Heptanuclear antiferromagnetic Fe(III)-d-(-)-quinato assemblies with an S = 3/2 ground state - PH-specific synthetic chemistry, spectroscopic, structural, and magnetic susceptibility studies

Melita Menelaou, E. Vournari, V. Psycharis, C. P. Raptopoulou, A. Terzis, V. Tangoulis, Y. Sanakis, C. Mateescu, A. Salifoglou

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    4 Citations (Scopus)

    Abstract

    Iron is an essential metal ion with numerous roles in biological systems and advanced abiotic materials. d-(-)-Quinic acid is a cellular metal ion chelator, capable of promoting reactions with metal M(II,III) ions under pH-specific conditions. In an effort to comprehend the chemical reactivity of well-defined forms of Fe(III)/Fe(II) toward α-hydroxycarboxylic acids, pH-specific reactions of: (a) [Fe3O(CH3COO) 6(H2O)3]·(NO3)·4H 2O with d-(-)-quinic acid in a molar ratio 1:3 at pH 2.5 and (b) Mohr's salt with d-(-)-quinic acid in a molar ratio 1:3 at pH 7.5, respectively, led to the isolation of the first two heptanuclear Fe(III)-quinato complexes, [Fe7O3(OH)3(C7H10O 6)6]·20.5H2O (1) and (NH 4)[Fe7(OH)6(C7H10O 6)6]·(SO4)2·18H 2O (2). Compounds 1 and 2 were characterized by analytical, spectroscopic (UV-vis, FT-IR, EPR, and Mössbauer) techniques, CV, TGA-DTG, and magnetic susceptibility measurements. The X-ray structures of 1 and 2 reveal heptanuclear assemblies of six Fe(III) ions bound by six doubly deprotonated quinates and one Fe(III) ion bound by oxido- and hydroxido-bridges (1), and hydroxido-bridges (2), all in an octahedral fashion. Mössbauer spectroscopy on 1 and 2 suggests the presence of Fe(III) ions in an all-oxygen environment. EPR measurements indicate that 1 and 2 retain their structure in solution, while magnetic measurements reveal an overall antiferromagnetic behavior with a ground state S = 3/2. The collective physicochemical properties of 1 and 2 suggest that the (a) nature of the ligand, (b) precursor form of iron, (c) pH, and (d) molecular stoichiometry are key factors influencing the chemical reactivity of the binary Fe(II,III)-hydroxycarboxylato systems, their aqueous speciation, and ultimately through variably emerging hydrogen bonding interactions, the assembly of multinuclear Fe(III)-hydroxycarboxylato clusters with distinct lattice architectures of specific dimensionality (2D-3D) and magnetic signature.

    Original languageEnglish
    Pages (from-to)13849-13860
    Number of pages12
    JournalInorganic chemistry
    Volume52
    Issue number24
    DOIs
    Publication statusPublished - 2013 Dec 16

    ASJC Scopus subject areas

    • Physical and Theoretical Chemistry
    • Inorganic Chemistry

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