Microporous Materials Constructed from the Interpenetrated Coordination Networks. Structures and Methane Adsorption Properties

Abstract

Five new coordination compounds with 4,4′-azopyridine (azpy), [Mn(azpy)(NO 3 ) 2 (H 2 O) 2 ]‚ 2EtOH (1‚2EtOH), [Co 2 (azpy) 3 (NO 3 ) 4 ]‚Me 2 CO‚3H 2 O (2‚Me 2 CO‚3H 2 O), [Co(azpy) 2 (NCS) 2 ]‚ 0.5EtOH (3‚0.5EtOH), [Cd(azpy) 2 (NO 3 ) 2 ]‚(azpy) (4‚azpy), and [Cd 2 (azpy) 3 (NO 3 ) 4 ]‚2Me 2 CO (5‚ 2Me 2 CO), have been synthesized and structurally characterized. The reaction of Mn(NO 3 ) 2 ‚ 6H 2 O with azpy in ethanol/acetone affords 1‚2EtOH, whose network consists of onedimensional chains of [Mn(azpy)(H 2 O) 2 ] n . The chains are associated by hydrogen bonding to provide a logcabin-type three-dimensional structure, which creates about 8 × 8 Å of channels, filled with ethanol molecules. The treatment of Co(NO 3 ) 2 ‚6H 2 O and Co(NCS) 2 ‚4H 2 O with azpy produces 2‚Me 2 CO‚3H 2 O and 3‚0.5EtOH, respectively, which have a brick-wall and a rhombus-type two-dimensional networks. The reaction of Cd(NO 3 ) 2 ‚4H 2 O with azpy affords 4‚azpy from the ethanol/H 2 O media, while the reaction in the ethanol/acetone media provides 5‚2Me 2 CO. 4‚azpy and 5‚2Me 2 CO form a square-grid-and a herringbone-type twodimensional networks, respectively. The two-dimensional sheets of 4‚azpy stack without interpenetration, leading to large size of channels, which are filled with free azpy molecules. The two-dimensional networks of 2‚Me 2 CO‚3H 2 O, 3‚0.5EtOH, and 5‚2Me 2 CO are quadruply, doubly, and triply interpenetrated, respectively. Despite the interpenetration, their networks create the microporous channels filled with guest solvent molecules. The dried compounds 2, 3, and 5 adsorb methane between 1 and 36 atm at 25°C, in which 3 and 5 exhibit Langmuir-type isotherms. The inherent micropore volumes for 3 and 5 are 0.685 and 3.30 mmol/g, respectively. XRPD measurements under reduced pressure at 100°C reveal that the channel structure of 3 is the most stable in these compounds; the observed XRPD pattern is in good agreement with that of the simulated pattern of the single-crystal model. Compounds 2 and 5 also retain the porous structures, however, their pore structures are distorted upon loss of guest included molecules.

One-Pot Synthesis, Crystal Structures and Thermal Properties of Two Three-Dimensional Cobalt(II) Complexes

“…[1][2][3][4][5][6][7][8][9] It is widely acknowledged that the coordinative bonding is the primary interaction to sustain the network, while supramolecular interactions, such as hydrogen bonding, π-π stacking interactions and Van der Waals forces are also believed to play important roles. [10][11][12][13][14][15][16][17] To date, a variety of supramolecular polymers with complicated architectures and interesting properties based on different bridging ligands especially aromatic polycarboxylate ligands have been synthesized successfully.…”

Crystal structure of diaqua-bis(trans-4,4′-azobispyridine)cadmium(II) perchlorate – methanol (1:2), [Cd(C10H8N4)2(H2O)2](ClO4)2 · 2CH3OH

“…Extended structures with linear bridging bidentate ligands such as 4,4'-bipyridine and 4,4'-azobispyridine and their analogues have attracted considerable interest in recent years [1][2][3][4][5]. In the title complex, the octahedrally coordinated Cd1 atom lies on an inversion center.…”

Crystal structure of poly[bis(µ2-1,4-bis((1H-imidazol-1-yl)methyl)benzene-κ2N:N’)dichloridonickel(II)]-1,3-dimethylimidazolidin-2-one (1:2) , C38H48Cl2N12NiO2

“…Ag reat many spectacular CPs have been reported, including one-dimensional (1D) chains and ladders [4][5][6], two-dimensional (2D) grids [7][8],t hree-dimensional (3D) networks [9][10][11]. Generally, the topological architectures and the application behaviors of CPs were found directly associated with avariety of factors, including the coordination geometries of central metal ions, and the shapes, functionalities, flexibilities,symmetries, lengths, and substituent groups of the organic ligands, as well as the reaction solvent.…”