In Situ Generation of Carboxylate: An Efficient Strategy for a One-Pot Synthesis of Homo- and Heterometallic Polynuclear Complexes

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• 作者：Konstantin S. Gavrilenko ; Sergey V. Punin ; Olivier Cador ; Sté ; phane Golhen ; Lahcè ; ne Ouahab ; and Vitaly V. Pavlishchuk
• 刊名：Journal of the American Chemical Society
• 出版年：2005
• 出版时间：September 7, 2005
• 年：2005
• 卷：127
• 期：35
• 页码：12246 - 12253
• 全文大小：276K
• 年卷期：v.127,no.35(September 7, 2005)
• ISSN：1520-5126

文摘

An efficient strategy for synthesis of a wide range of homo- and heterometallic polynuclearcomplexes is proposed. The synthesis protocol consists of a two-step one-pot reaction. The first step isthe in situ generation of carboxylate anions via oxidation of aromatic aldehydes by metal nitrates in air.The aldehydes act as solvents and are also involved in redox processes. Solutions containing solely transitionmetal cations and aromatic carboxylates are obtained following this procedure. The second step is a tunable"à la carte" formation of a series of various polynuclear carboxylato complexes from solutions obtained atthe former stage upon addition of different solvents. The polarity and donor properties of the solvents playa key role in determination of the nuclearities of the complexes. Hydrolytic processes can induce theformation of oxo- or hydroxo-bridges inside the polynuclear core as well. Complexes of various nuclearitiesare obtained: from discrete tri-, hexa-, or octanuclear units to 1D polymers. This protocol can be adaptedwith disconcerting simplicity to the synthesis of heterometallic species with similar molecular structures totheir homometallic analogues starting from stoichiometric mixture of metal nitrates under the same reactionconditions. Detailed description of synthesis and the molecular structure of one representative complex foreach series are presented in this paper. The temperature dependence of magnetic susceptibility of theheterometallic 1-D MnCo chain reveals typical behavior of a ferrimagnetic chain. The low-temperatureinvestigations on single crystals show significant Ising type magnetic anisotropy.