A family of ferrocene-rich Mn7, Mn8 and Mn13 clusters

doi:10.1016/j.poly.2006.11.014

Polyhedron

Volume 26, Issues 9–11, 15 June 2007, Pages 2276-2280

https://doi.org/10.1016/j.poly.2006.11.014 Get rights and content

Abstract

The use of ferrocene-1,1′-dicarboxylic acid (fdcH₂) in Mn cluster chemistry has led to a family of ferrocene-rich Mn₇, Mn₈ and Mn₁₃ clusters. The complexes are all mixed-valence. Solid-state DC and AC magnetic susceptibility studies have established the Mn₇, Mn₈ and Mn₁₃ complexes to possess S = 2, 5 and 9/2 ground states, respectively.

Graphical abstract

The reactions of ferrocene-1,1′-dicarboxylic acid with Mn reagents have led to the preparation of Mn₇, Mn₈ and Mn₁₃ clusters. The crystal structures and magnetic properties of these complexes are reported, which establishes that they possess S = 2, 5 and 9/2, respectively.

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Acknowledgement

We thank the National Science Foundation for supporting this work.

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N,C,N-intramolecularly coordinated antimony(III) and bismuth(III) oxides (ArMO)₂ [where Ar = [2,6-(Me₂NCH₂)₂C₆H₃]⁻, M = Sb (1) or Bi (2)] reacted with 1,1′-ferrocenedicarboxylic acid fc(COOH)₂ (fc = ferrocene-1,1′-diyl) under formation of corresponding carboxylates fc(COO)₂SbAr (4) and [fc(COO)₂BiAr]₂ (5). Similarly, the treatment of fc(COOH)₂ with tin(IV) carbonate ArSnPhCO₃ (3) led to the carboxylate fc(COO)₂Sn(Ph)Ar (6). All compounds were characterized by the help of multinuclear NMR, Raman, IR and UV–Vis spectroscopy and in the case of 4 and 5 using single-crystal X-ray diffraction analysis.
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The reaction of MnCl₂·4H₂O with t-BuPO₃H₂ in the presence of triethylamine afforded the tridecanuclear cage, [Mn^IIMn^III₁₂(μ₄-O)₆(μ-OH)₆(O₃P–t-Bu)₁₀(OH₂)₂(DMF)₄]·[2MeOH·4DMF] (1). The structural analysis of 1 reveals that it is a mixed-valent complex containing a [Mn^IIMn^III₁₂(μ₄-O)₆] core. The centre of the core is occupied by a Mn^II ion which is surrounded by 12 Mn^III ions. The latter are connected to each other by six μ-OH⁻ and 10 t-BuPO₃²⁻ ligands. The vacant coordination sites of six Mn^III ions situated in the periphery are occupied by four DMF and two water molecules. Magnetic studies on 1 reveal a frequency-dependent response which is characteristic of single-molecule magnets.
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Ferrocenecarboxylic acid is known since quite some time and its reactivity and reaction chemistry, respectively, has been viewed in terms of cluster synthesis [1,2], surface modification and bioinorganic applications including biosensors [3], and, for example, catalysis [4], since the ferrocene backbone is a brilliant building block for the construction of new molecules and materials with tailor-made properties, due to its robustness, well-established synthesis methodologies, and excellent redox properties. On the other hand, silver(I) carboxylates of type [AgO2CR] and [AgO2CR(Ln)], respectively, (R = single-bonded organic ligand) gained recently interest because they can be used as precursors in, for example, metallization processes using Chemical Vapor Deposition (CVD), Atomic Layer Deposition (ALD) [5,6], spin-coating [7], inkjet printing [8] or combustion-CVD [9] techniques to obtain silver films as well as patterns on different substrate materials. In addition, they are of importance as building blocks in the preparation of hetero(multi)nuclear transition metal complexes [10].
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The reaction of [Fe₃EuO₂(O₂CCCl₃)₈(H₂O)(THF)₃] or [Fe₂CaO(O₂CCCl₃)₆(THF)₄] and [Fe₃O(O₂CCMe₃)₆(H₂O)₃]NO₃ with 1,1′-ferrocenedicarboxylic acid (fcdcH₂) yielded penta- and hepta-nuclear [Fe₄O₂(O₂CCCl₃)₆(fcdc)(THF)₂(H₂O)₂] and [Fe₆O₂(OH)₂(O₂CCMe₃)₁₀(fcdc)(H₂O)₂], respectively, which are the first X-ray structurally characterized clusters comprising Fe(III) and the ferrocenedicarboxylic organometallic ligand. Variable-temperature solid-state magnetic susceptibility measurements in the temperature range 1.8–300 K were carried out, and for both complexes a predominantly antiferromagnetic exchange interaction between the metal centres was observed. Mössbauer investigations show the presence of different environments for the Fe(III) atoms and confirm that no electron-transfer from Fe(II) of the ferrocene unit to Fe(III) of the central core occurs.

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A family of ferrocene-rich Mn7, Mn8 and Mn13 clusters

Abstract

Graphical abstract

Section snippets

Acknowledgement

MRS Bull.

Struct. Bond.

Adv. Funct. Mater.

Angew. Chem., Int. Ed.

Chem. Rev.

Catal. Today

Dalton Trans.

Eur. J. Inorg. Chem.

Electroanalysis

A family of ferrocene-rich Mn₇, Mn₈ and Mn₁₃ clusters