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A ferromagnetically coupled Fe42 cyanide-bridged nanocage.

ABSTRACT: Self-assembly of artificial nanoscale units into superstructures is a prevalent topic in science. In biomimicry, scientists attempt to develop artificial self-assembled nanoarchitectures. However, despite extensive efforts, the preparation of nanoarchitectures with superior physical properties remains a challenge. For example, one of the major topics in the field of molecular magnetism is the development of high-spin (HS) molecules. Here, we report a cyanide-bridged magnetic nanocage composed of 18 HS iron(III) ions and 24 low-spin iron(II) ions. The magnetic iron(III) centres are ferromagnetically coupled, yielding the highest ground-state spin number (S = 45) of any molecule reported to date.

SUBMITTER: Kang S

PROVIDER: S-EPMC4354210 | biostudies-literature | 2015 Jan

REPOSITORIES: biostudies-literature

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A ferromagnetically coupled Fe42 cyanide-bridged nanocage.

Kang Soonchul S Zheng Hui H Liu Tao T Hamachi Kohei K Kanegawa Shinji S Sugimoto Kunihisa K Shiota Yoshihito Y Hayami Shinya S Mito Masaki M Nakamura Tetsuya T Nakano Motohiro M Baker Michael L ML Nojiri Hiroyuki H Yoshizawa Kazunari K Duan Chunying C Sato Osamu O

Nature communications 20150106

Self-assembly of artificial nanoscale units into superstructures is a prevalent topic in science. In biomimicry, scientists attempt to develop artificial self-assembled nanoarchitectures. However, despite extensive efforts, the preparation of nanoarchitectures with superior physical properties remains a challenge. For example, one of the major topics in the field of molecular magnetism is the development of high-spin (HS) molecules. Here, we report a cyanide-bridged magnetic nanocage composed of ...[more]

PMID: 25562786

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Project description:Recently, we reported the reaction of the (mu-oxo)diiron(III) complex 1 ([Fe(III)(2)(mu-O)(mu-O(2)H(3))(L)(2)](3+), L = tris(3,5-dimethyl-4-methoxypyridyl-2-methyl)amine) with 1 equiv of H(2)O(2) to yield a diiron(IV) intermediate, 2 (Xue, G.; Fiedler, A. T.; Martinho, M.; Munck, E.; Que, L., Jr. Proc. Natl. Acad. Sci. U.S.A. 2008, 105, 20615-20). Upon treatment with HClO(4), complex 2 converted to a species with an Fe(IV)(2)(mu-O)(2) diamond core that serves as the only synthetic model to date for the diiron(IV) core proposed for intermediate Q of soluble methane monooxygenase. Here we report detailed Mossbauer and density functional theory (DFT) studies of 2. The Mossbauer studies reveal that 2 has distinct Fe(IV) sites, a and b. Studies in applied magnetic fields show that the spins of sites a and b (S(a) = S(b) = 1) are ferromagnetically coupled to yield a ground multiplet with S = 2. Analysis of the applied field spectra of the exchange-coupled system yields for site b a set of parameters that matches those obtained for the mononuclear [LFe(IV)(O)(NCMe)](2+) complex, showing that site b (labeled Fe(O)) has a terminal oxo group. Using the zero-field splitting parameters of [LFe(IV)(O)(NCMe)](2+) for our analysis of 2, we obtained parameters for site a that closely resemble those reported for the nonoxo Fe(IV) complex [(beta-BPMCN)Fe(IV)(OH)(OO(t)Bu)](2+), suggesting that a (labeled Fe(OH)) coordinates a hydroxo group. A DFT optimization performed on 2 yielded an Fe-Fe distance of 3.39 A and an Fe-(mu-O)-Fe angle of 131 degrees , in good agreement with the results of our previous EXAFS study. The DFT calculations reproduce the Mossbauer parameters (A-tensors, electric field gradient, and isomer shift) of 2 quite well, including the observation that the largest components of the electric field gradients of Fe(O) and Fe(OH) are perpendicular. The ferromagnetic behavior of 2 seems puzzling given that the Fe-(mu-O)-Fe angle is large but can be explained by noting that the orbital structures of Fe(O) and Fe(OH) are such that the unpaired electrons at the two sites delocalize into orthogonal orbitals at the bridging oxygen, rationalizing the ferromagnetic behavior of 2. Thus, inequivalent coordinations at Fe(O) and Fe(OH) define magnetic orbitals favorable for ferromagnetic ineractions.

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A ferromagnetically coupled Fe42 cyanide-bridged nanocage.

Publications

A ferromagnetically coupled Fe42 cyanide-bridged nanocage.

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