Ferro- to Antiferromagnetic Crossover Angle in Diphenoxido- and Carboxylato-Bridged Trinuclear NiII2鈥揗nII Complexes: Experimental Observations and Theoretical Rational
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- 作者：Piya Seth ; Albert Figuerola ; Jes煤s Jover ; Eliseo Ruiz ; Ashutosh Ghosh
- 刊名：Inorganic Chemistry
- 出版年：2014
- 出版时间：September 2, 2014
- 年：2014
- 卷：53
- 期：17
- 页码：9296-9305
- 全文大小：456K
- ISSN：1520-510X
文摘
Three new trinuclear heterometallic NiII鈥揗nII complexes have been synthesized using a [NiL] metalloligand, where H2L = N,N鈥?bis(salicylidene)-1,3-propanediamine. The complexes [(NiL)2Mn(OCnn)2(CH3OH)2]路CH3OH (1), [(NiL)2Mn(OPh)2(CH3OH)2][(NiL)2Mn(OPh)2]路H2O (2), and [(NiL)2Mn(OSal)2(CH3OH)2]路2[NiL] (3) (where OCnn = cinnamate, OPh = phenylacetate, OSal = salicylate) have been structurally characterized. In all three complexes, in addition to the double phenoxido bridge, the two terminal NiII atoms are linked to the central MnII by means of a syn-syn bridging carboxylate, giving rise to a linear structure. Complexes 1 and 2 with Ni鈥揙鈥揗n angles of 97.24 and 96.43掳, respectively, exhibit ferromagnetic interactions (JNi鈥揗n = +1.38 and +0.50 cm鈥?, respectively), whereas 3 is antiferromagnetic (JNi鈥揗n = 鈭?.24 cm鈥?), having an Ni鈥揙鈥揗n angle of 98.51掳. DFT calculations indicate that there is a clear magneto-structural correlation between the Ni鈥揙鈥揗n angle and JNi鈥揗n values, which is in agreement with the experimental results.