Structure Lattice-Dimensionality and Spectroscopic Property Correlations in Novel Binary and Ternary Materials of Group 13 Elements with α‑Hydroxycarboxylic Benzilic Acid and Phenanthroline

To probe and understand the structural and coordinative flexibility of Group 13 ions with α-hydroxycarboxylic acids, leading to crystalline inorganic–organic hybrid materials with distinct lattice architecture, dimensionality, and spectroscopic properties, the systematic synthesis and physicochemical properties of binary and ternary B­(III), Al­(III), Ga­(III), In­(III), and Tl­(I)-benzilic acid-(phenanthroline) systems were investigated in water–alcohol mixtures. Stoichiometric reactions of Group 13 ions with benzilic acid and phenanthroline (phen) afforded the new materials [B­(C₁₄H₁₀O₃)₂]­(C₃H₅N₂)­·H₂O (<b>1</b>), [Al­(C₁₄H₁₁O₃)₃]­·0.5C₂H₅OH­·4.5H₂O (<b>2</b>), [Ga­(C₁₄H₁₁O₃)₃]­·CH₃OH­·3H₂O (<b>3</b>), [In­(C₁₄H₁₁O₃)₄]­·C₃H₅N₂­·C₂H₅OH­·H₂O (<b>4</b>), [Tl­(C₁₄H₁₁O₃)]_<i>n</i> (<b>5</b>), [Tl₂(C₁₄H₁₁O₃)₂­(phen)₂] (<b>6</b>), and [Tl­(C₁₄H₁₁O₃)­(phen)­(H₂O)]­(C₁₄H₁₂O₃)­(phen) (<b>7</b>). All materials were characterized by elemental analysis, Fourier transform infrared spectroscopy, ¹³C, ¹¹B, ²⁷Al, ⁷¹Ga, and ²⁰⁵Tl cross-polarization/magic-angle spinning NMR, thermogravimetric analysis, luminescence, and single crystal X-ray diffraction. The nature of the benzilate ligand and phenanthroline in the chemical reaction mixtures with Group 13 ions led to the emergence of distinct lattice composition-dimensionality (1D-2D) correlations at the binary-ternary level, providing spectroscopic fingerprint identity to M­(I,III)-coordination and luminescence activity. The interplay between the benzilate ligand, phenanthroline, and Group 13 ions, (a) reveals well-defined contributions of the chemical and structural factors influencing the arising binary and ternary interactions at the M­(I) and M­(III) oxidation levels, and (b) clarifies correlations between crystal-lattice architecture and dimensionality with unique heteronuclear solid-state NMR and optical property signatures in inorganic–organic hybrid materials

Structure Lattice-Dimensionality and Spectroscopic Property Correlations in Novel Binary and Ternary Materials of Group 13 Elements with α‑Hydroxycarboxylic Benzilic Acid and Phenanthroline

To probe and understand the structural and coordinative flexibility of Group 13 ions with α-hydroxycarboxylic acids, leading to crystalline inorganic–organic hybrid materials with distinct lattice architecture, dimensionality, and spectroscopic properties, the systematic synthesis and physicochemical properties of binary and ternary B­(III), Al­(III), Ga­(III), In­(III), and Tl­(I)-benzilic acid-(phenanthroline) systems were investigated in water–alcohol mixtures. Stoichiometric reactions of Group 13 ions with benzilic acid and phenanthroline (phen) afforded the new materials [B­(C₁₄H₁₀O₃)₂]­(C₃H₅N₂)­·H₂O (<b>1</b>), [Al­(C₁₄H₁₁O₃)₃]­·0.5C₂H₅OH­·4.5H₂O (<b>2</b>), [Ga­(C₁₄H₁₁O₃)₃]­·CH₃OH­·3H₂O (<b>3</b>), [In­(C₁₄H₁₁O₃)₄]­·C₃H₅N₂­·C₂H₅OH­·H₂O (<b>4</b>), [Tl­(C₁₄H₁₁O₃)]_<i>n</i> (<b>5</b>), [Tl₂(C₁₄H₁₁O₃)₂­(phen)₂] (<b>6</b>), and [Tl­(C₁₄H₁₁O₃)­(phen)­(H₂O)]­(C₁₄H₁₂O₃)­(phen) (<b>7</b>). All materials were characterized by elemental analysis, Fourier transform infrared spectroscopy, ¹³C, ¹¹B, ²⁷Al, ⁷¹Ga, and ²⁰⁵Tl cross-polarization/magic-angle spinning NMR, thermogravimetric analysis, luminescence, and single crystal X-ray diffraction. The nature of the benzilate ligand and phenanthroline in the chemical reaction mixtures with Group 13 ions led to the emergence of distinct lattice composition-dimensionality (1D-2D) correlations at the binary-ternary level, providing spectroscopic fingerprint identity to M­(I,III)-coordination and luminescence activity. The interplay between the benzilate ligand, phenanthroline, and Group 13 ions, (a) reveals well-defined contributions of the chemical and structural factors influencing the arising binary and ternary interactions at the M­(I) and M­(III) oxidation levels, and (b) clarifies correlations between crystal-lattice architecture and dimensionality with unique heteronuclear solid-state NMR and optical property signatures in inorganic–organic hybrid materials

Structure Lattice-Dimensionality and Spectroscopic Property Correlations in Novel Binary and Ternary Materials of Group 13 Elements with α‑Hydroxycarboxylic Benzilic Acid and Phenanthroline

To probe and understand the structural and coordinative flexibility of Group 13 ions with α-hydroxycarboxylic acids, leading to crystalline inorganic–organic hybrid materials with distinct lattice architecture, dimensionality, and spectroscopic properties, the systematic synthesis and physicochemical properties of binary and ternary B­(III), Al­(III), Ga­(III), In­(III), and Tl­(I)-benzilic acid-(phenanthroline) systems were investigated in water–alcohol mixtures. Stoichiometric reactions of Group 13 ions with benzilic acid and phenanthroline (phen) afforded the new materials [B­(C₁₄H₁₀O₃)₂]­(C₃H₅N₂)­·H₂O (<b>1</b>), [Al­(C₁₄H₁₁O₃)₃]­·0.5C₂H₅OH­·4.5H₂O (<b>2</b>), [Ga­(C₁₄H₁₁O₃)₃]­·CH₃OH­·3H₂O (<b>3</b>), [In­(C₁₄H₁₁O₃)₄]­·C₃H₅N₂­·C₂H₅OH­·H₂O (<b>4</b>), [Tl­(C₁₄H₁₁O₃)]_<i>n</i> (<b>5</b>), [Tl₂(C₁₄H₁₁O₃)₂­(phen)₂] (<b>6</b>), and [Tl­(C₁₄H₁₁O₃)­(phen)­(H₂O)]­(C₁₄H₁₂O₃)­(phen) (<b>7</b>). All materials were characterized by elemental analysis, Fourier transform infrared spectroscopy, ¹³C, ¹¹B, ²⁷Al, ⁷¹Ga, and ²⁰⁵Tl cross-polarization/magic-angle spinning NMR, thermogravimetric analysis, luminescence, and single crystal X-ray diffraction. The nature of the benzilate ligand and phenanthroline in the chemical reaction mixtures with Group 13 ions led to the emergence of distinct lattice composition-dimensionality (1D-2D) correlations at the binary-ternary level, providing spectroscopic fingerprint identity to M­(I,III)-coordination and luminescence activity. The interplay between the benzilate ligand, phenanthroline, and Group 13 ions, (a) reveals well-defined contributions of the chemical and structural factors influencing the arising binary and ternary interactions at the M­(I) and M­(III) oxidation levels, and (b) clarifies correlations between crystal-lattice architecture and dimensionality with unique heteronuclear solid-state NMR and optical property signatures in inorganic–organic hybrid materials

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 Pb­(II), leading to crystalline metal–organic hybrid materials with distinct lattice architecture, dimensionality, and spectroscopic properties, the synthesis and physicochemical properties of binary/ternary Pb­(II)–(O,S)-dicarboxylic acid–(phenanthroline) systems was investigated in aqueous media. pH-specific hydrothermal reactions of Pb­(II) with O- and S-dicarboxylic acid ligands and phenanthroline (phen) afforded the variable dimensionality metal–organic Pb­(II) polymers [Pb₃(oda)₃]_<i>n</i> (<b>1</b>), [Pb­(phen)­(oda)]_<i>n</i> (<b>2</b>), [Pb­(tda)]_<i>n</i> (<b>3</b>), and [Pb­(phen)­(tda)]_<i>n</i> (<b>4</b>). The choice of O- vs S-ligands in the aqueous systems of Pb­(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 Pb­(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 Pb­(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 [Pb­(Heida)]_<i>n</i>·<i>n</i>H₂O­(<b>1</b>), [Pb­(Phen)­(Heida)]·4H₂O­(<b>2</b>), and [Pb₃(NO₃)­(Dpot)]_<i>n</i>(<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 Pb­(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 Pb­(II)–Heida system projects species complementing the synthetic efforts, thereby lending credence to a global structural speciation strategy in investigating binary/ternary Pb­(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 Pb­(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 Pb­(II)-(hydroxy-carboxylate) structures, based on which new Pb­(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 Pb­(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 [Pb­(Heida)]_<i>n</i>·<i>n</i>H₂O­(<b>1</b>), [Pb­(Phen)­(Heida)]·4H₂O­(<b>2</b>), and [Pb₃(NO₃)­(Dpot)]_<i>n</i>(<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 Pb­(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 Pb­(II)–Heida system projects species complementing the synthetic efforts, thereby lending credence to a global structural speciation strategy in investigating binary/ternary Pb­(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 Pb­(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 Pb­(II)-(hydroxy-carboxylate) structures, based on which new Pb­(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–H₂O₂–ligand interactions relevant to that metal ion’s biological role, synthetic efforts were launched involving the physiological ligands betaine (Me₃N⁺CH₂CO₂^–) and H₂O₂. In a pH-specific fashion, V₂O₅, betaine, and H₂O₂ reacted and afforded three new, unusual, and unique compounds, consistent with the molecular formulation K₂[V₂O₂(O₂)₄{(CH₃)₃­NCH₂CO₂)}]·H₂O (<b>1</b>), (NH₄)₂[V₂O₂(O₂)₄{(CH₃)₃­NCH₂CO₂)}]·0.75H₂O (<b>2</b>), and {Na₂[V₂O₂(O₂)₄{(CH₃)₃­NCH₂CO₂)}₂]}_<i>n</i>·4<i>n</i>H₂O (<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^VO)­(O₂)₂] units interacting through long V–O bonds. The two V­(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 V­(V) ions. In the case of the third complex <b>3</b>, the two vanadium centers are not immediate neighbors, with Na⁺ 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 V­(V)–diperoxido units, thereby stabilizing a dinuclear V­(V)–tetraperoxido dianion. Structural comparisons of the anions in <b>1</b>–<b>3</b> with other known dinuclear V­(V)–tetraperoxido binary anionic species provide insight into the chemical reactivity of V­(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–H₂O₂–ligand interactions relevant to that metal ion’s biological role, synthetic efforts were launched involving the physiological ligands betaine (Me₃N⁺CH₂CO₂^–) and H₂O₂. In a pH-specific fashion, V₂O₅, betaine, and H₂O₂ reacted and afforded three new, unusual, and unique compounds, consistent with the molecular formulation K₂[V₂O₂(O₂)₄{(CH₃)₃­NCH₂CO₂)}]·H₂O (<b>1</b>), (NH₄)₂[V₂O₂(O₂)₄{(CH₃)₃­NCH₂CO₂)}]·0.75H₂O (<b>2</b>), and {Na₂[V₂O₂(O₂)₄{(CH₃)₃­NCH₂CO₂)}₂]}_<i>n</i>·4<i>n</i>H₂O (<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^VO)­(O₂)₂] units interacting through long V–O bonds. The two V­(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 V­(V) ions. In the case of the third complex <b>3</b>, the two vanadium centers are not immediate neighbors, with Na⁺ 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 V­(V)–diperoxido units, thereby stabilizing a dinuclear V­(V)–tetraperoxido dianion. Structural comparisons of the anions in <b>1</b>–<b>3</b> with other known dinuclear V­(V)–tetraperoxido binary anionic species provide insight into the chemical reactivity of V­(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–H₂O₂–ligand interactions relevant to that metal ion’s biological role, synthetic efforts were launched involving the physiological ligands betaine (Me₃N⁺CH₂CO₂^–) and H₂O₂. In a pH-specific fashion, V₂O₅, betaine, and H₂O₂ reacted and afforded three new, unusual, and unique compounds, consistent with the molecular formulation K₂[V₂O₂(O₂)₄{(CH₃)₃­NCH₂CO₂)}]·H₂O (<b>1</b>), (NH₄)₂[V₂O₂(O₂)₄{(CH₃)₃­NCH₂CO₂)}]·0.75H₂O (<b>2</b>), and {Na₂[V₂O₂(O₂)₄{(CH₃)₃­NCH₂CO₂)}₂]}_<i>n</i>·4<i>n</i>H₂O (<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^VO)­(O₂)₂] units interacting through long V–O bonds. The two V­(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 V­(V) ions. In the case of the third complex <b>3</b>, the two vanadium centers are not immediate neighbors, with Na⁺ 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 V­(V)–diperoxido units, thereby stabilizing a dinuclear V­(V)–tetraperoxido dianion. Structural comparisons of the anions in <b>1</b>–<b>3</b> with other known dinuclear V­(V)–tetraperoxido binary anionic species provide insight into the chemical reactivity of V­(V)–diperoxido systems and their potential link to cellular events such as insulin mimesis and anitumorigenicity modulated by the presence of betaine