6 research outputs found
Binary and Ternary Metal–Organic Hybrid Polymers in Aqueous Lead(II)–Dicarboxylic Acid–(Phen) Systems. The Influence of O- and S‑Ligand Heteroatoms on the Assembly of Distinct Lattice Architecture, Dimensionality, and Spectroscopic Properties
Poised
to understand the influence of O- and S-heteroatoms on the
chemical reactivity of dicarboxylic acids toward PbÂ(II), leading to
crystalline metal–organic hybrid materials with distinct lattice
architecture, dimensionality, and spectroscopic properties, the synthesis
and physicochemical properties of binary/ternary PbÂ(II)–(O,S)-dicarboxylic
acid–(phenanthroline) systems was investigated in aqueous media.
pH-specific hydrothermal reactions of PbÂ(II) with O- and S-dicarboxylic
acid ligands and phenanthroline (phen) afforded the variable dimensionality
metal–organic PbÂ(II) polymers [Pb<sub>3</sub>(oda)<sub>3</sub>]<sub><i>n</i></sub> (<b>1</b>), [PbÂ(phen)Â(oda)]<sub><i>n</i></sub> (<b>2</b>), [PbÂ(tda)]<sub><i>n</i></sub> (<b>3</b>), and [PbÂ(phen)Â(tda)]<sub><i>n</i></sub> (<b>4</b>). The choice of O- vs S-ligands
in the aqueous systems of PbÂ(II) and phenanthroline is linked to the
emergence of distinct lattice composition–dimensionality (2D–3D)
changes at the binary and ternary level, bestowing spectroscopic fingerprint
identity to PbÂ(II) coordination and luminescence activity
pH-Specific Hydrothermal Assembly of Binary and Ternary Pb(II)-(O,N-Carboxylic Acid) Metal Organic Framework Compounds: Correlation of Aqueous Solution Speciation with Variable Dimensionality Solid-State Lattice Architecture and Spectroscopic Signatures
Hydrothermal pH-specific reactivity in the binary/ternary
systems of PbÂ(II) with the carboxylic acids <i>N</i>-hydroxyethyl-iminodiacetic
acid (Heida), 1,3-diamino-2-hydroxypropane-<i>N</i>,<i>N</i>,<i>N</i>′,<i>N</i>′-tetraacetic
acid (Dpot), and 1,10-phenanthroline (Phen) afforded the new well-defined
crystalline compounds [PbÂ(Heida)]<sub><i>n</i></sub>·<i>n</i>H<sub>2</sub>OÂ(<b>1</b>), [PbÂ(Phen)Â(Heida)]·4H<sub>2</sub>OÂ(<b>2</b>), and [Pb<sub>3</sub>(NO<sub>3</sub>)Â(Dpot)]<sub><i>n</i></sub>(<b>3</b>). All compounds were characterized
by elemental analysis, FT-IR, solution or/and solid-state NMR, and
single-crystal X-ray diffraction. The structures in <b>1</b>–<b>2</b> reveal the presence of a PbÂ(II) center coordinated
to one Heida ligand, with <b>1</b> exhibiting a two-dimensional
(2D) lattice extending to a three-dimensional (3D) one through H-bonding
interactions. The concurrent aqueous speciation study of the binary
PbÂ(II)–Heida system projects species complementing the synthetic
efforts, thereby lending credence to a global structural speciation
strategy in investigating binary/ternary PbÂ(II)-Heida/Phen systems.
The involvement of Phen in <b>2</b> projects the significance
of nature and reactivity potential of N-aromatic chelators, disrupting
the binary lattice in <b>1</b> and influencing the nature of
the ultimately arising ternary 3D lattice. <b>3</b> is a ternary
coordination polymer, where PbÂ(II)-Dpot coordination leads to a 2D
metal–organic-framework material with unique architecture.
The collective physicochemical properties of <b>1</b>–<b>3</b> formulate the salient features of variable dimensionality
metal–organic-framework lattices in binary/ternary PbÂ(II)-(hydroxy-carboxylate)
structures, based on which new PbÂ(II) materials with distinct architecture
and spectroscopic signature can be rationally designed and pursued
synthetically
pH-Specific Hydrothermal Assembly of Binary and Ternary Pb(II)-(O,N-Carboxylic Acid) Metal Organic Framework Compounds: Correlation of Aqueous Solution Speciation with Variable Dimensionality Solid-State Lattice Architecture and Spectroscopic Signatures
Hydrothermal pH-specific reactivity in the binary/ternary
systems of PbÂ(II) with the carboxylic acids <i>N</i>-hydroxyethyl-iminodiacetic
acid (Heida), 1,3-diamino-2-hydroxypropane-<i>N</i>,<i>N</i>,<i>N</i>′,<i>N</i>′-tetraacetic
acid (Dpot), and 1,10-phenanthroline (Phen) afforded the new well-defined
crystalline compounds [PbÂ(Heida)]<sub><i>n</i></sub>·<i>n</i>H<sub>2</sub>OÂ(<b>1</b>), [PbÂ(Phen)Â(Heida)]·4H<sub>2</sub>OÂ(<b>2</b>), and [Pb<sub>3</sub>(NO<sub>3</sub>)Â(Dpot)]<sub><i>n</i></sub>(<b>3</b>). All compounds were characterized
by elemental analysis, FT-IR, solution or/and solid-state NMR, and
single-crystal X-ray diffraction. The structures in <b>1</b>–<b>2</b> reveal the presence of a PbÂ(II) center coordinated
to one Heida ligand, with <b>1</b> exhibiting a two-dimensional
(2D) lattice extending to a three-dimensional (3D) one through H-bonding
interactions. The concurrent aqueous speciation study of the binary
PbÂ(II)–Heida system projects species complementing the synthetic
efforts, thereby lending credence to a global structural speciation
strategy in investigating binary/ternary PbÂ(II)-Heida/Phen systems.
The involvement of Phen in <b>2</b> projects the significance
of nature and reactivity potential of N-aromatic chelators, disrupting
the binary lattice in <b>1</b> and influencing the nature of
the ultimately arising ternary 3D lattice. <b>3</b> is a ternary
coordination polymer, where PbÂ(II)-Dpot coordination leads to a 2D
metal–organic-framework material with unique architecture.
The collective physicochemical properties of <b>1</b>–<b>3</b> formulate the salient features of variable dimensionality
metal–organic-framework lattices in binary/ternary PbÂ(II)-(hydroxy-carboxylate)
structures, based on which new PbÂ(II) materials with distinct architecture
and spectroscopic signature can be rationally designed and pursued
synthetically
pH-Specific Structural Speciation of the Ternary V(V)–Peroxido–Betaine System: A Chemical Reactivity-Structure Correlation
Vanadium involvement in cellular processes requires deep
understanding of the nature and properties of its soluble and bioavailable
forms arising in aqueous speciations of binary and ternary systems.
In an effort to understand the ternary vanadium–H<sub>2</sub>O<sub>2</sub>–ligand interactions relevant to that metal ion’s
biological role, synthetic efforts were launched involving the physiological
ligands betaine (Me<sub>3</sub>N<sup>+</sup>CH<sub>2</sub>CO<sub>2</sub><sup>–</sup>) and H<sub>2</sub>O<sub>2</sub>. In a pH-specific
fashion, V<sub>2</sub>O<sub>5</sub>, betaine, and H<sub>2</sub>O<sub>2</sub> reacted and afforded three new, unusual, and unique compounds,
consistent with the molecular formulation K<sub>2</sub>[V<sub>2</sub>O<sub>2</sub>(O<sub>2</sub>)<sub>4</sub>{(CH<sub>3</sub>)<sub>3</sub>ÂNCH<sub>2</sub>CO<sub>2</sub>)}]·H<sub>2</sub>O (<b>1</b>), (NH<sub>4</sub>)<sub>2</sub>[V<sub>2</sub>O<sub>2</sub>(O<sub>2</sub>)<sub>4</sub>{(CH<sub>3</sub>)<sub>3</sub>ÂNCH<sub>2</sub>CO<sub>2</sub>)}]·0.75H<sub>2</sub>O (<b>2</b>),
and {Na<sub>2</sub>[V<sub>2</sub>O<sub>2</sub>(O<sub>2</sub>)<sub>4</sub>{(CH<sub>3</sub>)<sub>3</sub>ÂNCH<sub>2</sub>CO<sub>2</sub>)}<sub>2</sub>]}<sub><i>n</i></sub>·4<i>n</i>H<sub>2</sub>O (<b>3</b>). All complexes <b>1</b>–<b>3</b> were characterized by elemental analysis; UV/visible, FT-IR,
Raman, and NMR spectroscopy in solution and the solid state; cyclic
voltammetry; TGA-DTG; and X-ray crystallography. The structures of <b>1</b> and <b>2</b> reveal the presence of unusual ternary
dinuclear vanadium–tetraperoxido–betaine complexes containing
[(V<sup>V</sup>î—»O)Â(O<sub>2</sub>)<sub>2</sub>] units interacting
through long V–O bonds. The two VÂ(V) ions are bridged through
the oxygen terminal of one of the peroxide groups bound to the vanadium
centers. The betaine ligand binds only one of the two VÂ(V) ions. In
the case of the third complex <b>3</b>, the two vanadium centers
are not immediate neighbors, with Na<sup>+</sup> ions (a) acting as
efficient oxygen anchors and through Na–O bonds holding the
two vanadium ions in place and (b) providing for oxygen-containing
ligand binding leading to a polymeric lattice. In <b>1</b> and <b>3</b>, interesting 2D (honeycomb) and 1D (zigzag chains) topologies
of potassium nine-coordinate polyhedra (<b>1</b>) and sodium
octahedra (<b>3</b>), respectively, form. The collective physicochemical
properties of the three ternary species <b>1</b>–<b>3</b> project the chemical role of the low molecular mass biosubstrate
betaine in binding VÂ(V)–diperoxido units, thereby stabilizing
a dinuclear VÂ(V)–tetraperoxido dianion. Structural comparisons
of the anions in <b>1</b>–<b>3</b> with other known
dinuclear VÂ(V)–tetraperoxido binary anionic species provide
insight into the chemical reactivity of VÂ(V)–diperoxido systems
and their potential link to cellular events such as insulin mimesis
and anitumorigenicity modulated by the presence of betaine
pH-Specific Structural Speciation of the Ternary V(V)–Peroxido–Betaine System: A Chemical Reactivity-Structure Correlation
Vanadium involvement in cellular processes requires deep
understanding of the nature and properties of its soluble and bioavailable
forms arising in aqueous speciations of binary and ternary systems.
In an effort to understand the ternary vanadium–H<sub>2</sub>O<sub>2</sub>–ligand interactions relevant to that metal ion’s
biological role, synthetic efforts were launched involving the physiological
ligands betaine (Me<sub>3</sub>N<sup>+</sup>CH<sub>2</sub>CO<sub>2</sub><sup>–</sup>) and H<sub>2</sub>O<sub>2</sub>. In a pH-specific
fashion, V<sub>2</sub>O<sub>5</sub>, betaine, and H<sub>2</sub>O<sub>2</sub> reacted and afforded three new, unusual, and unique compounds,
consistent with the molecular formulation K<sub>2</sub>[V<sub>2</sub>O<sub>2</sub>(O<sub>2</sub>)<sub>4</sub>{(CH<sub>3</sub>)<sub>3</sub>ÂNCH<sub>2</sub>CO<sub>2</sub>)}]·H<sub>2</sub>O (<b>1</b>), (NH<sub>4</sub>)<sub>2</sub>[V<sub>2</sub>O<sub>2</sub>(O<sub>2</sub>)<sub>4</sub>{(CH<sub>3</sub>)<sub>3</sub>ÂNCH<sub>2</sub>CO<sub>2</sub>)}]·0.75H<sub>2</sub>O (<b>2</b>),
and {Na<sub>2</sub>[V<sub>2</sub>O<sub>2</sub>(O<sub>2</sub>)<sub>4</sub>{(CH<sub>3</sub>)<sub>3</sub>ÂNCH<sub>2</sub>CO<sub>2</sub>)}<sub>2</sub>]}<sub><i>n</i></sub>·4<i>n</i>H<sub>2</sub>O (<b>3</b>). All complexes <b>1</b>–<b>3</b> were characterized by elemental analysis; UV/visible, FT-IR,
Raman, and NMR spectroscopy in solution and the solid state; cyclic
voltammetry; TGA-DTG; and X-ray crystallography. The structures of <b>1</b> and <b>2</b> reveal the presence of unusual ternary
dinuclear vanadium–tetraperoxido–betaine complexes containing
[(V<sup>V</sup>î—»O)Â(O<sub>2</sub>)<sub>2</sub>] units interacting
through long V–O bonds. The two VÂ(V) ions are bridged through
the oxygen terminal of one of the peroxide groups bound to the vanadium
centers. The betaine ligand binds only one of the two VÂ(V) ions. In
the case of the third complex <b>3</b>, the two vanadium centers
are not immediate neighbors, with Na<sup>+</sup> ions (a) acting as
efficient oxygen anchors and through Na–O bonds holding the
two vanadium ions in place and (b) providing for oxygen-containing
ligand binding leading to a polymeric lattice. In <b>1</b> and <b>3</b>, interesting 2D (honeycomb) and 1D (zigzag chains) topologies
of potassium nine-coordinate polyhedra (<b>1</b>) and sodium
octahedra (<b>3</b>), respectively, form. The collective physicochemical
properties of the three ternary species <b>1</b>–<b>3</b> project the chemical role of the low molecular mass biosubstrate
betaine in binding VÂ(V)–diperoxido units, thereby stabilizing
a dinuclear VÂ(V)–tetraperoxido dianion. Structural comparisons
of the anions in <b>1</b>–<b>3</b> with other known
dinuclear VÂ(V)–tetraperoxido binary anionic species provide
insight into the chemical reactivity of VÂ(V)–diperoxido systems
and their potential link to cellular events such as insulin mimesis
and anitumorigenicity modulated by the presence of betaine
pH-Specific Structural Speciation of the Ternary V(V)–Peroxido–Betaine System: A Chemical Reactivity-Structure Correlation
Vanadium involvement in cellular processes requires deep
understanding of the nature and properties of its soluble and bioavailable
forms arising in aqueous speciations of binary and ternary systems.
In an effort to understand the ternary vanadium–H<sub>2</sub>O<sub>2</sub>–ligand interactions relevant to that metal ion’s
biological role, synthetic efforts were launched involving the physiological
ligands betaine (Me<sub>3</sub>N<sup>+</sup>CH<sub>2</sub>CO<sub>2</sub><sup>–</sup>) and H<sub>2</sub>O<sub>2</sub>. In a pH-specific
fashion, V<sub>2</sub>O<sub>5</sub>, betaine, and H<sub>2</sub>O<sub>2</sub> reacted and afforded three new, unusual, and unique compounds,
consistent with the molecular formulation K<sub>2</sub>[V<sub>2</sub>O<sub>2</sub>(O<sub>2</sub>)<sub>4</sub>{(CH<sub>3</sub>)<sub>3</sub>ÂNCH<sub>2</sub>CO<sub>2</sub>)}]·H<sub>2</sub>O (<b>1</b>), (NH<sub>4</sub>)<sub>2</sub>[V<sub>2</sub>O<sub>2</sub>(O<sub>2</sub>)<sub>4</sub>{(CH<sub>3</sub>)<sub>3</sub>ÂNCH<sub>2</sub>CO<sub>2</sub>)}]·0.75H<sub>2</sub>O (<b>2</b>),
and {Na<sub>2</sub>[V<sub>2</sub>O<sub>2</sub>(O<sub>2</sub>)<sub>4</sub>{(CH<sub>3</sub>)<sub>3</sub>ÂNCH<sub>2</sub>CO<sub>2</sub>)}<sub>2</sub>]}<sub><i>n</i></sub>·4<i>n</i>H<sub>2</sub>O (<b>3</b>). All complexes <b>1</b>–<b>3</b> were characterized by elemental analysis; UV/visible, FT-IR,
Raman, and NMR spectroscopy in solution and the solid state; cyclic
voltammetry; TGA-DTG; and X-ray crystallography. The structures of <b>1</b> and <b>2</b> reveal the presence of unusual ternary
dinuclear vanadium–tetraperoxido–betaine complexes containing
[(V<sup>V</sup>î—»O)Â(O<sub>2</sub>)<sub>2</sub>] units interacting
through long V–O bonds. The two VÂ(V) ions are bridged through
the oxygen terminal of one of the peroxide groups bound to the vanadium
centers. The betaine ligand binds only one of the two VÂ(V) ions. In
the case of the third complex <b>3</b>, the two vanadium centers
are not immediate neighbors, with Na<sup>+</sup> ions (a) acting as
efficient oxygen anchors and through Na–O bonds holding the
two vanadium ions in place and (b) providing for oxygen-containing
ligand binding leading to a polymeric lattice. In <b>1</b> and <b>3</b>, interesting 2D (honeycomb) and 1D (zigzag chains) topologies
of potassium nine-coordinate polyhedra (<b>1</b>) and sodium
octahedra (<b>3</b>), respectively, form. The collective physicochemical
properties of the three ternary species <b>1</b>–<b>3</b> project the chemical role of the low molecular mass biosubstrate
betaine in binding VÂ(V)–diperoxido units, thereby stabilizing
a dinuclear VÂ(V)–tetraperoxido dianion. Structural comparisons
of the anions in <b>1</b>–<b>3</b> with other known
dinuclear VÂ(V)–tetraperoxido binary anionic species provide
insight into the chemical reactivity of VÂ(V)–diperoxido systems
and their potential link to cellular events such as insulin mimesis
and anitumorigenicity modulated by the presence of betaine