Predesign and Systematic Synthesis of 11 Highly Porous Coordination Polymers with Unprecedented Topology

We propose and validate a simple strategy of vertex connection that can be used for framework design and pore size/type modulation to prepare a mother structure and another 10 highly porous isoreticular frameworks with unprecedented topology. Importantly, the potential accessible pore volumes (57–71%), pore sizes (6.8–11. 2 Å; 17.0–29.0 Å; 12.5–22.8 Å; 11.9–24.5 Å), and the pore shapes of this series of highly porous frameworks were simultaneously and systematically tuned. Interestingly, the pore size of IIa [Zn₄O­(L²)₂(BDC)_0.5]­{(CH₃)₂NH₂} decreased a little less than that of IIc [Zn₄O­(L²)₂(2,6-NDC)_0.5]­{(CH₃)₂NH₂}; however, its selectivity of CO₂ toward CH₄ increased by almost two times

Predesign and Systematic Synthesis of 11 Highly Porous Coordination Polymers with Unprecedented Topology

We propose and validate a simple strategy of vertex connection that can be used for framework design and pore size/type modulation to prepare a mother structure and another 10 highly porous isoreticular frameworks with unprecedented topology. Importantly, the potential accessible pore volumes (57–71%), pore sizes (6.8–11. 2 Å; 17.0–29.0 Å; 12.5–22.8 Å; 11.9–24.5 Å), and the pore shapes of this series of highly porous frameworks were simultaneously and systematically tuned. Interestingly, the pore size of IIa [Zn₄O­(L²)₂(BDC)_0.5]­{(CH₃)₂NH₂} decreased a little less than that of IIc [Zn₄O­(L²)₂(2,6-NDC)_0.5]­{(CH₃)₂NH₂}; however, its selectivity of CO₂ toward CH₄ increased by almost two times

Predesign and Systematic Synthesis of 11 Highly Porous Coordination Polymers with Unprecedented Topology

We propose and validate a simple strategy of vertex connection that can be used for framework design and pore size/type modulation to prepare a mother structure and another 10 highly porous isoreticular frameworks with unprecedented topology. Importantly, the potential accessible pore volumes (57–71%), pore sizes (6.8–11. 2 Å; 17.0–29.0 Å; 12.5–22.8 Å; 11.9–24.5 Å), and the pore shapes of this series of highly porous frameworks were simultaneously and systematically tuned. Interestingly, the pore size of IIa [Zn₄O­(L²)₂(BDC)_0.5]­{(CH₃)₂NH₂} decreased a little less than that of IIc [Zn₄O­(L²)₂(2,6-NDC)_0.5]­{(CH₃)₂NH₂}; however, its selectivity of CO₂ toward CH₄ increased by almost two times

Effects of Unsaturated Metal Sites on Radical Vinyl Polymerization in Coordination Nanochannels

Radical polymerization of vinyl monomers was performed in nanochannels of porous coordination polymers with unsaturated metal sites, [M(1,3,5-benzenetrisbenzoate)] (1Al, M = Al3+; 1Eu, M = Eu3+; 1Nd, M = Nd3+; 1Y, M = Y3+; 1La, M = La3+; and 1Tb, M = Tb3+). In this system, the polymerization behaviors are strongly dependent on the Lewis acidity of the metal sites. For example, polymerizability of monomers was influenced by the metal sites because of the interaction with the monomers. From the viewpoint of streteoregularity, composition of isotactic unit in the resulting poly(methyl methacrylate) (PMMA) increased as the Lewis acidity of the hosts becomes higher. Although discrete Tb3+ ions are not effective for changing the stereoregularity of PMMA in solution polymerization system, nanochannels of 1Tb gave PMMA with the increase in the isotactic unit, showing that the metal ions embedded in the pore walls of PCPs are useful for controlling stereoregularity of polymers

Temperature-Stable Compelled Composite Superhydrophobic Porous Coordination Polymers Achieved via an Unattainable <i>de Novo</i> Synthetic Method

We demonstrate a new de novo synthetic methodology to achieve high-temperature-stable compelled composite superhydrophobic porous coordination polymers (PCPs). These new PCPs were achieved based on coordination capabilities of first-row transition metal ions such as Co2+, Ni2+, and Zn2+. The obtained composite PCPs containing a [Zn2M2O]6+ (M = Co or Ni) bimetallic cluster core with open metal sites (OMSs) exhibited distinct isosteric heats of adsorption and surface areas due to the difference in their open metal Lewis acidic sites of solvent-free state. Additionally, these composite PCPs exhibit remarkable superhydrophobic properties with contact angles of 159.3° and 160.8° respectively for Zn–Co and Zn–Ni analogues. This superhydrophobic surface survives even at high temperature for longer time periods. As projected, these new composite PCPs exhibit better surface area and heats of adsorption compared to the PESD-1 (Zn) analogue due to a larger number of OMSs. Moreover, they display selective adsorption toward aromatic solvents such as benzene and toluene over aliphatic solvents such as cyclohexane due to corrugated and terminated aromatic hydrocarbon moieties toward the interactive surface. They also exhibit oil spill cleanup from the water surface in the powder form as well as pellet form up to 385 wt %. This study certainly offers a roadmap for designing and engineering new composite superhydrophobic porous materials for better water and thermal stability along with OMSs. This type of PCP exhibits a wide range of applications especially in catalysis, separation technology, and securing environmental problems such as oil spill cleanup in seawater

Temperature-Stable Compelled Composite Superhydrophobic Porous Coordination Polymers Achieved via an Unattainable <i>de Novo</i> Synthetic Method

We demonstrate a new de novo synthetic methodology to achieve high-temperature-stable compelled composite superhydrophobic porous coordination polymers (PCPs). These new PCPs were achieved based on coordination capabilities of first-row transition metal ions such as Co2+, Ni2+, and Zn2+. The obtained composite PCPs containing a [Zn2M2O]6+ (M = Co or Ni) bimetallic cluster core with open metal sites (OMSs) exhibited distinct isosteric heats of adsorption and surface areas due to the difference in their open metal Lewis acidic sites of solvent-free state. Additionally, these composite PCPs exhibit remarkable superhydrophobic properties with contact angles of 159.3° and 160.8° respectively for Zn–Co and Zn–Ni analogues. This superhydrophobic surface survives even at high temperature for longer time periods. As projected, these new composite PCPs exhibit better surface area and heats of adsorption compared to the PESD-1 (Zn) analogue due to a larger number of OMSs. Moreover, they display selective adsorption toward aromatic solvents such as benzene and toluene over aliphatic solvents such as cyclohexane due to corrugated and terminated aromatic hydrocarbon moieties toward the interactive surface. They also exhibit oil spill cleanup from the water surface in the powder form as well as pellet form up to 385 wt %. This study certainly offers a roadmap for designing and engineering new composite superhydrophobic porous materials for better water and thermal stability along with OMSs. This type of PCP exhibits a wide range of applications especially in catalysis, separation technology, and securing environmental problems such as oil spill cleanup in seawater

Temperature-Stable Compelled Composite Superhydrophobic Porous Coordination Polymers Achieved via an Unattainable <i>de Novo</i> Synthetic Method

We demonstrate a new de novo synthetic methodology to achieve high-temperature-stable compelled composite superhydrophobic porous coordination polymers (PCPs). These new PCPs were achieved based on coordination capabilities of first-row transition metal ions such as Co2+, Ni2+, and Zn2+. The obtained composite PCPs containing a [Zn2M2O]6+ (M = Co or Ni) bimetallic cluster core with open metal sites (OMSs) exhibited distinct isosteric heats of adsorption and surface areas due to the difference in their open metal Lewis acidic sites of solvent-free state. Additionally, these composite PCPs exhibit remarkable superhydrophobic properties with contact angles of 159.3° and 160.8° respectively for Zn–Co and Zn–Ni analogues. This superhydrophobic surface survives even at high temperature for longer time periods. As projected, these new composite PCPs exhibit better surface area and heats of adsorption compared to the PESD-1 (Zn) analogue due to a larger number of OMSs. Moreover, they display selective adsorption toward aromatic solvents such as benzene and toluene over aliphatic solvents such as cyclohexane due to corrugated and terminated aromatic hydrocarbon moieties toward the interactive surface. They also exhibit oil spill cleanup from the water surface in the powder form as well as pellet form up to 385 wt %. This study certainly offers a roadmap for designing and engineering new composite superhydrophobic porous materials for better water and thermal stability along with OMSs. This type of PCP exhibits a wide range of applications especially in catalysis, separation technology, and securing environmental problems such as oil spill cleanup in seawater

pH-Dependent Interpenetrated, Polymorphic, Cd²⁺- and BTB-based Porous Coordination Polymers with Open Metal Sites

Two polymorphic porous coordination polymers constructed from Cd²⁺ and benzene-1,3,5-tribenzoate and having interpenetrated two-dimensional (2D) (6,3) net topology and three-dimensional (3D) (10,3)-b net topology structures were synthesized. The number of single honeycomb-type layers interpenetrated dictates the dimensionality of the crystal structures of these two phases. The 2D structure has two interpenetrated layers, whereas the 3D structure has four interpenetrated layers. Interestingly, these two polymorphic forms selectively adsorb CO₂ over N₂, C₂H₄, and C₂H₆. Moreover, diffuse reflectance Fourier-transform infrared spectroscopy of CO₂ adsorbed on these two polymorphic phases indicates strong interaction between CO₂ and the open metal sites present on Cd²⁺ ions

Temperature-Stable Compelled Composite Superhydrophobic Porous Coordination Polymers Achieved via an Unattainable <i>de Novo</i> Synthetic Method

We demonstrate a new de novo synthetic methodology to achieve high-temperature-stable compelled composite superhydrophobic porous coordination polymers (PCPs). These new PCPs were achieved based on coordination capabilities of first-row transition metal ions such as Co2+, Ni2+, and Zn2+. The obtained composite PCPs containing a [Zn2M2O]6+ (M = Co or Ni) bimetallic cluster core with open metal sites (OMSs) exhibited distinct isosteric heats of adsorption and surface areas due to the difference in their open metal Lewis acidic sites of solvent-free state. Additionally, these composite PCPs exhibit remarkable superhydrophobic properties with contact angles of 159.3° and 160.8° respectively for Zn–Co and Zn–Ni analogues. This superhydrophobic surface survives even at high temperature for longer time periods. As projected, these new composite PCPs exhibit better surface area and heats of adsorption compared to the PESD-1 (Zn) analogue due to a larger number of OMSs. Moreover, they display selective adsorption toward aromatic solvents such as benzene and toluene over aliphatic solvents such as cyclohexane due to corrugated and terminated aromatic hydrocarbon moieties toward the interactive surface. They also exhibit oil spill cleanup from the water surface in the powder form as well as pellet form up to 385 wt %. This study certainly offers a roadmap for designing and engineering new composite superhydrophobic porous materials for better water and thermal stability along with OMSs. This type of PCP exhibits a wide range of applications especially in catalysis, separation technology, and securing environmental problems such as oil spill cleanup in seawater

Temperature-Stable Compelled Composite Superhydrophobic Porous Coordination Polymers Achieved via an Unattainable <i>de Novo</i> Synthetic Method

We demonstrate a new de novo synthetic methodology to achieve high-temperature-stable compelled composite superhydrophobic porous coordination polymers (PCPs). These new PCPs were achieved based on coordination capabilities of first-row transition metal ions such as Co2+, Ni2+, and Zn2+. The obtained composite PCPs containing a [Zn2M2O]6+ (M = Co or Ni) bimetallic cluster core with open metal sites (OMSs) exhibited distinct isosteric heats of adsorption and surface areas due to the difference in their open metal Lewis acidic sites of solvent-free state. Additionally, these composite PCPs exhibit remarkable superhydrophobic properties with contact angles of 159.3° and 160.8° respectively for Zn–Co and Zn–Ni analogues. This superhydrophobic surface survives even at high temperature for longer time periods. As projected, these new composite PCPs exhibit better surface area and heats of adsorption compared to the PESD-1 (Zn) analogue due to a larger number of OMSs. Moreover, they display selective adsorption toward aromatic solvents such as benzene and toluene over aliphatic solvents such as cyclohexane due to corrugated and terminated aromatic hydrocarbon moieties toward the interactive surface. They also exhibit oil spill cleanup from the water surface in the powder form as well as pellet form up to 385 wt %. This study certainly offers a roadmap for designing and engineering new composite superhydrophobic porous materials for better water and thermal stability along with OMSs. This type of PCP exhibits a wide range of applications especially in catalysis, separation technology, and securing environmental problems such as oil spill cleanup in seawater