A Covalent Organic Framework with 4 nm open pores.

The synthesis and characterization of a new mesoporous Covalent Organic Framework BTP-COF is described, the latter having fully accessible pores with an open diameter of 4.0 nm.

Reinvestigation of the M(II) (M = Ni, Co)/tetrathiafulvalenetetracarboxylate system using high-throughput methods: isolation of a molecular complex and its single-crystal-to-single-crystal transformation to a two-dimensional coordination polymer.

A high-throughput methodology combined with X-ray powder diffraction measurements was used to investigate the reactivity of the TetraThiaFulvalene TetraCarboxylic acid ((TTF-TC)H(4)) with divalent metals (M = Ni, Co) under various reaction conditions (stoichiometry, pH, temperature). Two new crystalline phases were identified and then studied by single crystal X-ray diffraction. Whereas the first one appears to be a simple salt, the second one, formulated {[M(H(2)O)(4)](2)(TTF-TC)}·4H(2)O, is built of 2:1 M:TTF-TC molecular complexes and labeled MIL-136(Ni, Co) (MIL stands for Materials Institute Lavoisier). The combination of thermogravimetric analysis and thermodiffraction studies reveals that MIL-136(Ni) exhibits a complex dehydration behavior. Indeed, a partial dehydration/rehydration process led to the single-crystal-to-single-crystal transformation of the molecular compound in a two-dimensional coordination polymer formulated {[Ni(2)(H(2)O)(5)(TTF-TC)]}·H(2)O (MIL-136'(Ni)). Magnetic and redox properties of MIL-136(Ni, Co) were investigated. Magnetic measurements indicate that all the magnetic coupling, intra- and intermolecular, are very weak; thus, the magnetic data of MIL-136(Ni, Co) have been interpreted in term of single-ion spin orbit coupling. Solid state cyclic voltammetry of MIL-136(Ni, Co) presents three reversible waves which were assigned to the redox activity of the TTF core and the metallic cations. In contrast to solids based on TTF linkers and alkaline ions, the MIL-136(Ni, Co) complexes do not act as excellent positive electrode materials for Li batteries, but present two reversible electron oxidation of the TTF core. These observations were tentatively related to the strength of the metal-carboxylate bond.

Giant pores in a chromium 2,6-naphthalenedicarboxylate open-framework structure with MIL-101 topology.

Large, larger, ... Replacement of 1,4-benzenedicarboxylate by 2,6-naphthalenedicarboxylate in the MIL-101 structure leads to an isoreticular mesoporous framework containing cages with diameters of 39 and 46 A. High-throughput methods are employed to determine appropriate reaction conditions. The microcrystalline compound is characterized by molecular simulation techniques, powder X-ray diffraction, N(2)-sorption, and TEM investigations.

Poly[[diaqua-µ(2)-hydroxido-(µ(7)-2-phos-pho-nato-ethane-sulfonato)-dicopper(II)] trihydrate].

The crystal structure of the title compound, [Cu(2)(C(2)H(4)O(6)PS)(OH)(H(2)O)(2)]·3H(2)O, consists of two Cu(2+) ions, one (O(3)PC(2)H(4)SO(3))(3-) ion and one OH(-) ion, as well as five water mol-ecules, two of which are coordinated to Cu(2+). The Cu(2+) ions are coordinated by six O atoms. The CuO(6) polyhedra are connected by µ- and µ(3)-O atoms into zigzag chains along the b axis. These chains are further connected by -CH(2)CH(2)- groups to form layers, in turn building a three-dimensional framework via hydrogen bonding.

Poly[[aqua-tri-µ(3)-hydroxido-(µ(4)-2-phos-phon-ato-ethane-sulfonato)-dierbium(III)] monohydrate].

The crystal structure of the title compound, {[Er(2)(C(2)H(4)O(6)PS)(OH)(3)(H(2)O)]·H(2)O}(n), consists of two Er(3+) ions, one (C(2)H(4)O(6)PS)(3-) ion, three OH(-) ions, and two water mol-ecule. The Er(3+) ions form ErO(8) polyhedra., which are connected by µ- and µ(3)-O atoms. Thus, inorganic Er-O-Er layers of edge- and face-sharing polyhedra are observed. Whereas most often in metal phosphono-sulfonates the organic linker bridges adjacent layers, in the title compound, the (O(3)PC(2)H(4)SO(3))(3-) anion is only connected to one Er-O-Er layer. Short interatomic O⋯O distances [2.898 (8), 2.997 (14) and 2.768 (10) Å] indicate hydrogen bonding between the layers. The noncoordinated water mol-ecules are located between the layers.

Systematic investigation of lanthanide phosphonatoethanesulfonate framework structures by high-throughput methods, Ln(O3P-C2H4-SO3)(H2O) (Ln=La-Dy).

Following the strategy of using polyfunctional phosphonic acids for the synthesis of new metal phosphonates, the flexible organic linker molecule 2-phosphonoethanesulfonic acid, H2O3P-C2H4-SO3H (H3L), was used in a high-throughput (HT) investigation of lanthanide phosphonatoethanesulfonates. Two HT experiments comprising 96 individual hydrothermal reactions were performed to systematically investigate the influence of pH, rare earth ion, molar ratio of Ln3+:H3L, and the counterion in the system LnX3/H3L/NaOH/H2O with X=NO3-, Cl-, and CH3COO-. Whereas under basic conditions Ln(OH)3 is formed, acidic reaction conditions lead to nine isotypic compounds Ln(O3P-C2H4-SO3)(H2O) with Ln=La (1), Ce (2), Pr (3), Nd (4), Sm (5), Eu (6), Gd (7), Tb (8), and Dy (9). The crystal size of the compounds is strongly dependent on the ionic radius of the lanthanides and the pH. No significant influence of the counterions of the rare earth salts is observed. For compounds 1, 2, 4, and 5 the crystal structures could be determined from single-crystal X-ray diffraction. The structures are built up from chains of edge-sharing LnO8 polyhedra that are connected by the phosphonate and sulfonate groups to layers. These layers are linked by the -CH2CH2- group to a three-dimensional framework. The compounds 6 and 8 display luminescence in the visible range (intensity maximum 612 and 544 nm, respectively). Thermogravimetric investigations and temperature-dependent X-ray powder diffraction demonstrate the stability of the crystal structure up to 270 degrees C. Furthermore IR, Raman, and solid-state MAS NMR spectra of 1 and magnetic property measurements of 7 are also presented.