摘要
Reaction of [Mn(TTF-salphen)][OAc](TTF-salphen2-=2,2'-((2-(4,5-bis(methylthio)-1,3-dithiol-2-ylidene)-1,3-benzodithiole-5,6-diyl)bis(nitrilomethylidyne)bis(phenolate)dianion) and the cyanometalate building blocks [n-Bu4N][(Tp)Fe(CN)3](Tp=Tris(pyrazolyl)hydroborate) or [n-Bu4N][Ru(salen)(CN)2](salen2-=N,N′-ethylenebis(salicylideneimine)dianion) resulted in the formation of two redox-active complexes, the dinuclear heterometallic complex [(Tp)Fe(CN)3Mn(TTF-salphen)·CH3OH](1) and the one dimensional complex [Ru(salen)(CN)2Mn(TTF-salphen)]n(2). Both complexes were characterized by X-ray crystallography and solid state electrochemistry, in addition to static and dynamic magnetic measurements. Antiferromagnetic couplings are found to be operative between metal ion centers bridged by cyanide in both complexes. Complex 1 exhibited field-induced SMM behavior with an energy barrier of 13.8 K. The introduction of the redox-active TTF unit into cyanidebridged complexes with interesting magnetic properties renders them promising candidates for the construction of new hybrid inorganic-organic materials.
Reaction of [Mn（TTF-salphen）][OAc] （TTF-salphen2=2,2＇-（（2-（4,5-bis（methylthio）-1,3-dithiol-2-ylidene）-1,3-benzodithiole- 5,6-diyl）bis（nitrilomethylidyne）bis（pbenolate）dianion） and the cyanometalate building blocks [n-Bu4N][（Tp）Fe（CN）3] （Tp =Tris（pyrazolyl）hydroborate） or [n-Bu4N][Ru（salen）（CN）2] （salen2 =N,N＇-ethylenebis（salicylideneimine）dianion） resulted in the formation of two redox-active complexes, the dinuclear heterometallic complex [（Tp）Fe（CN）3Mn（TTF-salphen）＇CH3OH] （1） and the one dimensional complex [Ru（salen）（CN）2Mn（TTF-salphen）]n （2）. Both complexes were characterized by X-ray crystallography and solid state electrochemistry, in addition to static and dynamic magnetic measurements. Antiferromagnetic couplings are found to be operative between metal ion centers bridged by cyanide in both complexes. Complex 1 exhibited field-induced SMM behavior with an energy barrier of 13.8 K. The introduction of the redox-active TTF unit into cyanidebridged complexes with interesting magnetic properties renders them promising candidates for the construction of new hybrid inorganic-organic materials.
基金
supported by the National Basic Research Program of China(2011CB808704,2013CB922101)
the National Natural Science Foundation of China(51173075,91022031)
the Australian Research Council
