Halide-templated assembly of polynuclear lanthanide-hydroxo complexes

A series of pentadecanuclear lanthanide-hydroxo complexes possessing a common core of the formula [Ln(15)(mu(3)-OH)(20)(mu(5)-X)](24+)(1, Ln = Eu, X = Cl-; 2, Ln = Nd, X = Cl-; 3, Ln = Gd, X = Cl-; 4, Ln = Pr, X = Br-; 5, Ln = Eu, X = 130 were prepared by L-tyrosine-controlled hydrolysis of corresponding lanthanide perchlorates in the presence of added Cl- or Br-. The cationic cluster core comprises five vertex-sharing cubane-like [Ln(4)(mu(3)-OH)(4)](8+) units centered on the halide template. In the case of templating I-, dodecanuclear complexes were isolated instead. The core component, [Ln(12)(mu(3)-OH)(16)(I)(2)](18+) (6, Ln = Dy; 7, Ln = Er), consists of four vertex-sharing cubane-like [Ln(4)(mu(3)-OH)(4)](8+) units and exists as a square-shaped cyclic structure with one I- located on each side of the square plane. An analogous hydrolytic reaction involving Er(NO3)(3)1 L-tyrosine, and NaOH affords the known hexanuclear complex [Er-6(mu(6)-O)(mu(3)-OH)(8)(NO3)(6)(H2O)(12)](NO3)(2) whose core component is a face-capped octahedral [Er-6(mu(6)-O)(mu(3)-OH)(8)](8+) cluster with an interstitial mu(6)-oxo group (Wang, R.; Carducci, M. D.; Zheng, Z. Inorg. Chem. 2000, 39, 1836-1837.). The efficient self-assembly of halide-encapsulating multicubane complexes (1-7) and the inability to produce an analogous nitrate-containing complex demonstrate the superior templating roles played by the halide ion(s). Further credence for the halide template effects was provided by the isolation of the cationic pentadecanuclear complex 3 as the sole product when tyrosine-supported hydrolysis of Gd(NO3)3 was carried out in the presence of competitive Cl-. Magnetic moments of complexes 1-7 measured at room temperature by using Evans' method are in excellent agreement with those calculated by the Van Vleck equation, assuming magnetically noninteractive lanthanide ions.http://gateway.webofknowledge.com/gateway/Gateway.cgi?GWVersion=2&SrcApp=PARTNER_APP&SrcAuth=LinksAMR&KeyUT=WOS:000173482700015&DestLinkType=FullRecord&DestApp=ALL_WOS&UsrCustomerID=8e1609b174ce4e31116a60747a720701Chemistry, Inorganic & NuclearSCI(E)185ARTICLE2278-2864