Designed layer assembly: a three-dimensional framework with 74% extra-framework volume by connection of infinite two-dimensional sheets

A coordination polymer with 74% extra-framework volume is prepared by predictable linking of the honeycomb network to generate a framework-structured solid designed with two distinct connecting ligands.     

A metal-organic bilayer open framework with a dynamic component: single-crystal-to-single-crystal transformations

A metal-organic bilayered open framework, [Ni2(C26H52N10)]3[BTC]4.6C5H5N.36H2O (BOF-1, 1), has been prepared by the self-assembly of a new bismacrocyclic nickel(II) complex [Ni2(C26H52N10)(Cl)4].H2O (A) and sodium 1,3,5-benzenetricarboxylate (Na3BTC) in the mixture of water/DMSO/pyridine. The X-ray crystal structure of 1 shows that 2D layers with the cavities of brick-wall motifs (22.6 x 14.3 A2) are formed by the coordination of the nickel(II) complex with BTC3- ions and that the two 2D layers are linked with the p-xylyl bridging groups of the bismacrocycles as pillars to generate 3D channels in the bilayered framework. The voids of the channels occupy 61% of the total volume, which are filled with pyridine and water guest molecules. When 1 was dried at 75 degrees C for 1.5 h, [Ni2(C26H52N10)]3[BTC]4.4H2O (2) resulted by maintaining the single-crystallinity, which exhibited a dramatic decrease in the interlayer spacing as well as changes in the cell parameters. Solid 2 differentiates various alcohols such as MeOH, EtOH, isopropyl alcohol, and benzyl alcohol in toluene. When 1 was immersed in insoluble solvents such as pyridine and benzene, some guest molecules were exchanged with the aromatic molecules to give [Ni2(C26H52N10)]3[BTC]4.20pyridine.6H2O (3) and [Ni2(C26H52N10)]3[BTC]4.14benzene.19H2O (4), respectively. The guest-exchange processes also involve single-crystal-to-single-crystal transformation.     

Anion-directed assembly of a three-dimensional metal-organic rotaxane framework

A three-dimensional extended, metal-organic rotaxane framework (MORF) that incorporates encircled "struts" has been synthesized through a one-pot self-assembly process involving a macrocyclic tetraimidazolium "molecular box", naphthalene dicaboxylate dianion, and Zn(II) cations. The present system represents progress towards controlling the features of three-dimensional metal-organic frameworks.     

A three-dimensional metal-organic framework with a distorted Kagome related layer showing canted antiferromagnetic behaviour

Three-dimensional [Mn(3){C(6)H(3)(COO)(3)}(2)] comprising two-dimensional -Mn-O-Mn- distorted Kagome layers, formed by two geometrically different hexa-coordinated Mn(2+) ions, show less frustration and spin canted long range ordering possibly due to antisymmetric exchange.     

pH-dependent assembly of two inorganic-organic hybrid compounds based on octamolybdates: an unusual intercalated layer and a 3D 4-connected framework

Two novel inorganic-organic hybrid compounds based on octamolybdates, namely, [Cu(H(2)L)(2)(γ-Mo(8)O(26))]·(Mo(6)O(19))·2H(2)O (1) and [Cu(H(2)L)(γ-Mo(8)O(26))(H(2)O)(2)]·5H(2)O (2), where L = 1,1'-(1,5-pentanediyl)bis[2-(4-pyridyl)benzimidazole], have been successfully synthesized at different pH values under hydrothermal conditions. Compound 1, which is hydrothermally prepared at pH ≈ 3.5, exhibits an entirely new type of intercalated layer. The nanosized hexamolybdate anions as guests are introduced into the layers. When the pH value is adjusted to 2, a structurally-different complex 2 was obtained. Compound 2 shows a unique 3D 4-connected framework constructed by inorganic layers and H(2)L(2+) ligands as bridges. The two compounds were characterized by elemental analyses, IR spectra and TGA. In addition, the electrochemical properties of 1-modified carbon paste electrode (CPE) have also been investigated in 1 M H(2)SO(4) aqueous solution.     

Self assembly of two novel three-dimensional supramolecular networks with blue photoluminescence

Two novel photoluminescent coordination polymers of the formula [Cd(Haip)₂(H₂O)₂] · 2H₂O (1) and [Zn(aip)(atz)] · 3H₂O (2) (H₂aip = 5-aminoisophthalic acid; atz = 3-amino-1,2,4-triazole) have been synthesized through the self-assembly of metal(II) ions with H₂aip and N-containing ligands [2-amino-5-mercapto-1,3,4-thiadiazole for 1 and 3-amino-1,2,4-triazole for 2, respectively] in the presence of NaOH. These complexes were characterized by FT-IR spectroscopy, thermogravimetric analysis (TG), elemental analysis and X-ray analysis. X-ray crystallographic studies of the complexes reveal that 1 is a first example where only one carboxylate group of the H₂aip ligand participates in coordination with the metal(II) ion and it exhibits a two-dimensional framework which further assembles into a three-dimensional supramolecular network via interlayer π–π stacking interactions and strong hydrogen bonds, while 2 exhibits a two-dimensional porous architecture. The extensively strong hydrogen bonds and interlayer π–π stacking interactions in 2 lead to the formation of a three-dimensional supramolecular network. Photoluminescence properties of the compounds 1 and 2 have been examined in the solid state at room temperature. These compounds have been found to exhibit blue photoluminescence and may be good candidates for photoactive materials.     

A dodecameric self-assembled calix[4]arene aggregate with two types of cavities

Twelve molecules of β-carbonyl-para-octyl-calix[4]arene assemble in an aggregate containing two types of cavities filled by water molecules and they pack in a cubic structure. Both the aggregates and the packing resemble that observed for inverse micelles.     

Hydrogen adsorption in a nickel based coordination polymer with open metal sites in the cylindrical cavities of the desolvated framework

The solvent contained within the cylindrical one-dimensional pores of the novel three-dimensional metal organic framework Ni2(dhtp)(H2O)2.8H2O can be removed without decomposition of the network, allowing gas storage within the cavities.     

The topology of three-dimensional 4-connected nets: Classification of zeolite framework types using coordination sequences

Coordination sequences provide a practical numerical scale for expressing the degree of similarity of three-dimensional 4-connected nets found in zeolite structures when weighted mean values are used for topologically heterogeneous nets. Values of coordination sequences limited to 5 terms have been determined for nearly all of the known zeolite framework types. They are shown to be useful for classifying zeolite frameworks on purely topological grounds and also for finding the maximum possible space group symmetry in more difficult cases.     

Rational assembly of a 3D metal-organic framework for gas adsorption with predesigned cubic building blocks and 1D open channels

A novel 3D metal-organic framework with predesigned cubic building blocks and 1D open channels exhibiting significant N2 adsorption has been synthesized and characterized by single crystal X-ray diffraction analysis.     

Four-component assembly of chiral N-B heterocycles with a natural product-like framework

The dative N-B bond was used to simply assemble heterocycles with a skeleton akin to the 5-oxofuro[2,3-b]furan motif. Twenty-five new N-B heterocycles were prepared via a highly efficient one-pot four-component reaction in yields and diastereoselectivities up to 95% and >97%, respectively. Several reaction intermediates were discovered using electrospray ionization mass spectroscopy which set the basis for the mechanism elucidation using DFT calculations.     

Crystal structure of zeolite MCM-68: a new three-dimensional framework with large pores

The crystal structure of the aluminosilicate MCM-68 was solved from synchrotron powder diffraction data by the program FOCUS. The unit cell framework contains Si100.6Al11.4O224. This material crystallizes in space group P42/mnm, where, after Rietveld refinement, a=18.286(1) A and c=20.208(2) A. A three-dimensional framework is found that contains continuous 12-ring channels and two orthogonal, intersecting, undulating 10-ring channels. Rietveld refinement of the model coordinates optimizes the framework geometry, to match the observed intensity profile by Rwp=0.1371, R(F2)=0.1411. It is not possible to determine the location of approximately 0.84 K+ cations remaining in the unit cell after the material is steamed and then dehydrated. The framework model also successfully predicts observed electron diffraction data in two projections, and the tetragonal projection can be determined independently from these data by direct methods. The calculated density of the framework structure is 1.66 g/cm3, and the T-site framework density is 16.6 T/1000 A3.     

Control of a double helix DNA assembly by use of cross-linked oligonucleotides

Disulfide cross-linked oligonucleotides for connecting two DNA double helixes have been designed, synthesized, and characterized. Employing these cross-linked oligonucleotides, two double helixes can be arranged side by side, and the orientations can be controlled both in parallel and antiparallel ways by addition of a specific complementary DNA strand.     

Hydrothermal reversible interconversion of two zincophosphates with three-dimensional open frameworks containing diprotonated 1,4-diazacycloheptane molecules

A new zincophosphate (ZnPO), (C₅H₁₄N₂)[Zn₂(HPO₄)₃] (I), has been synthesized in the presence of 1,4-diazacycloheptane under mild hydrothermal conditions (160 °C) and the crystal structure determined by single-crystal X-ray crystallography. Corner-sharing ZnO₄ and HPO₄ tetrahedra are arranged into layers that are based on the 2D, three-connected 4.8² net and linked together by tetrahedral HPO₄ pillars into the 3D interrupted open framework. The 3D intersecting channel system is filled with diprotonated amine molecules. It has been observed that I forms via hydrothermal transformation of a known ZnPO hydrate, (C₅H₁₄N₂)[Zn₂(HPO₄)₃]·H₂O (II), with a closely related 3D open-framework structure, involving dehydration and reconstruction of Zn-O-P linkages. Interestingly, this transformation is completely reversible under hydrothermal conditions at temperatures between 100 and 160 °C with II and I being stable at low and high temperature, respectively. Also, I and II can be interconverted via solid-gas reactions. Crystal data for I: Orthorhombic, space group Pca2₁, Z=16, a=14.6595(9), b=14.557(1), , .     

A Cu-based metal-organic framework with two types of connecting nodes as catalyst for oxygen activation

Using a ditopic organic linker 4-(1H-pyrazol-4-yl)benzoic acid (H₂pba), FICN-6, a metal-organic framework containing both Cu₂(O₂CR)₄ and Cu₃(OH)(pyz)₃(O₂CR) secondary building units (SBUs), was synthesized. FICN-6 adopts in an unusual intercatenated structure with SBUs from two distinct networks connecting to each other. Presence of Cu₃ clusters makes FICN-6 a good heterogeneous catalyst for oxygen activation and aerobic oxidative C-C coupling of organic boronic acids.     

Phosphonated oligoallylamine: Synthesis,characterization in water,and development of layer by layer assembly

The work focuses on the synthesis and layer by layer (LbL) assembly of oligoallylamine and phosphonated oligoallylamine. To this aim, the synthesis of oligoallylamine and the phosphonated form have been done by free radical polymerization in aqueous media. First, radical polymerization of acid salt of allylamine was performed. This charged polymer could not be characterized using classical analytical techniques such as size‐exclusion chromatography and matrix‐assisted laser desorption/ionisation‐time of flight mass spectroscopy due to presence of cations. This work demonstrated the interest of capillary electrophoresis (CE) to analyze charged oligomers, using very small amounts of samples. Entangled polymer solution CE was used as a size‐based separation technique for the characterization of the molar mass distribution using indirect ultraviolet detection and calibration based on vinyl pyridine standards. Phosphorus‐containing oligoallylamines having a number‐average molar mass of 1600 g mol^?1 and a 2.3 polydispersity index were obtained. When combined using the LbL approach, prepared polymers showed an exponential growth regime as demonstrated by Fourier transform infrared spectroscopy measurements. Furthermore, thermogravimetric analyses of the LbL‐assembled polymers showed an extraordinary thermal and thermo‐oxidative stability. © 2013 Wiley Periodicals, Inc. J Polym Sci Part B: Polym. Phys. 2013 , 51, 1244–1251     

Na7Sn12: a binary Zintl phase with a two-dimensional covalently bonded tin framework

Na(7)Sn(12) was synthesized by quenching of stoichiometric amounts of the elements (700 degrees C) in a sealed niobium ampule and further thermal treatment at 270 degrees C for 40 days. Single crystals of Na(7)Sn(12) were obtained from a mixture with the composition Na(6)SrSn(16). The structure of Na(7)Sn(12) consists of two-dimensional polyanions 2 (infinity) [Sn(12)(7-)], which are separated by Na atoms. Bonding Sn-Sn contacts in the polyanion vary between 2.827(2) and 3.088(2) A. Crystal data: monoclinic, P2/n, Z = 4, a = 13.375(3) A, b = 9.239(2) A, c = 17.976(4) A, gamma = 90.15(3) degrees, V = 2243.0(8) A(3), mu = 13.22 mm(-1), d(calc) = 4.694 g cm(-3), R1(F) = 6.1% (for all reflections). Extended-Hückel tight-binding calculations with the implementation the electron localization function (ELF) reveal that Na(7)Sn(12) can be viewed as an intermetallic compound with exclusively localized bonding and nonbonding regions as expected from the 8 - N rule. Thus Na(7)Sn(12) is a Zintl phase with the formula (Na(+))(7)[(2b)Sn(2)(-)](1)[(3b)Sn(-)](5)[(4b)Sn(0)](6).