TY - JOUR
T1 - Hydrothermal synthesis and characterization of 2D M(II)-quinate (M = Co,Zn) metal-organic lattice assemblies
T2 - Solid-state solution structure correlation in M(II)-hydroxycarboxylate systems
AU - Menelaou, M.
AU - Konstantopai, A.
AU - Lalioti, N.
AU - Raptopoulou, C. P.
AU - Psycharis, V.
AU - Terzis, A.
AU - Mateescu, C.
AU - Tsarhopoulos, K.
AU - Rigas, P.
AU - Salifoglou, A.
PY - 2010/12/20
Y1 - 2010/12/20
N2 - Co(II) and Zn(II) ions exhibit variable reactivity toward O-containing ligands in aqueous media, affording isolable materials with distinct solid-state lattice properties. d-(-)-quinic acid is a cellular α-hydroxycarboxylate metal ion binder, which reacts with Co(II) and Zn(II) under pH-specific hydrothermal conditions, leading to the isolation of two new species [Co 2(C7H11O6)4] n•nH2O (1) and [Zn3(C7H 11O6)6]n•nH2O (2). Compound 1 was characterized by elemental analysis, spectroscopic techniques (FT-IR, UV-visible, EPR), magnetic studies, and X-ray crystallography. Compound 2 was characterized by elemental analysis, spectroscopic techniques (FT-IR, ESI-MS), and X-ray crystallography. The 2D molecular lattices in 1 and 2 reveal the presence of octahedral M(II) units bound exclusively to quinate in a distinct fashion, thereby projecting a unique chemical reactivity in each investigated system. The magnetic susceptibility and solid-state/frozen solution EPR data on 1 support the presence of a high-spin octahedral Co(II) in an oxygen environment, having a ground state with an effective spin of S = 1/2. Concurrent aqueous speciation studies on the binary Zn(II)-quinate system unravel the nature and properties of species arising from Zn(II)-quinate interactions as a function of pH and molar ratio. The physicochemical profiles of 1 and 2, in the solid state and in solution, earmark the importance of (a) select synthetic hydrothermal reactivity conditions, affording new well-defined lattice dimensionality and nuclearity M(II)-quinate materials, (b) structural speciation approaches delineating solid state-aqueous solution correlations in the binary M(II)-quinate systems, and (c) pH-specific chemical reactivity in binary M(II)-quinate systems reflecting structurally unique associations of simple aqueous complexes into distinctly assembled 2D crystalline lattices.
AB - Co(II) and Zn(II) ions exhibit variable reactivity toward O-containing ligands in aqueous media, affording isolable materials with distinct solid-state lattice properties. d-(-)-quinic acid is a cellular α-hydroxycarboxylate metal ion binder, which reacts with Co(II) and Zn(II) under pH-specific hydrothermal conditions, leading to the isolation of two new species [Co 2(C7H11O6)4] n•nH2O (1) and [Zn3(C7H 11O6)6]n•nH2O (2). Compound 1 was characterized by elemental analysis, spectroscopic techniques (FT-IR, UV-visible, EPR), magnetic studies, and X-ray crystallography. Compound 2 was characterized by elemental analysis, spectroscopic techniques (FT-IR, ESI-MS), and X-ray crystallography. The 2D molecular lattices in 1 and 2 reveal the presence of octahedral M(II) units bound exclusively to quinate in a distinct fashion, thereby projecting a unique chemical reactivity in each investigated system. The magnetic susceptibility and solid-state/frozen solution EPR data on 1 support the presence of a high-spin octahedral Co(II) in an oxygen environment, having a ground state with an effective spin of S = 1/2. Concurrent aqueous speciation studies on the binary Zn(II)-quinate system unravel the nature and properties of species arising from Zn(II)-quinate interactions as a function of pH and molar ratio. The physicochemical profiles of 1 and 2, in the solid state and in solution, earmark the importance of (a) select synthetic hydrothermal reactivity conditions, affording new well-defined lattice dimensionality and nuclearity M(II)-quinate materials, (b) structural speciation approaches delineating solid state-aqueous solution correlations in the binary M(II)-quinate systems, and (c) pH-specific chemical reactivity in binary M(II)-quinate systems reflecting structurally unique associations of simple aqueous complexes into distinctly assembled 2D crystalline lattices.
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U2 - 10.1021/ic1013945
DO - 10.1021/ic1013945
M3 - Article
C2 - 21082809
AN - SCOPUS:78650343299
SN - 0020-1669
VL - 49
SP - 11449
EP - 11462
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 24
ER -