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[摘要]：Bis(3-cyano-pentane-2,4-dionato) (CNacac) metal complex, [M-(CNacac)2], which acts as both a metal-ion-like and a ligand-like building unit, forms supramol. structures by self-assembly. Co-grinding of the metal acetates of MnII, CoII, NiII, CuII and ZnII with CNacacH formed a CNacac complex in all cases: mononuclear complex was formed in the cases of MnII, CuII and ZnII, whereas polymeric ones were formed in the cases of FeII, CoII and NiII. Subsequent annealing converted the mononuclear complexes of MnII, CuII and ZnII to their corresponding polymers as a result of dehydration of the mononuclear complexes. The resultant MnII, FeII, CoII, NiII and ZnII polymeric complexes had a common 3-dimensional structure with high thermal stability. In the case of CuII, a 1 D polymer was obtained. The MnII, CuII and ZnII polymeric complexes returned to their original mononuclear complexes on exposure to H2O vapor but they reverted to the polymeric complexes by re-annealing. Co-grinding of metal chlorides with CNacacH and annealing of the mononuclear CNacac complexes prepd. from soln. reactions were also examd. for comparison. [Mn(CNacac)2(H2O)2], [M(CNacac)2(H2O)] (M = CuII and ZnII) and [M(CNacac)2]?(M = MnII, FeII and ZnII) are new compds., which clearly indicated the power of the combined mechanochem./annealing method for the synthesis of varied metal coordination complexes. |
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