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

Study of Proton Conductivity of a 2D Flexible MOF and a 1D Coordination Polymer at Higher Temperature

We report the proton conduction properties of a 2D flexible MOF and a 1D coordination polymer having the molecular formulas {[Zn­(C₁₀H₂O₈)_0.5(C₁₀S₂N₂H₈)]·5H₂O]}_<i>n</i> (<b>1</b>) and {[Zn­(C₁₀H₂O₈)_0.5(C₁₀S₂N₂H₈)]·2H₂O]}_<i>n</i> (<b>2</b>), respectively. Compounds <b>1</b> and <b>2</b> show high conductivity values of 2.55 × 10^–7 and 4.39 × 10^–4 S cm^–1 at 80 °C and 95% RH. The conductivity value of compound <b>1</b> is in the range of those for previously reported flexible MOFs, and compound <b>2</b> shows the highest proton conductivity among the carboxylate-based 1D CPs. The dimensionality and the internal hydrogen bonding connectivity play a vital role in the resultant conductivity. Variable-temperature experiments of both compounds at high humidity reveal that the conductivity values increase with increasing temperature, whereas the variable humidity studies signify the influence of relative humidity on high-temperature proton conductivity. The time-dependent measurements for both compounds demonstrate their ability to retain conductivity up to 10 h

Study of Proton Conductivity of a 2D Flexible MOF and a 1D Coordination Polymer at Higher Temperature

We report the proton conduction properties of a 2D flexible MOF and a 1D coordination polymer having the molecular formulas {[Zn­(C₁₀H₂O₈)_0.5(C₁₀S₂N₂H₈)]·5H₂O]}_<i>n</i> (<b>1</b>) and {[Zn­(C₁₀H₂O₈)_0.5(C₁₀S₂N₂H₈)]·2H₂O]}_<i>n</i> (<b>2</b>), respectively. Compounds <b>1</b> and <b>2</b> show high conductivity values of 2.55 × 10^–7 and 4.39 × 10^–4 S cm^–1 at 80 °C and 95% RH. The conductivity value of compound <b>1</b> is in the range of those for previously reported flexible MOFs, and compound <b>2</b> shows the highest proton conductivity among the carboxylate-based 1D CPs. The dimensionality and the internal hydrogen bonding connectivity play a vital role in the resultant conductivity. Variable-temperature experiments of both compounds at high humidity reveal that the conductivity values increase with increasing temperature, whereas the variable humidity studies signify the influence of relative humidity on high-temperature proton conductivity. The time-dependent measurements for both compounds demonstrate their ability to retain conductivity up to 10 h

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

Synthesis and Characterization of Polyhedral-Based Metal–Organic Frameworks Using a Flexible Bipyrazole Ligand: Topological Analysis and Sorption Property Studies

Six porous metal–organic frameworks (MOFs), {[Ni­(BTC)_0.66­(BPz)₂]­·2MeOH­·4H₂O}_<i>n</i> (<b>1</b>), {[Co­(BTC)_0.66­(BPz)₂]­·2MeOH­·4H₂O}<i>_n</i> (<b>2</b>), {[Mn­(BTC)_0.66­(BPz)₂]­·2MeOH­·4H₂O}_<i>n</i> (<b>3</b>), {[Cd­(BDC)­(BPz)­(H₂O)]­·2MeOH­·DMF}<i>_n</i> (<b>4</b>), {[Cd₂(NH₂-BDC)₂­(BPz)­(H₂O)]­·MeOH­·H₂O­·DMF}<i>_n</i> (<b>5</b>), and {[Co­(BDC)­(BPz)­(H₂O)]}<i>_n</i> (<b>6</b>) (where H₃BTC = 1,3,5-benzenetricarboxylic acid, H₂BDC = 1,4-benzenedicarboxylic acid, NH₂-H₂BDC = 2-amino-1,4-benzenedicarboxylic acid, and BPz = 3,3′,5,5′-tetramethyl-4,4′-bipyrazole), were obtained through a solvent diffusion technique and characterized. The networks exhibit a variety of topologies: <b>1</b>, <b>2</b>, and <b>3</b> are isostructural and possess octahedral and cuboctahedra type cages and exhibit 3,6-c binodal net having <i><b>loh</b></i><b>1</b> topology, <b>4</b> is a two-dimensional MOF having one-dimensional open channels with a 4-c uninodal net having <i><b>sql</b></i> topology, <b>5</b> exhibits a three-dimensional (3D) porous MOF having a 3,3,4,8-c net with a new topology having the name, <i><b>skr</b></i><b>1</b>, whereas <b>6</b> discloses a 3D nonporous network which exhibits a 4-c uninodal net having CdSO₄ topology. Being isostructural, gas sorption studies of <b>1</b>–<b>3</b> show nearly the same CO₂ sorption at 195 K of ∼90 mL g^–1, whereas <b>4</b> and <b>5</b> show a maximum uptake of 42 and 37 mL g^–1 at 195 K. Vapor sorption studies of <b>1</b>–<b>3</b> reveal stepwise uptake of water with a final amount reached to nearly 350 mL g^–1, whereas <b>4</b> and <b>5</b> show maximum uptake of 110 and 90 mL g^–1, respectively. Compared to the free ligand BPz, photoluminescence studies of <b>4</b> and <b>5</b> show red shifts and emit in the blue-green region with λ_max at 430 and 472 nm for <b>4</b> and <b>5</b>, respectively

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

Synthesis and Characterization of Polyhedral-Based Metal–Organic Frameworks Using a Flexible Bipyrazole Ligand: Topological Analysis and Sorption Property Studies

Six porous metal–organic frameworks (MOFs), {[Ni­(BTC)_0.66­(BPz)₂]­·2MeOH­·4H₂O}_<i>n</i> (<b>1</b>), {[Co­(BTC)_0.66­(BPz)₂]­·2MeOH­·4H₂O}<i>_n</i> (<b>2</b>), {[Mn­(BTC)_0.66­(BPz)₂]­·2MeOH­·4H₂O}_<i>n</i> (<b>3</b>), {[Cd­(BDC)­(BPz)­(H₂O)]­·2MeOH­·DMF}<i>_n</i> (<b>4</b>), {[Cd₂(NH₂-BDC)₂­(BPz)­(H₂O)]­·MeOH­·H₂O­·DMF}<i>_n</i> (<b>5</b>), and {[Co­(BDC)­(BPz)­(H₂O)]}<i>_n</i> (<b>6</b>) (where H₃BTC = 1,3,5-benzenetricarboxylic acid, H₂BDC = 1,4-benzenedicarboxylic acid, NH₂-H₂BDC = 2-amino-1,4-benzenedicarboxylic acid, and BPz = 3,3′,5,5′-tetramethyl-4,4′-bipyrazole), were obtained through a solvent diffusion technique and characterized. The networks exhibit a variety of topologies: <b>1</b>, <b>2</b>, and <b>3</b> are isostructural and possess octahedral and cuboctahedra type cages and exhibit 3,6-c binodal net having <i><b>loh</b></i><b>1</b> topology, <b>4</b> is a two-dimensional MOF having one-dimensional open channels with a 4-c uninodal net having <i><b>sql</b></i> topology, <b>5</b> exhibits a three-dimensional (3D) porous MOF having a 3,3,4,8-c net with a new topology having the name, <i><b>skr</b></i><b>1</b>, whereas <b>6</b> discloses a 3D nonporous network which exhibits a 4-c uninodal net having CdSO₄ topology. Being isostructural, gas sorption studies of <b>1</b>–<b>3</b> show nearly the same CO₂ sorption at 195 K of ∼90 mL g^–1, whereas <b>4</b> and <b>5</b> show a maximum uptake of 42 and 37 mL g^–1 at 195 K. Vapor sorption studies of <b>1</b>–<b>3</b> reveal stepwise uptake of water with a final amount reached to nearly 350 mL g^–1, whereas <b>4</b> and <b>5</b> show maximum uptake of 110 and 90 mL g^–1, respectively. Compared to the free ligand BPz, photoluminescence studies of <b>4</b> and <b>5</b> show red shifts and emit in the blue-green region with λ_max at 430 and 472 nm for <b>4</b> and <b>5</b>, respectively

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