A Family of Metal–Organic Frameworks Based on Carboxylates and a Neutral, Long, and Rigid Ligand: Their Structural Revelation, Magnetic, and Luminescent Property Study

Four new two-dimensional/three-dimensional (2D/3D) bpmh-based metal organic frameworks, namely, {[Zn­(1,3-adaa)­(bpmh)]}_<i>n</i> (<b>1</b>), {[Cd­(1,3-adaa)­(bpmh)]}<i>_n</i> (<b>2</b>), {[Zn­(1,4-pdaa)­(bpmh)]}_<i>n</i> (<b>3</b>), and {[Co­(1,4-pdaa)­(bpmh)]}_<i>n</i> (<b>4</b>) (bpmh = <i>N</i>,<i>N</i>-bis-pyridin-4-ylmethylene-hydrazine, 1,3-adaa = 1,3-adamantane diacetic acid, 1,4-pdaa = 1,4-phenylene diacetic acid) have been synthesized through the slow diffusion technique. Structural determination reveals that compounds <b>1</b> and <b>2</b> have 2D layered architectures with similar framework topology, whereas <b>3</b> and <b>4</b> are isostuctural 3D frameworks. Both <b>1</b> and <b>2</b> perceives a common secondary building unit (SBU) [M₂(adaa)₄(bpmh)₄] [M = Zn­(<b>1</b>) and Cd­(<b>2</b>)]. In compound <b>1</b>, 1,3-adaa exhibits both μ- 1,1 and μ- 1,2 bridging modes, whereas in <b>2</b> it shows both μ-1,1 and μ-1,1,2 bridging modes. The difference in the bridging mode of 1,3-adaa in <b>1 </b>(Zn) and <b>2 </b>(Cd) is responsible for the shorter M···M contacts in <b>2</b> (3.872 Å) than in <b>1</b> (4.13 Å) in the SBU. The 1,3-adaa ligands are sandwiched between the bpmh linkers in compounds <b>1</b> and <b>2.</b> In compounds <b>3</b> and <b>4</b>, 1,4-pdaa exhibits both μ-1 and μ-1,1 bridging modes and are isostructural in nature. The metal centers are arranged in a helical fashion around 2₁ screw axis in <b>3</b> and <b>4</b>. In compounds <b>1</b>–<b>4</b>, the used dicarboxylic acids act as pillars between the metal-bpmh layers. Solid-state photoluminescent properties of compounds <b>1</b>–<b>3</b> show ligand (n → π* and π → π*)-based florescence. The magnetic studies of compound <b>4</b> show presence of the antiferromagnetic exchange between the metal centers

A Family of Metal–Organic Frameworks Based on Carboxylates and a Neutral, Long, and Rigid Ligand: Their Structural Revelation, Magnetic, and Luminescent Property Study

Four new two-dimensional/three-dimensional (2D/3D) bpmh-based metal organic frameworks, namely, {[Zn­(1,3-adaa)­(bpmh)]}_<i>n</i> (<b>1</b>), {[Cd­(1,3-adaa)­(bpmh)]}<i>_n</i> (<b>2</b>), {[Zn­(1,4-pdaa)­(bpmh)]}_<i>n</i> (<b>3</b>), and {[Co­(1,4-pdaa)­(bpmh)]}_<i>n</i> (<b>4</b>) (bpmh = <i>N</i>,<i>N</i>-bis-pyridin-4-ylmethylene-hydrazine, 1,3-adaa = 1,3-adamantane diacetic acid, 1,4-pdaa = 1,4-phenylene diacetic acid) have been synthesized through the slow diffusion technique. Structural determination reveals that compounds <b>1</b> and <b>2</b> have 2D layered architectures with similar framework topology, whereas <b>3</b> and <b>4</b> are isostuctural 3D frameworks. Both <b>1</b> and <b>2</b> perceives a common secondary building unit (SBU) [M₂(adaa)₄(bpmh)₄] [M = Zn­(<b>1</b>) and Cd­(<b>2</b>)]. In compound <b>1</b>, 1,3-adaa exhibits both μ- 1,1 and μ- 1,2 bridging modes, whereas in <b>2</b> it shows both μ-1,1 and μ-1,1,2 bridging modes. The difference in the bridging mode of 1,3-adaa in <b>1 </b>(Zn) and <b>2 </b>(Cd) is responsible for the shorter M···M contacts in <b>2</b> (3.872 Å) than in <b>1</b> (4.13 Å) in the SBU. The 1,3-adaa ligands are sandwiched between the bpmh linkers in compounds <b>1</b> and <b>2.</b> In compounds <b>3</b> and <b>4</b>, 1,4-pdaa exhibits both μ-1 and μ-1,1 bridging modes and are isostructural in nature. The metal centers are arranged in a helical fashion around 2₁ screw axis in <b>3</b> and <b>4</b>. In compounds <b>1</b>–<b>4</b>, the used dicarboxylic acids act as pillars between the metal-bpmh layers. Solid-state photoluminescent properties of compounds <b>1</b>–<b>3</b> show ligand (n → π* and π → π*)-based florescence. The magnetic studies of compound <b>4</b> show presence of the antiferromagnetic exchange between the metal centers

A Family of Metal–Organic Frameworks Based on Carboxylates and a Neutral, Long, and Rigid Ligand: Their Structural Revelation, Magnetic, and Luminescent Property Study

Four new two-dimensional/three-dimensional (2D/3D) bpmh-based metal organic frameworks, namely, {[Zn­(1,3-adaa)­(bpmh)]}_<i>n</i> (<b>1</b>), {[Cd­(1,3-adaa)­(bpmh)]}<i>_n</i> (<b>2</b>), {[Zn­(1,4-pdaa)­(bpmh)]}_<i>n</i> (<b>3</b>), and {[Co­(1,4-pdaa)­(bpmh)]}_<i>n</i> (<b>4</b>) (bpmh = <i>N</i>,<i>N</i>-bis-pyridin-4-ylmethylene-hydrazine, 1,3-adaa = 1,3-adamantane diacetic acid, 1,4-pdaa = 1,4-phenylene diacetic acid) have been synthesized through the slow diffusion technique. Structural determination reveals that compounds <b>1</b> and <b>2</b> have 2D layered architectures with similar framework topology, whereas <b>3</b> and <b>4</b> are isostuctural 3D frameworks. Both <b>1</b> and <b>2</b> perceives a common secondary building unit (SBU) [M₂(adaa)₄(bpmh)₄] [M = Zn­(<b>1</b>) and Cd­(<b>2</b>)]. In compound <b>1</b>, 1,3-adaa exhibits both μ- 1,1 and μ- 1,2 bridging modes, whereas in <b>2</b> it shows both μ-1,1 and μ-1,1,2 bridging modes. The difference in the bridging mode of 1,3-adaa in <b>1 </b>(Zn) and <b>2 </b>(Cd) is responsible for the shorter M···M contacts in <b>2</b> (3.872 Å) than in <b>1</b> (4.13 Å) in the SBU. The 1,3-adaa ligands are sandwiched between the bpmh linkers in compounds <b>1</b> and <b>2.</b> In compounds <b>3</b> and <b>4</b>, 1,4-pdaa exhibits both μ-1 and μ-1,1 bridging modes and are isostructural in nature. The metal centers are arranged in a helical fashion around 2₁ screw axis in <b>3</b> and <b>4</b>. In compounds <b>1</b>–<b>4</b>, the used dicarboxylic acids act as pillars between the metal-bpmh layers. Solid-state photoluminescent properties of compounds <b>1</b>–<b>3</b> show ligand (n → π* and π → π*)-based florescence. The magnetic studies of compound <b>4</b> show presence of the antiferromagnetic exchange between the metal centers

A Family of Metal–Organic Frameworks Based on Carboxylates and a Neutral, Long, and Rigid Ligand: Their Structural Revelation, Magnetic, and Luminescent Property Study

Four new two-dimensional/three-dimensional (2D/3D) bpmh-based metal organic frameworks, namely, {[Zn­(1,3-adaa)­(bpmh)]}_<i>n</i> (<b>1</b>), {[Cd­(1,3-adaa)­(bpmh)]}<i>_n</i> (<b>2</b>), {[Zn­(1,4-pdaa)­(bpmh)]}_<i>n</i> (<b>3</b>), and {[Co­(1,4-pdaa)­(bpmh)]}_<i>n</i> (<b>4</b>) (bpmh = <i>N</i>,<i>N</i>-bis-pyridin-4-ylmethylene-hydrazine, 1,3-adaa = 1,3-adamantane diacetic acid, 1,4-pdaa = 1,4-phenylene diacetic acid) have been synthesized through the slow diffusion technique. Structural determination reveals that compounds <b>1</b> and <b>2</b> have 2D layered architectures with similar framework topology, whereas <b>3</b> and <b>4</b> are isostuctural 3D frameworks. Both <b>1</b> and <b>2</b> perceives a common secondary building unit (SBU) [M₂(adaa)₄(bpmh)₄] [M = Zn­(<b>1</b>) and Cd­(<b>2</b>)]. In compound <b>1</b>, 1,3-adaa exhibits both μ- 1,1 and μ- 1,2 bridging modes, whereas in <b>2</b> it shows both μ-1,1 and μ-1,1,2 bridging modes. The difference in the bridging mode of 1,3-adaa in <b>1 </b>(Zn) and <b>2 </b>(Cd) is responsible for the shorter M···M contacts in <b>2</b> (3.872 Å) than in <b>1</b> (4.13 Å) in the SBU. The 1,3-adaa ligands are sandwiched between the bpmh linkers in compounds <b>1</b> and <b>2.</b> In compounds <b>3</b> and <b>4</b>, 1,4-pdaa exhibits both μ-1 and μ-1,1 bridging modes and are isostructural in nature. The metal centers are arranged in a helical fashion around 2₁ screw axis in <b>3</b> and <b>4</b>. In compounds <b>1</b>–<b>4</b>, the used dicarboxylic acids act as pillars between the metal-bpmh layers. Solid-state photoluminescent properties of compounds <b>1</b>–<b>3</b> show ligand (n → π* and π → π*)-based florescence. The magnetic studies of compound <b>4</b> show presence of the antiferromagnetic exchange between the metal centers

El Compostelano : diario independiente: Ano II Número 536 - 1921 novembro 24

This report describes the synthesis, characterization, and magnetic properties of two novel phosphonate-based Co^II cages. Structural investigation reveals some interesting geometrical features in the molecular core that may provide new models in single molecular magnetic materials

A Family of Metal–Organic Frameworks Based on Carboxylates and a Neutral, Long, and Rigid Ligand: Their Structural Revelation, Magnetic, and Luminescent Property Study

Four new two-dimensional/three-dimensional (2D/3D) bpmh-based metal organic frameworks, namely, {[Zn­(1,3-adaa)­(bpmh)]}_<i>n</i> (<b>1</b>), {[Cd­(1,3-adaa)­(bpmh)]}<i>_n</i> (<b>2</b>), {[Zn­(1,4-pdaa)­(bpmh)]}_<i>n</i> (<b>3</b>), and {[Co­(1,4-pdaa)­(bpmh)]}_<i>n</i> (<b>4</b>) (bpmh = <i>N</i>,<i>N</i>-bis-pyridin-4-ylmethylene-hydrazine, 1,3-adaa = 1,3-adamantane diacetic acid, 1,4-pdaa = 1,4-phenylene diacetic acid) have been synthesized through the slow diffusion technique. Structural determination reveals that compounds <b>1</b> and <b>2</b> have 2D layered architectures with similar framework topology, whereas <b>3</b> and <b>4</b> are isostuctural 3D frameworks. Both <b>1</b> and <b>2</b> perceives a common secondary building unit (SBU) [M₂(adaa)₄(bpmh)₄] [M = Zn­(<b>1</b>) and Cd­(<b>2</b>)]. In compound <b>1</b>, 1,3-adaa exhibits both μ- 1,1 and μ- 1,2 bridging modes, whereas in <b>2</b> it shows both μ-1,1 and μ-1,1,2 bridging modes. The difference in the bridging mode of 1,3-adaa in <b>1 </b>(Zn) and <b>2 </b>(Cd) is responsible for the shorter M···M contacts in <b>2</b> (3.872 Å) than in <b>1</b> (4.13 Å) in the SBU. The 1,3-adaa ligands are sandwiched between the bpmh linkers in compounds <b>1</b> and <b>2.</b> In compounds <b>3</b> and <b>4</b>, 1,4-pdaa exhibits both μ-1 and μ-1,1 bridging modes and are isostructural in nature. The metal centers are arranged in a helical fashion around 2₁ screw axis in <b>3</b> and <b>4</b>. In compounds <b>1</b>–<b>4</b>, the used dicarboxylic acids act as pillars between the metal-bpmh layers. Solid-state photoluminescent properties of compounds <b>1</b>–<b>3</b> show ligand (n → π* and π → π*)-based florescence. The magnetic studies of compound <b>4</b> show presence of the antiferromagnetic exchange between the metal centers

Two Isostructural 3D Lanthanide Coordination Networks (Ln = Gd³⁺, Dy³⁺) with Squashed Cuboid-Type Nanoscopic Cages Showing Significant Cryogenic Magnetic Refrigeration and Slow Magnetic Relaxation

Two isostructural lanthanide-based 3D coordination networks [Ln = Gd³⁺ (<b>1</b>), Dy³⁺(<b>2</b>)] with densely packed distorted cuboid nanoscopic cages are reported for the first time. Magnetic characterization reveals that complex <b>1</b> shows a significant cryogenic magnetocaloric effect (−Δ<i>S</i>_m = 44 J kg^–1 K^–1), whereas <b>2</b> shows slow relaxation of magnetization

Correction to Serendipitous Assemblies of Two Large Phosphonate Cages: A Co₁₅ Distorted Molecular Cube and a Co₁₂ Butterfly Type Core Structure

Correction to Serendipitous Assemblies of Two Large Phosphonate Cages: A Co₁₅ Distorted Molecular Cube and a Co₁₂ Butterfly Type Core Structur

Serendipitous Assemblies of Two Large Phosphonate Cages: A Co₁₅ Distorted Molecular Cube and a Co₁₂ Butterfly Type Core Structure

This report describes the synthesis, characterization, and magnetic properties of two novel phosphonate-based Co^II cages. Structural investigation reveals some interesting geometrical features in the molecular core that may provide new models in single molecular magnetic materials

A 3D Iron(II)-Based MOF with Squashed Cuboctahedral Nanoscopic Cages Showing Spin-Canted Long-Range Antiferromagnetic Ordering

The reaction of dilithium squarate with Fe­(II) perchlorate led to the formation of a new Fe­(II)-based 3D MOF, [Fe₃(OH)₃(C₄O₄)­(C₄O₄)_0.5]_<i>n</i> (<b>1</b>), with homoleptic squashed cuboctahedral cages. Complex <b>1</b> crystallizes in the monoclinic <i>C</i>2/<i>c</i> space group. Fe­(II) centers in the complex are octahedrally coordinated by four squarate dianions in axial and equatorial positions and two hydroxyl groups in the remaining equatorial positions. The interesting structural feature of <b>1</b> is that the three-dimensional framework is an infinite extension of nanoscopic cuboctahedral cages. The framework also contains two types of voids; the larger hydrophobic ones are surrounded by aromatic squarate ligands, while the smaller ones are hydrophilic with hydroxyl groups on the surface connected by bifurcated hydrogen bonding interaction. A variable temperature magnetic study shows spin-canted long-range antiferromagnetic ordering in the low temperature regime