Hedinger Roman, Ghisletta Michele, Hegetschweiler Kaspar, Tóth Eva, Merbach André E., Sessoli Roberta, Gatteschi Dante, Gramlich Volker
Laboratorium für Anorganische Chemie, ETH Zentrum, CH-8092 Zürich, Switzerland, Universität des Saarlandes, Fachrichtung Anorganische Chemie, Postfach 15 11 50, D-66041 Saarbrücken, Germany, Institut de Chimie Minérale et Analytique, Université de Lausanne-BCH, CH-1015 Lausanne, Switzerland, Dipartimento di Chimica, Università di Firenze, 50144 Florence, Italy, and Institut für Kristallographie, ETH Zentrum, CH-8092 Zürich, Switzerland.
Inorg Chem. 1998 Dec 28;37(26):6698-6705. doi: 10.1021/ic980685s.
A variety of trinuclear complexes M(3)(H(-)(3)L)(2) [M = Y, La, Eu, Gd, Dy; L = 1,3,5-triamino-1,3,5-trideoxy-cis-inositol (taci) and 1,3,5-trideoxy-1,3,5-tris(dimethylamino)-cis-inositol (tdci)] was prepared as solid materials of the composition M(3)(H(-)(3)L)(2)X(3).pH(2)O.qEtOH (X = Cl, NO(3); 2.5 </= p </= 9; q = 0, 0.33) and characterized by elemental analyses, NMR spectroscopy, and FAB(+) mass spectrometry. The crystal structures of [La(3)(H(-)(3)taci)(2)(H(2)O)(4)Cl]Cl(2).3H(2)O and [Gd(3)(H(-)(3)taci)(2)(H(2)O)(6)]Cl(3).3H(2)O were elucidated by single-crystal X-ray diffraction studies. The La complex crystallizes in the orthorhombic space group Pbca, a = 17.10(2) Å, b = 16.20(4) Å, c = 20.25(4) Å, Z = 8 for C(12)Cl(3)H(38)La(3)N(6)O(13). The Gd complex crystallizes in the monoclinic space group P2(1)/n, a = 10.294(3) Å, b = 15.494(5) Å, c = 19.994(6) Å, beta = 95.36(2) degrees, Z = 4 for C(12)Cl(3)Gd(3)H(42)N(6)O(15). The two complexes exhibited a unique, sandwich-type cage structure, where the two triply deprotonated taci ligands encapsulate an equilateral triangle of the three metal centers. The metal cations are coordinated to the equatorial, terminal amino groups and are bridged by the axial &mgr;(2)-alkoxo groups. The coordination spheres are completed by additional peripheral ligands such as H(2)O or Cl(-) counterions. The coordination number of the metal cations is 8. Magnetic susceptibility measurements of the Gd complex revealed very weak antiferromagnetic coupling interactions between the three Gd centers. Complex formation and species distribution in aqueous solution was investigated by potentiometry and pD-dependent NMR spectroscopy. An exclusive formation of the Eu(3)(H(-)(3)taci)(2) unit in solution was found in the range 7 </= pH </= 10. The formation constants were determined for the Y, Eu, Gd, Dy, and Lu complexes with taci. The stability of the lanthanoid complexes increased monotonically with decreasing ionic radius of the metal center.
制备了多种三核配合物M(3)(H(-)(3)L)(2) [M = Y、La、Eu、Gd、Dy；L = 1,3,5 - 三氨基 - 1,3,5 - 三脱氧 - 顺式 - 肌醇(taci)和1,3,5 - 三脱氧 - 1,3,5 - 三(二甲氨基) - 顺式 - 肌醇(tdci)]，其为组成M(3)(H(-)(3)L)(2)X(3).pH(2)O.qEtOH的固体材料(X = Cl、NO(3)；2.5 ≤ p ≤ 9；q = 0、0.33)，并通过元素分析、核磁共振光谱和快原子轰击(+)质谱进行了表征。通过单晶X射线衍射研究阐明了[La(3)(H(-)(3)taci)(2)(H(2)O)(4)Cl]Cl(2).3H(2)O和[Gd(3)(H(-)(3)taci)(2)(H(2)O)(6)]Cl(3).3H(2)O的晶体结构。La配合物结晶于正交晶系空间群Pbca中，对于C(12)Cl(3)H(38)La(3)N(6)O(13)，a = 17.10(2) Å，b = 16.20(4) Å，c = 20.25(4) Å，Z = 8。Gd配合物结晶于单斜晶系空间群P2(1)/n中，对于C(12)Cl(3)Gd(3)H(42)N(6)O(15)，a =
