NDLI: Exploring the Effect of Metal Ions and Counteranions on the Structure and Magnetic Properties of Five Dodecanuclear $Co^{II}$ and $Ni^{II}$ Clusters

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Exploring the Effect of Metal Ions and Counteranions on the Structure and Magnetic Properties of Five Dodecanuclear $Co^{II}$ and $Ni^{II}$ Clusters

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Exploring the Effect of Metal Ions and Counteranions on the Structure and Magnetic Properties of Five Dodecanuclear $Co^{II}$ and $Ni^{II}$ Clusters

Content Provider	World Health Organization (WHO)-Global Index Medicus
Author	Zhou, Yan-ling Liang, Hong Liu, Xiao-chun Zeng, Ming-hua Kurmoo, Mohamedally
Description	Author Affiliation: Zhou YL ( Key Laboratory for the Chemistry and Molecular Engineering of Medicinal Resources (Ministry of Education of China), School of Chemistry and Chemical Engineering, Guangxi Normal University, Guilin 541004, P.R. China.)
Abstract	We present the synthesis, characterization of the structures, and magnetic properties of five isostructural dodecanuclear coordination clusters of $Ni^{II}$ and $Co^{II}:$ $[Co_{12}(bm)_{12}(NO_{3})-$ $(O_{2}CMe)_{6}(EtOH)_{6}](NO_{3})_{5}$ (1), $[Ni_{12}(bm)_{12}(NO_{3})(O_{2}CMe)_{6}(H_{2}O)_{3}-$ $(EtOH)_{3}](NO_{3})_{5}⋅2 H_{2}O$ (2), mixed-metal composition (Ni/Co 1:1) $[Co_{6}Ni_{6}(bm)_{12}(NO_{3})(O_{2}CMe)_{6}(EtOH)_{6}](NO_{3})_{5}$ (3), and $[M_{12}(bm)_{12}(NO_{3})-$ $(O_{2}CMe)_{6}(EtOH)_{6}](ClO_{4})_{5}$ (M=Co (4), Ni (5)), in which Hbm=(1H-benzimidazol-2-yl)methanol. They consist of analogous structural cores that are constructed by three cubanes $(M_{4}O_{4})$ that surround the templating nitrate and bridging auxiliary acetate and the directing ligands bm. They have different magnetic behaviors. Whereas there is the absence of the out-of-phase ac susceptibility (χ′′) for the $Ni^{II}-based$ compounds 2 and 5, the $Co^{II}-containing$ compounds 1, 3, and 4 have prominent χ′′ signals that exhibit frequency dependence, which indicates slow magnetic relaxation behavior above 1.8 K. In particular, the larger perchlorate counterions in 4 further change the overall correlation interaction between clusters, thus leading to an enhanced blocking temperature for the less-symmetrical 4 $(pseudo-C_{3})$ relative to 1 and 3 (true $C_{3}).$ Interestingly, electrospray ionization mass spectrometry (ESI-MS) indicates that the three dodecanuclear clusters of 1–3 retain their compositions in solution. The mixed-metal cluster cores of 3 are formed based on the nature of the interchangeability between metal centers in solution.
ISSN	09476539
e-ISSN	15213765
Journal	Chemistry - A European Journal
Issue Number	50
Volume Number	17
Language	English
Publisher	Wiley-VCH;ChemPubSoc Europe
Publisher Date	2011-12-09
Publisher Place	Germany
Access Restriction	Open
Subject Keyword	Benzimidazoles Chemistry Cobalt Ions Nickel Organometallic Compounds Crystallography, X-Ray Ligands Magnetics Molecular Structure Research Support, Non-U.S. Gov't
Content Type	Text
Resource Type	Article
Subject	Organic Chemistry Catalysis

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