini, Sergio, Peruzzo, Valentina, Benetollo, Franco, Vigato, P. Alessandro
• Format: Article
• Language: English
• Subjects: Heteronuclear complexes; Lanthanides; Macrocycles; Schiff bases
• ISSN: 1434-1948; 1099-0682
• DOI: 10.1002/ejic.200901165

The [2+2] compartmental macrocyclic complexes [Ln(H2‐L)(NO3)], where H2‐L is the cyclic Schiff base, derived from the condensation of 2,6‐diformyl‐4‐chlorophenol (H‐LA) or 2,6‐diformyl‐4‐methylphenol (H‐LB) and N,N‐bis(2‐aminoethyl)‐2‐hydroxybenzylamine·3HCl (HA′·3HCl), contains a free N3O3 coordination chamber and can act as a ligand toward an identical or a different lanthanide(III) ion and a d transition metal(II) ion to give the related f,f homodinuclear [Ln2(L)(X)2] and f,f′ heterodinuclear [LnLn′(L)(X)2] or d,f heterodinuclear [LnM(L)(X)] complexes. They have been characterized by ESEM‐EDS, ESI‐MS, and IR and 1H and 13C NMR spectroscopy. The X‐ray single‐crystal analysis of the [2+1] acyclic complex [Lu2(L′)2], derived from partial hydrolysis of the related [2+2] homodinuclear complex [Lu2(L)(Cl)2], followed by the loss of one lutetium(III) ion with the free formyl groups turning into diacetal ones, is also reported. A [2+2] symmetric compartmental macrocycle bearing two ‐CH2C6H4OH pendant arms and the related d,f heterodinuclear, f,f homodinuclear, and f,f′ heterodinuclearcomplexes were obtained through a template or step‐by‐step procedure. Their properties were investigated in the solid state and in solution.