화학공학소재연구정보센터
Inorganic Chemistry, Vol.46, No.22, 9312-9322, 2007
Tuneable intramolecular intermetallic interactions as a new tool for programming linear heterometallic 4f-4f complexes
Statistical mechanics predicts that the design of pure organized heteropolymetallic chains of metal ions bound to linear receptors depends on controlled deviations from the mixing rule triangle E-MMj = 1/2 (triangle E-MMi + triangle E-mjmj), whereby triangle E-MiMj is the intramolecular intermetallic interaction between neighboring metal i and metal j along the receptor. A thorough investigation of linear polymetallic trivalent lanthanide triple-stranded helicates shows that such deviations are amplified by an increase in the nuclearity of the final complexes and are thus easily evidenced in the tetranuclear heterobimetallic helicates [La-4_Lu-y(y) (L6)(3)](12+) (y = 0-4). The chemical and physical origins of this unprecedented behavior are discussed together with its practical consequences for programming pure heteropolymetallic 4f-4f complexes.