Stable organic radical stacked by in situ coordination to rare earth cations in MOF materials

With the correct choice of the solvothermal conditions, we have achieved the unprecedented in situ formation of the free radical form of the anthraquinone-1,5-disulfonate molecule, and its favorable organization. The semiquinone radicals are coordinated to rare-earth cations to produce a 2D framework with a very high charge mobility and electric conductivity through the π-π-interactions. The existence of AQDS 3- anion radicals is proven on the base of: i) the electrical neutrality: elemental analyses for the different lanthanide RPF-8 bulks, the maximum residual electron densities in the structure, rule out the existence of any other neutralizing ion, ii) the geometrical modifications in the antraquinone molecules, and iii) although less definitive, due to the low magnetic moment μ = 0.39 μ B, the exhibited paramagnetism for the La (3+) with no unpaired electrons. © 2012 The Royal Society of Chemistry.This work has been supported by Spanish MCYT Projects Mat 2007-60822, 2010-17571, and 2008-06542-C04, the Project Consolider-Ingenio CSD2006-2001, and the Project of Comunidad Autónoma de Madrid (S2009/MAT-1756).Peer Reviewe

Development of homogeneous and heterogenized rhodium(i) and palladium(ii) complexes with ligands based on a chiral proton sponge building block and their application as catalysts

Depto. de Química en Ciencias FarmacéuticasFac. de FarmaciaTRUEpu

Material órgano-inorgánico microporoso cristalino basado en cationes alcalinotérreos, procedimiento de preparación y usos

Material órgano-inorgánico microporoso cristalino basado en cationes alcalinotérreos, procedimiento de preparación y usos. La presente invención se refiere a una familia de materiales órgano-inorgánicos microporosos cristalinos conteniendo cationes alcalinotérreos y ácidos dicarboxílicos, su procedimiento de preparación y su uso como catalizadores heterogéneos reutilizables para reacciones en química orgánica, como tamices moleculares y como absorbentes de gases y líquidos.Peer reviewedConsejo Superior de Investigaciones Científicas (España), Instituto Madrileño de Estudios Avanzados en Energía (IMDEA-ENERGÍA)A1 Solicitud de patentes con informe sobre el estado de la técnic

Material órgano-inorgánico cristalino basado en cationes del grupo XIII de la tabla periódica, procedimiento de preparación y uso

[EN] The invention relates to a family of crystalline organic-inorganic materials containing cations of the group XIII (Al, Ga and In) and the chemical combination thereof, and polycarboxylic acids, their preparation method and the use thereof as reusable heterogeneous catalysts for reactions in organic chemistry.[ES] La presente invención se refiere a una familia de materiales órgano-inorgánicos cristalinos conteniendo cationes del grupo XIII (Al, Ga e In) y la combinación química de éstos, y ácidos policarboxílicos, su procedimiento de preparación y su uso como catalizadores heterogéneos reutilizables para reacciones en química orgánica.Peer reviewedConsejo Superior de Investigaciones Científicas (España)A1 Solicitud de patente con informe sobre el estado de la técnic

Indium metal-organic frameworks as catalysts in solvent-free cyanosilylation reaction

Two new Indium MOFs with the bending multicarboxylate ligand H 2dpmda as a linker and different N-donor ancillary ligands were obtained; the two compounds are isoreticular with 2D-hcb uninodal 3-connected nets. Comparison of their activity in cyanosilylation reactions with another eight In-MOFs is also reported. Eight out of the ten resulted in being good catalysts under mild and environmentally friendly conditions. Correlations between indium coordination number (CN), framework topology and catalytic activity are made and discussed, demonstrating that among the studied MOFs, the indium material named InPF-6 with the formula [In2(dpa) 3(1,10-phen)2]·H2O is the most effective catalyst. A possible catalytic mechanism is discussed. © 2013 The Royal Society of Chemistry.L. M. A.-D acknowledges a FPI scholarship from the Spanish Ministry of Economy and Competitiveness (MINECO), and Fondo Social Europeo from the EU. This work has been supported by the Spanish MCYT Projects MAT2010-17571, MAT2011-29020-C02-02, FAMA S2009/MAT-1756 Comunidad Autónoma de Madrid, and Consolider-Ingenio CSD2006-2001.Peer Reviewe

Toward understanding the structure-catalyst activity relationship of new indium MOFs as catalysts for solvent-free ketone cyanosilylation

Four new indium metal–organic frameworks, MOFs, namely [In2(hfipbb)3(1,10-phen)2]·2H2O (InPF-12), [In2(hfipbb)3(2,2′-bipy)2]·2H2O (InPF-13), [In2(hfipbb)3(4,4′-bipy)] (InPF-14) and [In4(OH)4(hfipbb)4(4,4′-bipy)] (InPF-15), (InPF = indium polymeric framework, hfipbb = hexafluoroisopropylidene bisbenzoate, phen = phenantroline, bipy = bipyridine), have been hydrothermally obtained and result in efficient Lewis acid catalysts in solvent-free cyanosilylation of carbonyl compounds. For acetophenone: (i) the coordination number and μ-OH groups presence seem to be decisive factors to obtain a better catalytic behavior and (ii) the presence of Lewis base moieties (C[double bond, length as m-dash]O groups not coordinated to indium cation), besides the Lewis acid sites, creates a two-component catalytic system, based on the “dual activation” phenomenon that makes InPF-15 the best catalyst in this type of reaction. It was also found that the use of this highly reactive, recyclable and environmentally benign catalyst allows the efficient synthesis of various trimethylsilyl cyanohydrins from a wide range of cyclic, aliphatic and aromatic ketones.L.M.A.-D. acknowledges a FPI scholarship from the Spanish Ministry of Economy and Competitiveness (MINECO) and Fondo Social Europeo from the EU. This work has been supported by the Spanish MCYT Projects MAT2010-17571, MAT2013-45460 R, MAT2011-29020-C02-02, FAMA S2009/MAT-1756 Comunidad Autonoma de Madrid, and Consolider-Ingenio CSD2006-2001

Crystalline organic-inorganic material based on cations of the group xiii of the periodic table, preparation method and use thereof

Material órgano-inorgánico cristalino basado en cationes del grupo XIII de la tabla periódica, procedimiento de preparación y uso. La presente invención se refiere a una familia de materiales órgano-inorgánicos cristalinos conteniendo cationes del grupo XIII (Al, Ga e In) y la combinación química de éstos, y ácidos policarboxílicos, su procedimiento de preparación y su uso como catalizadores heterogéneos reutilizables para reacciones en química orgánica.Peer reviewedConsejo Superior de Investigaciones Científicas (España)B1 Patente sin examen previ

Insight into lewis acid catalysis with alkaline-earth MOFs: The role of polyhedral symmetry distortions

We propose a multidisciplinary approach to face the interpretation of heterogeneous catalysis with alkaline-earth metal-organic frameworks (MOFs). Their oxygen-based polyhedra, which do not exhibit regular geometries, do act as very active Lewis acid sites. Four novel alkaline-earth MOFs that belong to three different structural types - Mg-AEPF-11, Mg-APF-12, Ca-AEPF-13 and Sr-APF-13 - are reported, together with their net topologies, and a study of the symmetry distortions around the alkaline-earth metal polyhedra by using a continuous shape mapping (CShM) description. These MOFs are good catalysts in the selective hydrogenation of styrene. Even more, Sr-AEPF-13 shows the best conversions ever published with alkaline-earth MOFs for the hydrogenation of activated alkenes under mild conditions. A combination of crystallographic and topological analysis and theoretical calculations, together with experimental catalytic results, has been applied to understand the catalytic activity of these four novel alkaline-earth MOFs. This work demonstrates that the presence of symmetry-distorted alkaline-earth polyhedra gives rise to highly catalytic-active MOFs in the hydrogenation of activated alkenes. A matter of shape! There are many aspects that remain poorly understood in catalysis with alkaline-earth metal-organic frameworks (MOFs). Their metal polyhedra, which do not exhibit regular geometries, act as very active Lewis acids. In this work a new multidisciplinary approach is proposed to understand the catalytic activity of four novel alkaline-earth MOFs in the selective hydrogenation of alkenes (see figure). Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.This work has been supported by the Spanish MCYT Project Mat 2010-17571, PHAMA S2009/Mat-1756 Comunidad de Madrid, and Consolider-Ingenio CSD2006-2001. A.E.P.P. acknowledges a JAE fellowship from the CSIC and the Fondo Social Europeo from the EU.Peer Reviewe

Synchronizing substrate activation rates in multicomponent reactions with metal-organic framework catalysts

A study on the influence of the cation coordination number, number of Lewis acid centers, concurrent existence of Lewis base sites, and structure topology on the catalytic activity of six new indium MOFs, has been carried out for multicomponent reactions (MCRs). The new indium polymeric frameworks, namely [In(OH)(popha)(HO)]·3 HO (InPF-16), [In(popha)(2,2′-bipy)]·3 HO (InPF-17), [In(OH)(popha)(4,4′-bipy)]·4 HO (InPF-18), [In(popha)(4,4′-bipy)]·3 HO (InPF-19), [In(OH)(Hpopha)]·0.5 (1,7-phen) (InPF-20), and [In(popha)(1,10-phen)]·4 HO (InPF-21) (InPF=indium polymeric framework, Hpopha=5-(4-carboxy-2-nitrophenoxy)isophthalic acid, phen=phenanthroline, bipy=bipyridine), have been hydrothermally obtained by using both conventional heating (CH) and microwave (MW) procedures. These indium frameworks show efficient Lewis acid behavior for the solvent-free cyanosilylation of carbonyl compounds, the one pot Passerini 3-component (P-3CR) and the Ugi 4-component (U-4CR) reactions. In addition, InPF-17 was found to be a highly reactive, recyclable, and environmentally benign catalyst, which allows the efficient synthesis of α-aminoacyl amides. The relationship between the Lewis base/acid active site and the catalytic performance is explained by the 2D seven-coordinated indium framework of the catalyst InPF-17. This study is an attempt to highlight the main structural and synthetic factors that have to be taken into account when planning a new, effective MOF-based heterogeneous catalyst for multicomponent reactions.This work has been supported by the Spanish Ministry of Economy and Competitiveness (MINECO) projects MAT2010‐17571, MAT2013‐45460‐R, MAT2011‐29020‐C02‐02, FAMA S2009/MAT‐1756, Comunidad Autónoma de Madrid, and Consolider‐Ingenio CSD2006‐2001. L.M.A.‐D. acknowledges a FPI scholarship from MINECO and Fondo Social Europeo from the European Union