Two Novel 3d-4f Heterometallic Frameworks Assembled from a Flexible Bifunctional Macrocyclic Ligand

Two novel 3d-4f heterometallic porous metal–organic frameworks with a flexible bifunctional macrocyclic ligand have been successfully synthesized and characterized. The mononuclear [M­(TETA)]^2– complexes exhibiting two kinds of connection models to lanthanide ions give rise to three-dimensional pillared-layer frameworks with highly solvent accessible volume. Interpenetration is avoided by using the nanosized secondary building units of transition metal macrocyclic complex

Two Novel 3d-4f Heterometallic Frameworks Assembled from a Flexible Bifunctional Macrocyclic Ligand

Two novel 3d-4f heterometallic porous metal–organic frameworks with a flexible bifunctional macrocyclic ligand have been successfully synthesized and characterized. The mononuclear [M­(TETA)]^2– complexes exhibiting two kinds of connection models to lanthanide ions give rise to three-dimensional pillared-layer frameworks with highly solvent accessible volume. Interpenetration is avoided by using the nanosized secondary building units of transition metal macrocyclic complex

Microwave-Assisted Synthesis of a Series of Lanthanide Metal–Organic Frameworks and Gas Sorption Properties

A series of isostructural microporous lanthanide metal–organic frameworks (MOFs) formulated as [Ln₂(TPO)₂(HCOO)]·(Me₂NH₂)·(DMF)₄·(H₂O)₆ {Ln = Y (<b>1</b>), Sm (<b>2</b>), Eu (<b>3</b>), Gd (<b>4</b>), Tb (<b>5</b>), Dy (<b>6</b>), Ho (<b>7</b>), Er (<b>8</b>), Tm (<b>9</b>), Yb (<b>10</b>), and Lu (<b>11</b>); H₃TPO = tris-(4-carboxylphenyl)­phosphineoxide; DMF = <i>N</i>,<i>N</i>-dimethylformamide} has been synthesized under microwave-assisted solvothermal reaction for 30 min. Alternatively, if a conventional solvothermal reaction is carried out under the same temperature, a much longer time (3 days) is needed for the same phase in similar yield. Structure analysis reveals that the framework is a 4,8-connected network with point symbol (4¹⁰·6¹⁶·8²) (4⁵·6)², which is the subnet of <i><b>alb</b></i> net. Thermal gravimetric analyses performed on as-synthesized MOFs reveal that the frameworks have high thermal stability. The luminescent properties of <b>2</b>, <b>3</b>, <b>5</b>, and <b>6</b> were investigated and show characteristic emissions for Sm­(III), Eu­(III), Tb­(III), and Dy­(III) at room temperature, respectively. Gas sorption properties of <b>1</b> and <b>3</b> were studied by experimentally measuring nitrogen, argon, carbon dioxide, methane, and hydrogen sorption isotherms. The resulting materials show high and preferential CO₂ adsorption over N₂ gas at ambient temperature, indicating that the present materials can be applied in a CO₂ capture process

Microwave-Assisted Synthesis of a Series of Lanthanide Metal–Organic Frameworks and Gas Sorption Properties

A series of isostructural microporous lanthanide metal–organic frameworks (MOFs) formulated as [Ln₂(TPO)₂(HCOO)]·(Me₂NH₂)·(DMF)₄·(H₂O)₆ {Ln = Y (<b>1</b>), Sm (<b>2</b>), Eu (<b>3</b>), Gd (<b>4</b>), Tb (<b>5</b>), Dy (<b>6</b>), Ho (<b>7</b>), Er (<b>8</b>), Tm (<b>9</b>), Yb (<b>10</b>), and Lu (<b>11</b>); H₃TPO = tris-(4-carboxylphenyl)­phosphineoxide; DMF = <i>N</i>,<i>N</i>-dimethylformamide} has been synthesized under microwave-assisted solvothermal reaction for 30 min. Alternatively, if a conventional solvothermal reaction is carried out under the same temperature, a much longer time (3 days) is needed for the same phase in similar yield. Structure analysis reveals that the framework is a 4,8-connected network with point symbol (4¹⁰·6¹⁶·8²) (4⁵·6)², which is the subnet of <i><b>alb</b></i> net. Thermal gravimetric analyses performed on as-synthesized MOFs reveal that the frameworks have high thermal stability. The luminescent properties of <b>2</b>, <b>3</b>, <b>5</b>, and <b>6</b> were investigated and show characteristic emissions for Sm­(III), Eu­(III), Tb­(III), and Dy­(III) at room temperature, respectively. Gas sorption properties of <b>1</b> and <b>3</b> were studied by experimentally measuring nitrogen, argon, carbon dioxide, methane, and hydrogen sorption isotherms. The resulting materials show high and preferential CO₂ adsorption over N₂ gas at ambient temperature, indicating that the present materials can be applied in a CO₂ capture process

Microwave-Assisted Synthesis of a Series of Lanthanide Metal–Organic Frameworks and Gas Sorption Properties

A series of isostructural microporous lanthanide metal–organic frameworks (MOFs) formulated as [Ln₂(TPO)₂(HCOO)]·(Me₂NH₂)·(DMF)₄·(H₂O)₆ {Ln = Y (<b>1</b>), Sm (<b>2</b>), Eu (<b>3</b>), Gd (<b>4</b>), Tb (<b>5</b>), Dy (<b>6</b>), Ho (<b>7</b>), Er (<b>8</b>), Tm (<b>9</b>), Yb (<b>10</b>), and Lu (<b>11</b>); H₃TPO = tris-(4-carboxylphenyl)­phosphineoxide; DMF = <i>N</i>,<i>N</i>-dimethylformamide} has been synthesized under microwave-assisted solvothermal reaction for 30 min. Alternatively, if a conventional solvothermal reaction is carried out under the same temperature, a much longer time (3 days) is needed for the same phase in similar yield. Structure analysis reveals that the framework is a 4,8-connected network with point symbol (4¹⁰·6¹⁶·8²) (4⁵·6)², which is the subnet of <i><b>alb</b></i> net. Thermal gravimetric analyses performed on as-synthesized MOFs reveal that the frameworks have high thermal stability. The luminescent properties of <b>2</b>, <b>3</b>, <b>5</b>, and <b>6</b> were investigated and show characteristic emissions for Sm­(III), Eu­(III), Tb­(III), and Dy­(III) at room temperature, respectively. Gas sorption properties of <b>1</b> and <b>3</b> were studied by experimentally measuring nitrogen, argon, carbon dioxide, methane, and hydrogen sorption isotherms. The resulting materials show high and preferential CO₂ adsorption over N₂ gas at ambient temperature, indicating that the present materials can be applied in a CO₂ capture process

Construction of a Polyhedral Metal–Organic Framework via a Flexible Octacarboxylate Ligand for Gas Adsorption and Separation

A flexible octacarboxylate ligand, tetrakis­[(3,5-dicarboxyphenyl)­oxamethyl]­methane (H₈X), has been used to construct a highly porous metal–organic framework (In₂X)­(Me₂NH₂)₂(DMF)₉(H₂O)₅ (<b>1</b>), which is comprised of octahedral and cuboctahedral cages and shows a rare (4,8)-connected scu topology. Gas adsorption studies of N₂, H₂ on the actived <b>1</b> at 77 K reveal a Langmuir surface area of 1707 m² g^–1, a BET surface area of 1555 m² g^–1, a total pore volume of 0.62 cm³ g^–1, and a H₂ uptake of 1.49 wt % at 1 bar and 3.05 wt % at 16 bar. CO₂, CH₄, and N₂ adsorption studies at 195, 273, 285, and 298 K and also ideal adsorbed solution theory (IAST) calculations demonstrate that <b>1</b> has high selectivites of CO₂ over CH₄ and N₂. The resulting framework represents a MOF with the highest gas uptakes and gas selectivities (CO₂ over CH₄ and N₂) constructed by flexible ligands

Construction of a Polyhedral Metal–Organic Framework via a Flexible Octacarboxylate Ligand for Gas Adsorption and Separation

A flexible octacarboxylate ligand, tetrakis­[(3,5-dicarboxyphenyl)­oxamethyl]­methane (H₈X), has been used to construct a highly porous metal–organic framework (In₂X)­(Me₂NH₂)₂(DMF)₉(H₂O)₅ (<b>1</b>), which is comprised of octahedral and cuboctahedral cages and shows a rare (4,8)-connected scu topology. Gas adsorption studies of N₂, H₂ on the actived <b>1</b> at 77 K reveal a Langmuir surface area of 1707 m² g^–1, a BET surface area of 1555 m² g^–1, a total pore volume of 0.62 cm³ g^–1, and a H₂ uptake of 1.49 wt % at 1 bar and 3.05 wt % at 16 bar. CO₂, CH₄, and N₂ adsorption studies at 195, 273, 285, and 298 K and also ideal adsorbed solution theory (IAST) calculations demonstrate that <b>1</b> has high selectivites of CO₂ over CH₄ and N₂. The resulting framework represents a MOF with the highest gas uptakes and gas selectivities (CO₂ over CH₄ and N₂) constructed by flexible ligands

Scrophularia appendiculata

Based on a semirigid tetracarboxylate ligand 5-(3,5-dicarboxybenzyloxy)­isophthalic acid (H₄DBIP), 11 coordination polymers formulated as [M₂DBIP­(H₂O)₄(μ₂-H₂O)]·6H₂O [M = Mg (<b>1</b>), Co (<b>2</b>)], [Cd₃(DBIP)₂]·(Me₂NH₂)₂·(H₂O)₃ (<b>3</b>), [Cd₂DBIP­(H₂O)₂DMA]·5DMA·5H₂O (<b>4</b>), (InDBIP)·(Me₂NH₂)·3DMA·2H₂O (<b>5</b>), and (LnDBIP)·(Me₂NH₂)·(H₂O)₂ [Ln = Eu (<b>6</b>), Gd (<b>7</b>), Tb (<b>8</b>), Dy (<b>9</b>), Ho (<b>10</b>), and Yb (<b>11</b>)] (Me₂NH₂⁺ = dimethylammonium cation; DMA = <i>N</i>,<i>N</i>-dimethylacetamide) were synthesized under solvothermal conditions and characterized by single-crystal X-ray structural, thermogravimetric, and photoluminescent studies. Compounds <b>1</b>–<b>2</b> are isomorphous and feature 2-fold interpenetrating <b>dia</b> networks. Compound <b>3</b> possesses a rare (4,8)-connected anionic network with <b>flu</b> topology built from 8-connected [Cd₃(COO)₈] clusters and 4-connected DBIP^4– ligands. Compound <b>4</b> is a 3D framework with <b>pts</b> topology based on 4-connected rectangular DBIP^4– ligands. Compound <b>5</b> shows a 3D anionic framework with <b>lon</b> topology. Compounds <b>6</b>–<b>11</b> display a 6-connected uninodal net with <b>msw</b> topology. In the 11 structures, the ligand H₄DBIP exhibits two different conformations owing to its flexibility, serving as 4-connected or 6-connected nodes in the resultant structures. Luminescent properties have also been investigated

<i>In Situ</i> Growth of Metal–Organic Framework Thin Films with Gas Sensing and Molecule Storage Properties

New porous metal–organic framework (MOF) films based on the flexible ligand 1,3,5-tris­[4-(carboxyphenyl)­oxamethyl]-2,4,6-trimethylbenzene (H₃TBTC) were fabricated on α-Al₂O₃ substrates under solvent thermal conditions. The factors affecting the fabrication of films, such as the temperature of pre-activation and the dosage of the reagents, were investigated. Tuning the subtle factors on film fabrications, a series of MOF thin films with different morphologies and grain sizes were prepared. The morphology and grain size of the films are monitored by scanning electron microscopy (SEM). X-ray diffraction (XRD) and attenuated total reflection infrared (ATR–IR) were also used to characterize the MOF films. The results indicate that the temperature of pre-activation and the dosage of the reagents are the key parameters during the process of film formation. The properties of the films, especially the sensing and sorption behavior, have been studied by an optical digital cameral and ultraviolet–visible (UV–vis) spectra. The evidence shows that the films are sensitive to small organic molecules, such as methanol and pyridine. Meanwhile, the films can adsorb small dye molecules. Thus, the films may have potential applications in either organic vapor sensing or storage of small dye molecules

Structure Versatility of Coordination Polymers Constructed from a Semirigid Tetracarboxylate Ligand: Syntheses, Structures, and Photoluminescent Properties

Based on a semirigid tetracarboxylate ligand 5-(3,5-dicarboxybenzyloxy)­isophthalic acid (H₄DBIP), 11 coordination polymers formulated as [M₂DBIP­(H₂O)₄(μ₂-H₂O)]·6H₂O [M = Mg (<b>1</b>), Co (<b>2</b>)], [Cd₃(DBIP)₂]·(Me₂NH₂)₂·(H₂O)₃ (<b>3</b>), [Cd₂DBIP­(H₂O)₂DMA]·5DMA·5H₂O (<b>4</b>), (InDBIP)·(Me₂NH₂)·3DMA·2H₂O (<b>5</b>), and (LnDBIP)·(Me₂NH₂)·(H₂O)₂ [Ln = Eu (<b>6</b>), Gd (<b>7</b>), Tb (<b>8</b>), Dy (<b>9</b>), Ho (<b>10</b>), and Yb (<b>11</b>)] (Me₂NH₂⁺ = dimethylammonium cation; DMA = <i>N</i>,<i>N</i>-dimethylacetamide) were synthesized under solvothermal conditions and characterized by single-crystal X-ray structural, thermogravimetric, and photoluminescent studies. Compounds <b>1</b>–<b>2</b> are isomorphous and feature 2-fold interpenetrating <b>dia</b> networks. Compound <b>3</b> possesses a rare (4,8)-connected anionic network with <b>flu</b> topology built from 8-connected [Cd₃(COO)₈] clusters and 4-connected DBIP^4– ligands. Compound <b>4</b> is a 3D framework with <b>pts</b> topology based on 4-connected rectangular DBIP^4– ligands. Compound <b>5</b> shows a 3D anionic framework with <b>lon</b> topology. Compounds <b>6</b>–<b>11</b> display a 6-connected uninodal net with <b>msw</b> topology. In the 11 structures, the ligand H₄DBIP exhibits two different conformations owing to its flexibility, serving as 4-connected or 6-connected nodes in the resultant structures. Luminescent properties have also been investigated