Materials Institute Lavoisier Research Articles

Reinvestigation of the MII (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.

Evaluation of Heterogeneous Metal−Organic Framework Organocatalysts Prepared by Postsynthetic Modification

A metal-organic framework (MOF) containing 2-amino-1,4-benzenedicarboxylate (NH(2)-BDC) as a building block is shown to undergo chemical modification with a set of cyclic anhydrides. The modification of the aluminum-based MOF known as MIL-53(Al)-NH(2) (MIL = Material Institut Lavoisier) by these reagents is demonstrated by using a variety of methods, including NMR and electrospray ionization mass spectrometry (ESI-MS), and the structural integrity of the modified MOFs has been confirmed by thermal gravimetric analysis (TGA) and powder X-ray diffraction (PXRD). Reaction with these cyclic anhydrides produces MOFs that display carboxylic acid functional groups within their pores. Furthermore, it is shown that maleic acid functionalized MIL-53(Al)-AMMal can act as a Brønsted acid catalyst and facilitate the methanolysis of several small epoxides. Experiments show that MIL-53(Al)-AMMal acts in a heterogeneous manner and is recyclable with consistent activity over at least three catalytic cycles. The findings presented here demonstrate several important features of covalent postsynthetic modification (PSM) on MOFs, including (1) facile introduction of catalytic functionality using simple organic reagents (e.g., anhydrides); (2) the ability to utilize and recycle organocatalytic MOFs; (3) control of catalytic activity through choice of functional group. The findings clearly illustrate that covalent postsynthetic modification represents a powerful means to access new MOF compounds that serve as organocatalytic materials.

MOFs, MILs and more: concepts, properties and applications for porous coordination networks (PCNs)

This review (over 380 references) summarizes metal–organic frameworks (MOFs), Materials Institute Lavoisier (MILs), iso-reticular metal–organic frameworks (IR-MOFs), porous coordination networks (PCNs), zeolitic metal–organic frameworks (ZMOFs) and porous coordination polymers (PCPs) with selected examples of their structures, concepts for linkers, syntheses, post-synthesis modifications, metal nanoparticle formations in MOFs, porosity and zeolitic behavior for applications in gas storage for hydrogen, carbon dioxide, methane and applications in conductivity, luminescence and catalysis.

Evidence of flexibility in the nanoporous iron(iii) carboxylate MIL-89

The very large expansion upon adsorption of liquids, up to 160% in cell volume, has been observed in the iron(iii) trans,trans muconate MIL-89 [(MIL = Material Institut Lavoisier]. The structure of lutidine-containing MIL-89 (lutidine = 2,6-dimethylpyridine) has been determined using X-ray powder diffraction and computer simulations. Finally, the consequences of adsorption of various polar and apolar liquids have been evaluated using ex situ synchrotron X-ray powder diffraction data and reveals that the swelling behavior of MIL-89 is selective but slightly different from the MIL-88 analogues.

Comparative study of two layered lanthanide dicarboxylates based on europium(III) dimers

The new rare-earth dicarboxylate solid Eu 2(H 2O) 4{C 6H 10–(CO 2) 2} 3·2H 2O or MIL-94 has been isolated under hydrothermal conditions. Its layered structure, which was solved using X-ray powder diffraction data, is built up from dimers of nine-coordinated edge-sharing polyhedra linked through 1,3-cyclohexane dicarboxylate (1,3-CHC) moieties. A comparative study of MIL-94 and the layered lanthanide dicarboxylate EuBDC or Eu 2(H 2O) 2{C 6H 4–(CO 2) 2} 3, which is built up from dimers of corner-sharing polyhedra and 1,3-benzenedicarboxylate (1,3-BDC) linkers, is also reported. Crystal data for MIL-94: orthorhombic space group Pnma (no. 62) with a = 8.8470(1) Å, b = 25.0148(1) Å, c = 14.3716(4) Å and Z = 4. MIL stands for Material Institut Lavoisier.

Structural changes upon dehydration of Pr (III)(H 2O){C 6H 3[sbnd](CO 2) 3} or MIL-81: A new three-dimensional praseodymium 1,2,4-benzenetricarboxylate with a one dimensional inorganic sub-network

A new three-dimensional lanthanide(III) tricarboxylate, MIL-81 1 1 MIL for Material Institut Lavoisier. or Pr (III)(H 2O)(C 6H 3 (CO 2) 3) has been obtained under hydrothermal conditions. Its three-dimensional structure, which has been determined using X-ray powder diffraction data, is built-up from edge-sharing chains of nine coordinated praseodymium(III) capped square antiprisms linked through 1,2,4-Benzenetricarboxylate (1,2,4-BTC) moieties. Its thermal behaviour has been investigated using TGA and X-ray thermodiffractometry and reveals that dehydration is followed by an irreversible structural change giving the solid MIL-81ht or Pr (III)(C 6H 3 (CO 2) 3) with both a change in the environment of the rare earth and in the connection mode of the carboxylate. Crystal data for MIL-81: monoclinic space group P 2 1 with a = 10.272 ( 1 ) Å , b = 7.057 ( 1 ) Å , c = 6.232 ( 1 ) Å , β = 93.668 ( 4 ) ° and Z = 2 . Crystal data for MIL-81ht: triclinic space group P-1 with a = 9.864 ( 1 ) Å , b = 7.054 ( 1 ) Å , c = 5.784 ( 1 ) Å , α = 90.862 ( 9 ) ° , β = 92.439 ( 6 ) ° , γ = 91.594 ( 8 ) ° and Z = 2 .

Synthesis, Structure and Properties of Related Microporous N,N‘-Piperazinebismethylenephosphonates of Aluminum and Titanium

A porous framework titanium(IV) N,N‘-piperazinebis(methylenephosphonate) (MIL-91(Ti)) and its aluminum analogue have been prepared under hydrothermal conditions (MIL = Material Institut Lavoisier). The structure of the aluminum analogue, AlOH(H2L)·nH2O (n ∼ 3, L = O3P−CH2−NC4H8N−CH2−PO3) was solved from a small single crystal and refined against laboratory powder X-ray diffraction data. The structure of the titanium form (TiO(H2L)·nH2O (n ∼ 4.5)) was determined using the structure of the aluminum form as a starting model and refining it against laboratory X-ray data. Their structures are built up from trans corner-sharing chains of TiO6 or AlO6 octahedra linked together in two directions via the diphosphonate groups. In each case this gives rise to a three-dimensional hybrid network with small channels along the b axis, filled with free water molecules. Thermogravimetric analysis and X-ray thermodiffractometry of the samples reveal that water is lost reversibly below 423 K and that both structures are stable up to 463 K. Dehydration gives porous solids (pore size ∼ 3.5 × 4.0 Å2) which adsorb nitrogen at 77 K to give Langmuir surface areas close to 500 m2·g-1. Crystal data for MIL-91(Ti) are as follows: space group C2/m (No. 12) with a = 19.415(2) Å, b = 7.071(1) Å, c = 11.483(1) Å, β = 92.78(1)°, V = 1574.70(1) Å3, and Z = 2. Crystal Data for MIL-91(Al) are as follows: space group C2/m (No. 12) with a = 18.947(2) Å, b = 6.915(1) Å, c = 11.295(1) Å, β = 90.45(1)°, and V = 1479.90(1)Å3.

An Open-Framework Rare-Earth Acetylenedicarboxylate: MIL-95, EuIII2(H2O)2(CO3)2·{O2C−C2−CO2}·{H2O}x

The first three-dimensional rare-earth acetylenedicarboxylate solid, MIL-95 (MIL = Material Institut Lavoisier), has been isolated and its structure solved from single-crystal X-ray diffraction data. Its two-dimensional inorganic subnetwork, built up from chains of edge-sharing nine-coordinated europium-capped square antiprisms and carbonate moieties, is pillared by the acetylenedicarboxylate groups. This leads to an open framework where small pores are filled with water molecules interacting with terminal water bound to the metal centers. TGA and X-ray thermodiffractometry show that dehydration leads to an irreversible pore contraction. The whole structure collapses above 230 degrees C. Crystal data for MIL-95: orthorhombic space group Pba2 (No. 32), with a = 7.6762(2) A, b = 17.8448(4) A, and c = 4.8105(2) A.

Synthesis and characterization of a new three-dimensional lanthanide carboxyphosphonate: Ln(4)(H(2)O)(7)[O(2)C-C(5)H(10)N-CH(2)(-)PO(3)](4)(H(2)O)(5).

The first open-framework lanthanide carboxyphosphonate has been obtained under hydrothermal conditions. The three-dimensional structure of MIL-84(Pr) (MIL = Material Institut Lavoisier) or Pr(4)(H(2)O)(7)[O(2)C-C(5)H(10)N-CH(2)(-)PO(3)](4)(H(2)O)(5) has been solved from X-ray diffraction single-crystal data (a = 23.481(1) A, b = 10.159(1) A, c = 23.006(1) A, beta = 105.63(1) degrees, V = 5284.6(6) A(3), space group Cc (No. 9)). Its framework is built up from chains of edged-sharing eight or nine-coordinated monocapped square antiprism polyhedra and carboxyphosphonate anions, creating a three-dimensional structure with small pores filled with water molecules. The thermal behavior of MIL-84(Pr) has been investigated using TGA and X-ray thermodiffractometry and indicates that MIL-84(Pr) is stable up to 523 K with a reversible hydration-dehydration process. The optical study of its yttrium analogue doped at 3.4% with europium (MIL-84(Y,Eu)) reveals a significant red-orange emission under UV radiation.