Synthesis and characterization of a 2-periodic cadmium-based metal-organic framework: A study on reversible water adsorption.

A previously-reported cadmium-based two-periodic metal-organic framework [Cd1.5(BTC)(H2O)4.5] n ·nH2O (CP1) has been re-synthesized, where H3BTC = 1,3,5-benzenetricarboxylic acid. CP1 was characterized with single crystal X-ray diffraction (SCXRD), powder X-ray diffraction (PXRD) followed by various thermal analyses such as thermogravimetric analysis (TGA), hot stage microscopy (HSM) and differential scanning calorimetry (DSC). CP1 is composed of 2-periodic layers, which are interdigitated. Heating can effectively remove the uncoordinated and coordinated water molecules resulting in an amorphous product CP1'. The original framework can be regenerated by readsorption of water from the atmosphere, indicating that the dehydration is reversible.

Ligated Solvent Influence on Interpenetration and Carbon Dioxide and Water Sorption Hysteresis in a System of 2D Isoreticular MOFs.

Four two-dimensional (2D), fluorinated metal-organic frameworks (MOFs), [Cu(hfipbb)(DMF)]n·0.5(DMF)n (1), [Cu(hfipbb)(DEF)]n (2), [Cu3(hfipbb)3(DMA)3]n·6(DMA)n·2(H2O)n (3), and [Cu2(hfipbb)2(DEA)2]n·2(DEA)n·2(H2O)n (4), have been synthesized where hfipbb = 4,4'-(hexafluoroisopropylidene)bis(benzoate), DMF = N,N'-dimethylformamide, DEF = N,N'-diethylformamide, DMA = N,N'-dimethylacetamide, and DEA = N,N'-diethylacetamide. The choice of either a formamide or acetamide solvent ligand leads to a 2D, doubly interpenetrated (1 and 2) or noninterpenetrated (3 and 4) MOF structure. Despite their lower potential void spaces, the doubly interpenetrated structures have superior carbon dioxide and hydrogen sorption properties. Their 195 K CO2 sorption isotherms display inflection points, followed by ∼3-fold increases in their sorption capacities and very large extents of hysteretic behavior. This shows that small changes in the identity of the ligated solvent ligand can affect whether the resulting MOF is interpenetrated or noninterpenetrated and so drastically affect the sorption properties. In addition, the activated phase of a fifth MOF, synthesized through DMF ligand exchange with water in 1 (1W), does not display an inflection point and subsequent increased CO2 sorption at 195 K, despite having the same degree of interpenetration, showing that even more subtle differences in the desolvated phases can lead to marked differences in their sorption behavior.

Large Differences in Carbon Dioxide and Water Sorption Capabilities in a System of Closely Related Isoreticular Cd(II)-based Mixed-Ligand Metal-Organic Frameworks.

We report the synthesis of two isoreticular, mixed-ligand metal-organic frameworks (MOFs), [Cd(µ2-mia)(µ2-bpe)]n·n(DMF)0.5·n(H2O)0.5 (1) and [Cd(µ2-nia)(µ2-bpee)]n·nDMF (2), where mia = 5-methoxyisophthalate, nia = 5-nitroisophthalate, bpe = 1,2-bis(4-pyridyl)ethane, bpee = 1,2-bis(4-pyridyl)ethylene, and DMF = N,N'-dimethylformamide. Variable-temperature powder X-ray diffraction studies confirmed that both MOFs remain crystalline with activation at high temperatures. Variable-temperature single-crystal X-ray diffraction studies were performed on 1, 2, and a previously published, isoreticular structure, [Cd(µ2-nia)(µ2-bpe)1.5]n·nDMF0.84 (3). These studies show that upon desolvation that monocrystallinity is retained to significantly higher temperatures for 2 and 3 when compared to 1 for which only a partially desolvated crystal structure could be obtained. Carbon dioxide sorption is negligible for 1 at 195 and 298 K, while it is higher for 2 than 3 at 298 K and reversed at 195 K. Water vapor sorption increases in the order 1, 2, and 3. On the contrary, water liquid sorption was significantly higher for 1 when compared to 2. The variable-temperature structures of the (partially) desolvated forms of 1, 2, and 3 give some insight into the reasons for the remarkably different gas, vapor, and liquid sorption properties.

Metal-Organic Frameworks of Cu(II) Constructed from Functionalized Ligands for High Capacity H2 and CO2 Gas Adsorption and Catalytic Studies.

Two Cu(II)-based metal-organic frameworks (MOFs) having paddle-wheel secondary building units (SBUs), namely, 1Me and 1ipr, were synthesized solvothermally using two new bent di-isophthalate ligands incorporating different substituents. The MOFs showed high porosity (BET surface area, 2191 m2/g for 1Me and 1402 m2/g for 1ipr). For 1Me, very high CO2 adsorption (98.5 wt % at 195 K, 42.9 wt % at 273 K, 23.3 wt % at 298 K) at 1 bar was found, while for 1ipr, it was significantly less (14.3 wt % at 298 K and 1 bar, 54.4 wt % at 298 K at 50 bar). 1Me exhibited H2 uptake of 3.2 wt % at 77 K and 1 bar of pressure, which compares well with other benchmark MOFs. For 1ipr, the H2 uptake was found to be 2.54 wt % under similar experimental conditions. The significant adsorption of H2 and CO2 for 1Me could be due to the presence of micropores as well as unsaturated metal sites in these MOFs besides the presence of substituents that interact with the gas molecules. The experimental adsorption behavior of the MOFs could be justified by theoretical calculations. Additionally, catalytic conversions of CO2 and CS2 into useful chemicals like cyclic carbonates, cyclic trithiocarbonates, and cyclic dithiocarbonates could be achieved.

Interchanged Hysteresis for Carbon Dioxide and Water Vapor Sorption in a Pair of Water-Stable, Breathing, Isoreticular, 2-Periodic, Zn(II)-Based Mixed-Ligand Metal-Organic Frameworks.

We report the synthesis of two isoreticular mixed-ligand metal-organic frameworks (MOFs), namely, [Zn(µ2-ia)(µ2-bpe)] n· nDMF (1) and [Zn(µ2-mia)(µ2-bpe)] n· nDMF (2), where ia = isophthalate, mia = 5-methoxyisophthalate, bpe = 1,2-bis(4-pyridyl)ethane, and DMF = N, N'-dimethylformamide. Single-crystal X-ray diffraction studies revealed that the structures of 1 and 2 consist of a 2-periodic, layer sql motif. Structures exhibit entanglement through interpenetration of neighboring frameworks to form a two-dimensional bilayer. Variable-temperature powder X-ray diffraction studies confirmed both structures retain crystallinity upon desolvation up to ∼500 K. Although structurally similar, activated samples of 1 and 2 showed differing gas and vapor sorption capabilities. Despite activated 2 having the higher actual void space, activated 1 showed significantly higher sorption for carbon dioxide at 195 K, as well as significant hysteresis upon desorption. Empirical evidence points toward weaker bilayer···bilayer interactions, which allow the separation of the bilayers, illustrating that small changes in functional groups within an isoreticular pair of MOFs may have a large tuning effect on sorption properties.

The synthesis, structure, topology and catalytic application of a novel cubane-based copper(II) metal-organic framework derived from a flexible amido tripodal acid.

A novel chiral metal-organic framework, [Cu4(HL)2(H2O)4(MeO)4]n (), has been successfully synthesized from a tripodal flexible ligand (2S,2'S,2''S)-2,2',2''-(benzenetricarbonyltris(azanediyl))tripropanoic acid (H3L). Compound was characterized by IR and X-ray powder diffraction analysis. The structure was determined by X-ray single crystal diffraction analysis revealing that possesses a 3D network, featuring a tetranuclear cubane-type secondary building block [Cu4(MeO)4](4+), formed via the connection of four metal ions to four methoxide ions. These secondary building blocks are linked by four different HL(2-) ligands to construct a porous three dimensional framework of the dia topology with one-dimensional channels. Compound also acts as a heterogeneous catalyst for the diastereoselective nitroaldol (Henry) reaction, providing high yields (up to 91%) and good diastereoselectivities under ambient conditions. This catalyst can be recycled without significant loss of activity.

Topological studies of three related metal-organic frameworks of GdIII and 5-nitroisophthalate.

The reaction of 5-nitroisophthalic acid (H(2)NIA) with Gd(NO(3))(3)·6H(2)O in DMF afforded three new metal-organic frameworks: [Gd(NIA)(1.5)(DMF)(2)]·DMF (I), [Gd(2)(NIA)(3)(DMF)(4)]·xH(2)O (II) and [Gd(4)(NIA)(6)(DMF)(5.5)(H(2)O)(3)]·4DMF·H(2)O (III). These compounds can be prepared through a variety of methods. Compounds (I) and (II) are more reproducibly formed than compound (III). Network analysis revealed (I) to have a (4(12).6(3))-pcu topology, while (II) displays a (4(2).8(4))(4(2).8(4))-pts topology. Compound (III) was found to present the uncommon 4,5,6T11 topological net, which combines aspects of both the pcu and pts topologies. The short symbol of this net is (4(4).6(2))(4(6).6(4))(2)(4(8).6(6).8).

The structure of water in p-sulfonatocalix[4]arene.

Tetrasodium p-sulfonatocalix[4]arene exists as a hydrate with approximately 14 water molecules and has three polymorphic modifications, all of which contain a water molecule in the molecular cavity that is engaged in OH···π interactions. Single-crystal neutron structures are reported for two of these three forms and reveal a "compressed" water molecule with short OH bonds. Partial atomic charges and hardness analysis (PACHA) calculations based on the neutron coordinates give an OH···π interaction energy of 6.9-7.5 kJ mol(-1). The PACHA analysis also reveals the dominance of the charge-assisted hydrogen bonds from the Na(+)-coordinated water molecules. The instability of the crystal towards dehydration can be traced to an uncoordinated lattice water site. The remarkable calixarene-Na(+)-hydrate motif is conserved almost unchanged across all three polymorphs. A single-crystal neutron structure is also reported for pentasodium p-sulfonatocalix[4]arene·12H(2)O, which exhibits an intracavity water molecule that is engaged in both OH···π and OH···O hydrogen bonding. The shorter covalent bond to the hydrogen atom that forms the interaction with the aromatic ring is again apparent.

Quininium mandelates--a systematic study of chiral discrimination in crystals of diastereomeric salts.

The selectivity profile for the resolution of mandelic acid by quinine is dominated by structures comprising (QUIN(+))(MAND(-)) salts with Z' = 3 which contain (R)-, (R)- and (S)-mandelate anions.

Anionic zinc-trimesic acid MOFs with unusual topologies: reversible hydration studies.

The reaction of 1,3,5-benzenetricarboxylic acid (H(3)BTC) with ZnSO(4).6H(2)O in a DMF-water solution afforded two new metal-organic frameworks [Zn(6)(mu(3)-OH)(2)(BTC)(4)(DMF)(2.5)(H(2)O)(2)].[Zn(H(2)O)(3)(DMF)(3)].3.1H(2)O (1) and Zn(2)(HBTC)(BTC)(H(2)O)(3)].DMA.3H(2)O (2). Both compounds are thermally stable and can be prepared reproducibly. Rehydration experiments on compound 2 demonstrate reversible dehydration and rehydration while 1 rehydrates to a different crystalline material. Network analysis revealed a binodal (3,6)-net for 1 and a (3,5)-net for 2, both rare topologies.