Third-Generation Breathing Metal–Organic Framework with Selective, Stepwise, Reversible, and Hysteretic Adsorption Properties

A new 2D interdigitated and highly flexible, breathing metal–organic framework has been synthesized through a diffusion technique by using the aldrithiol linker and pyromellitate ligand. The compound shows selective, stepwise, reversible, and hysteretic adsorption properties for CO₂ gas and H₂O, MeOH, and CH₃CN vapors

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

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

Exploration of Structural Topologies in Metal–Organic Frameworks Based on 3‑(4-Carboxyphenyl)propionic Acid, Their Synthesis, Sorption, and Luminescent Property Studies

Four new compounds (two coordination polymers (CPs) and two metal organic frameworks (MOFs)), namely, [Zn­(cpp)­(H₂O)]_<i>n</i> (<b>1</b>), [Cu­(cpp)­(4-bpmh)]_<i>n</i><i>­·n</i>H₂O­·<i>n</i>MeOH (<b>2</b>), [Cd₂(cpp)₂­(3-bpmh)₂]_<i>n</i>­4<i>n</i>H₂O­·2<i>n</i>MeOH (<b>3</b>), and [Cd­(cpp)­(bpy)­(H₂O)₂]_<i>n</i>­·2<i>n</i>H₂O (<b>4</b>), have been synthesized through the slow diffusion technique using cpp ligand and different neutral linkers (H₂cpp = 3-(4-carboxyphenyl)­propionic acid, 4-bpmh = <i>N</i>,<i>N</i>-bis-pyridin-4-ylmethylene-hydrazine, 3-bpmh = <i>N</i>,<i>N</i>-bis-pyridin-3-ylmethylene-hydrazine, bpy = 4,4-bipyridine). Single crystal X-ray analysis of compounds <b>1</b>–<b>4</b> reveals their structural diversities which might have been generated due to both rigidity (aryl carboxylate) and flexibility (aliphatic carboxylates) of cpp ligands as well their bridging modes and the orientation of nitrogen atoms of the neutral linkers. In addition, the dihedral angle in the aliphatic carboxylates of cpp ligand is also playing an important role in directing the final structural arrangement. Compound <b>1</b> exhibits a uninodal 6-connected three-dimensional (3D) coordination polymer with point Schälfli symbol {3³.5⁹.6³} and shows an uncommon <i>lcy; 6/3/c1</i> topological type. Compound <b>2</b> reveals a 6-connected uninodal 3D framework with point Schälfli symbol {4⁸.6⁶.8} and shows a rare <i>rob</i> topology. Compound <b>3</b> formed a 4-connected uninodal two-dimensional framework with point Schälfli symbol {4⁴.6²} and displays a <i>sql/Shubnikov tetragonal plane</i> net topology, whereas <b>4</b> forms a one-dimensional CP which subsequently extended to 3D supramolecular networks through hydrogen bonding interactions. Gas adsorption studies reveal that compounds <b>1</b> and <b>2</b> show selective adsorption of CO₂ over other gases (N₂, CH₄) at low temperature, whereas <b>3</b> and <b>4</b> show no uptake. Vapor sorption studies reveal that compounds <b>1</b>,<b> 2</b>, and <b>4</b> show high uptake capacities for H₂O over MeOH and EtOH. Solid state luminescence studies of compounds <b>1</b>,<b> 3</b>, and <b>4</b> display significant red shifts compared to free ligands