Binnemans Koen, Lodewyckx Katleen, Donnio Bertrand, Guillon Daniel
Department of Chemistry, Katholieke Universiteit Leuven, Celestijnenlaan 200F, 3001 Leuven, Belgium.
Chemistry. 2002 Mar 1;8(5):1101-5. doi: 10.1002/1521-3765(20020301)8:5<1101::aid-chem1101>3.0.co;2-9.
This paper describes the first examples of heteropolynuclear metallomesogens that contain both a transition metal ion and a trivalent lanthanide ion. Adducts were formed between a mesomorphic [Cu(salen)] complex (salen=2,2'-N,N'-bis(salicylidene)ethylenediamine) with six terminal tetradecyloxy chains and a lanthanide nitrate (Ln=La, Gd). Different stoichiometries were found, depending on the lanthanide ion: a trinuclear copper-lanthanum-copper complex [La(NO(3))(3)(Cu(salen))(2)] and a binuclear copper-gadolinium complex [Gd(NO(3))(3)Cu(salen)]. The compounds exhibit a hexagonal columnar mesophase (Col(H)) over a wide temperature-range with rather low melting temperatures. Although the clearing point could be observed for the parent [Cu(salen)] complex, the mixed f-d complexes decomposed in the high-temperature part of the mesomorphic domain before clearing. On the basis of X-ray diffraction measurements and molecular modelling, a structural model for the mesophase of the metal complexes is proposed.
本文描述了首例同时含有过渡金属离子和三价镧系离子的杂多核金属介晶。一种具有六个末端十四烷氧基链的介晶[Cu(salen)]配合物(salen = 2,2'-N,N'-双(水杨醛)乙二胺)与硝酸镧(Ln = La、Gd)形成了加合物。根据镧系离子的不同,发现了不同的化学计量比:一种三核铜 - 镧 - 铜配合物[La(NO(3))(3)(Cu(salen))(2)]和一种双核铜 - 钆配合物[Gd(NO(3))(3)Cu(salen)]。这些化合物在较宽的温度范围内呈现六方柱状介晶相(Col(H)),且熔点相当低。尽管母体[Cu(salen)]配合物能观察到清亮点,但混合的f - d配合物在介晶区域的高温部分清亮点之前就分解了。基于X射线衍射测量和分子建模,提出了金属配合物介晶相的结构模型。