Functionalization of Cu3BTC2@IL composites with Pd(II) for catalytic applications

Comunicación en forma de panel presentada en el congreso 2nd European Conference on Metal Organic Frameworks and Porous Polymers del 29 de octubre al 1 denoviembre de 2017 en Delft, HolandaMetal-organic frameworks could be excellent supports for active catalytic species in order to obtain heterogeneous and reusable catalysts, easily removable from the reaction media.[1,2] Additionally, the presence of unsaturated metal centres in their pores provides a superb opportunity to tackle with reactions that requires more than one type of metal centre.[3] In order to obtain heterometallic catalyst we have immobilized Pd(II) into the pores of the well studied Cu3BTC2 MOF (BTC= benzene-1,3,5-tricarboxilate) with the help of imidazolium derivated ionic liquids (IL). The preparation of the catalyst was made in two steps. Firstly, the Cu3BTC2 was charged with [BMIM][BF4] and [BMIM][PF6] ionic liquids(BMIM= 1-Butyl-3-methylimidazolium). The stability of the composite materials, both chemical and thermal, was studied. Then, the insertion of palladium was made in basic media. By means of EDX the presence of Pd into the structural pores was proved and the quantification was made by ICP-AES. The powder DRX of the Cu3BTC2@[BMIM][Cation]-Pd samples show no structural changes with respect to the pristine Cu3BTC2. The functionalized material was tested as heterogeneous catalyst for Suzuki-Miyaura coupling reactions. The reactions were made in methanol at 70 ºC and using K2CO3 as base. The Pd:substrate molar ratio was set at 0.1 %. The activity was firstly studied using 4-bromotoluene and phenylboronic acid as reagents. The total conversion of the reaction reached 91 % in 1.5 hours with a selectivity towards the cross-coupling product of 67 %. Afterwards, other substrates were tested to study the scope of the reaction. When using 4-bromoanisole and phenylboronic acid, 67% of conversion was reached after 4 hours with a 100 % of selectivity towards the cross-coupling product. References: [1] P. Valvekens, F. Vermoortele and D. D. Vos, Catal. Sci. Technol., 2013, 3, 1435–1445. [2] E. S. Larrea, R. Fernández de Luis, J. Orive, M. Iglesias and M. I. Arriortua, Eur. J. Inorg. Chem., 2015, 2015, 4699–4707. [3] D. Saha, R. Sen, T. Maity and S. Koner, Langmuir, 2013, 29, 3140–3151

Functionalization of Cu3BTC2@IL composites with Pd(II) for catalytic applications

Comunicación en forma de panel presentada en el congreso 2nd European Conference on Metal Organic Frameworks and Porous Polymers del 29 de octubre al 1 denoviembre de 2017 en Delft, HolandaMetal-organic frameworks could be excellent supports for active catalytic species in order to obtain heterogeneous and reusable catalysts, easily removable from the reaction media.[1,2] Additionally, the presence of unsaturated metal centres in their pores provides a superb opportunity to tackle with reactions that requires more than one type of metal centre.[3] In order to obtain heterometallic catalyst we have immobilized Pd(II) into the pores of the well studied Cu3BTC2 MOF (BTC= benzene-1,3,5-tricarboxilate) with the help of imidazolium derivated ionic liquids (IL). The preparation of the catalyst was made in two steps. Firstly, the Cu3BTC2 was charged with [BMIM][BF4] and [BMIM][PF6] ionic liquids(BMIM= 1-Butyl-3-methylimidazolium). The stability of the composite materials, both chemical and thermal, was studied. Then, the insertion of palladium was made in basic media. By means of EDX the presence of Pd into the structural pores was proved and the quantification was made by ICP-AES. The powder DRX of the Cu3BTC2@[BMIM][Cation]-Pd samples show no structural changes with respect to the pristine Cu3BTC2. The functionalized material was tested as heterogeneous catalyst for Suzuki-Miyaura coupling reactions. The reactions were made in methanol at 70 ºC and using K2CO3 as base. The Pd:substrate molar ratio was set at 0.1 %. The activity was firstly studied using 4-bromotoluene and phenylboronic acid as reagents. The total conversion of the reaction reached 91 % in 1.5 hours with a selectivity towards the cross-coupling product of 67 %. Afterwards, other substrates were tested to study the scope of the reaction. When using 4-bromoanisole and phenylboronic acid, 67% of conversion was reached after 4 hours with a 100 % of selectivity towards the cross-coupling product. References: [1] P. Valvekens, F. Vermoortele and D. D. Vos, Catal. Sci. Technol., 2013, 3, 1435–1445. [2] E. S. Larrea, R. Fernández de Luis, J. Orive, M. Iglesias and M. I. Arriortua, Eur. J. Inorg. Chem., 2015, 2015, 4699–4707. [3] D. Saha, R. Sen, T. Maity and S. Koner, Langmuir, 2013, 29, 3140–3151

Catalytic performance of a new 1D Cu(II) coordination polymer {Cu(NO3)(H2O)}(HTae)(4,4'-Bpy)

Abstract y comunicación en formato poster: 5th International Conference on Multifunctional, Hybrid and Nanomaterials (6-10 March 2017 | Lisbon, Portugal)There has been extensive interest in the synthesis and design of new porous coordination polymers [1] because of their potential applicability in different areas. One interesting crystal engineering approach to construct new coordination polymers is the selection of metal chelating ligands different from those commonly used. [2] In this regard, the β-diketonates, and concretely the metal β-diketonates, have been recently started to be used as structural building blocks in coordination polymers. [3] Deprotonated β-diketonates act as metal chelating agents; hence, in order to obtain extended structures other substituents are necessary to make them act as bridging ligands. This is the case of bis(β-diketonate) 1,1,2,2-tetraacetylethane (H2Tae) which can act as bischelating ligand bridging two metal centres. During the course of our research with the system Cu−Tae−4,4´-Bpy, we have obtained the 1D {Cu(NO3)(H2O)}(HTae)(4,4’-Bpy) coordination polymer.[4] The crystal structure consists in parallel and oblique {Cu(HTae)(4,4’-Bpy)} zig-zag metal-organic chains stacked along the [100] crystallographic direction. Copper atoms are in octahedral coordination environment linked to two nitrogen atoms of two bridging 4,4’-Bipy and to two oxygen atoms of one HTae molecule. The occupation of the other two positions varies from one copper atom to another with different combinations of water and nitrate molecules, giving rise to a commensurate super-structure. By means of thermal removal of water molecules we were able to obtain copper coordinatively unsaturated centres which could act as Lewis acid active sites in several heterogeneous catalytic reactions. Therefore, we have tested the anhydrous compound as heterogeneous catalyst for Knoevenagel condensation reactions. {Cu(NO3)(H2O)}(HTae)(4,4’-Bpy) is an efficient catalyst for the condensation of benzaldehyde and malonitrile in mild conditions (60 ºC in toluene, 5 % catalyst). The scope of the reaction was studied with various substrates. Recycling and leaching tests were also performed.Ministerio de Economía y Competitividad: MAT2013-42092-R Gobierno Vasco: IT-630-13 Dpto. Desarrollo Economico y Competitividad, programa ELKARTEK: ACTIMAT-KK-2015/0009

Catalytic Performance of a New 1D Cu(II) Coordination Polymer {Cu(NO3)(H2O)}(HTae)(4,40-Bpy) for Knoevenagel Condensation

11 p.The {Cu(NO3)(H2O)}(HTae)(4,40-Bpy) (H2Tae = 1,1,2,2-tetraacetylethane, 4,40-Bpy = 4,40-Dipyridyl) 1D coordination polymer has been obtained by slow evaporation. The crystal structure consists of parallel and oblique {Cu(HTae)(4,40-Bpy)} zig-zag metal–organic chains stacked along the [100] crystallographic direction. Copper(II) ions are in octahedral coordination environment linked to two nitrogen atoms of two bridging 4,40-Bpy and to two oxygen atoms of one HTae molecule in the equatorial plane. The occupation of the axial positions varies from one copper atom to another, with different combinations of water molecules and nitrate anions, giving rise to a commensurate super-structure. By means of the thermal removal of water molecules, copper coordinatively unsaturated centres are obtained. These open metal sites could act as Lewis acid active sites in several heterogeneous catalytic reactions. The dehydrated compound, CuHTaeBpy_HT, has been tested as a heterogeneous recoverable catalyst for Knoevenagel condensation reactions. The catalyst is active and heterogeneous for the condensation of aldehydes with malononitrile at 60 ºC using a molar ratio catalyst:substrate of 3 % and toluene as solvent. The catalyst suffers a partial loss of activity when reusing it, but can be reused at least four times.Ministerio de Economía y Competitividad: MAT2013-42092-R Gobierno Vasco: IT-630-13, KK-2015/0009

MOF@IL composite materials as Pd(II) supports for heterogeneous organocatalytic reactions

Comunicación Oral realizada en World Congress & Expo on Chemical Engineering & Catalysis (23-24 julio 2018, Osaka, Japón)Metal-Organic Frameworks (MOFs) have experienced a rapid emerge in the last two decades because they offer unique advantages for many applications due to their ordered structures, high thermal stability, tunable chemical functionality, ultra-high porosity and the availability of hundreds of well characterized structures.[1] Among the properties that they may present, they have shown interesting activity as heterogeneous catalysts.[2] Additionally, MOFs could be excellent supports for active catalytic species, due to their porous nature, in order to obtain heterogeneous and reusable catalysts,[3] providing superb opportunities to tackle with reactions that requires more than one type of active centre.[4] In order to obtain heterometallic catalyst we have immobilized Pd(II) into the pores of the well studied Cu3BTC2 MOF (BTC= benzene-1,3,5-tricarboxilate) with the help of imidazolium derivated ionic liquids (IL). The preparation of the catalyst was made in two steps. Firstly, the Cu3BTC2 was charged with [BMIM][BF4] ionic liquid (BMIM= 1-Butyl-3-methylimidazolium). Then, the insertion of palladium was made in basic media by the formation of a Pd organometallic complex with the N-heterocyclic carbine from the IL. The material was tested as heterogeneous catalyst for several organocatalytic reactions such as Suzuki-Miyaura and Sonogashira cross-coupling reactions, amine alkylation… The different conversion and selectivity results obtained for each type of reaction have allowed analyzing what is the role of each of the metals (Cu and Pd) in each reaction. References [1] H. Furukawa, K. E. Cordova, M. O’Keeffe, O. M. Yaghi, Science, 2013, 341(6149), 1230444-01–12; J. Adams, D. Pendlebury, Materials Science & Technology, Thomson Reuters, 2011. [2] P. García-García, M. Müller, A. Corma, Chem. Sci. 2014, 5, 2979–3007; J. Liu, L. Chen, H. Cui, J. Zhang, L. Zhang, C.-Y. Su, Chem. Soc. Rev. 2014, 43, 6011–6061. [3] P. Valvekens, F. Vermoortele, D. D. Vos, Catal. Sci. Technol. 2013, 3, 1435–1445; E. S. Larrea, R. Fernández de Luis, J. Orive, M. Iglesias, M. I. Arriortua, Eur. J. Inorg. Chem. 2015, 2015, 4699–4707. [4] D. Saha, R. Sen, T. Maity, S. Koner, Langmuir, 2013, 29, 3140–3151.Aknowledgements: This work has been financially supported by the “Ministerio de Economía, Industria y Competitividad” (MAT2016-76739-R (AEI/FEDER, UE)), the “Gobierno Vasco” (Basque University Research System Group, IT-630-13 and Dept. of Economic Development and Competitiveness, ELKARTEK program, LISOL (KK-2016/00095) projects), which we gratefully acknowledge. The authors thank the technicians of SGIker (UPV/EHU)

Crystal structure of K0.75[FeII 3.75FeIII 1.25(HPO3)6]- 0.5H2O, an open-framework iron phosphite with mixed-valent FeII/FeIII ions

Single crystals of the title compound, potassium hexaphosphitopentaferrate( II,III) hemihydrate, K0.75[FeII 3.75FeIII 1.25(HPO3)6] 0.5H2O, were grown under mild hydrothermal conditions. The crystal structure is isotypic with Li1.43[FeII 4.43FeIII 0.57(HPO3)6] 1.5H2O and (NH4)2[FeII 5(HPO3)6] and exhibits a [FeII 3.75FeIII 1.25(HPO3)6]0.75 open framework with disordered K+ (occupancy 3/4) as counter-cations. The anionic framework is based on (001) sheets of two [FeO6] octahedra (one with point group symmetry 3.. and one with point group symmetry .2.) linked along [001] through [HPO3]2 oxoanions. Each sheet is constructed from 12-membered rings of edge-sharing [FeO6] octahedra, giving rise to channels with a radius of ca 3.1 A ˚ where the K+ cations and likewise disordered water molecules (occupancy 1/4) are located. O O contacts between the water molecule and framework O atoms of 2.864 (5) A ˚ indicate hydrogen-bonding interactions of medium strength. The infrared spectrum of the compound shows vibrational bands typical for phosphite and water groups. The Mössbauer spectrum is in accordance with the presence of FeII and FeIII ions.Ministerio de Economía y Competitividad, MAT2013–42092-R // Gobierno Vasco, IT-630–13 y SAI12/82 // Universidad del País Vasco, UPV/EHU, UFI-11/1

Ionic liquids in the control of the poly(vinylidene fluoride-co- hexafluoropropylene) membranes morphology [Poster]

Poster presentado en: New Materials for a Better life! 2017 Workshop, 27/10/2017, Facultad de Ciencia y Tecnología, Universidad del País VascoThe development of polymer membranes with tailored micro-morphology and wettability are a demand in the areas of filtration, sensors or tissue engineering, among others. Poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) is a thermoplastic copolymer and one of the most interesting polymers to be used in these areas due to its good mechanical and thermal properties, biocompatibility and low density. The control of the morphology on this material is crucial for its performance. However, for the moment this is a complicated task and is mostly restricted to the use of solvent evaporation (SE) and non-solvent-induced phase separation (NIPS) techniques. In this way, this work consists in a systematic study of the use of ionic liquids in the control of these membranes properties. Ionic liquids are molten salts with melting points lower than 100 °C, which stand out for their good properties, such as high good thermal stability, low vapor pressure, nonflammability and their ability to act as solvents of various materials and they have already been studied for the control of morphology in certain materials. In this work, the production and the characterization of PVDF-HFP@ionic liquid composite membranes using different ionic liquids (Diethylmethylammonium trifluoromethanesulfonate, 1-Methylimidazolium bis(trifluoromethylsulfonyl)imide and 1-Methylimidazolium chloride) and methodologies (solvent evaporation temperature) are described in detail. The results demonstrate how aspects such as morphology, wettability or mechanical properties change depending on the production methodology employed and on the type of used ionic liquid. In view of the results, it is concluded that the morphology of a polymer composite can be tuned by use ILs and this control of the morphology could open up new possibilities for their use in different applications.“Ministerio de Economía, Industria y Competitividad” (MAT2016-76739-R(AEI/FEDER, UE)). “Gobierno Vasco” ( KK-2016/00095-LISOL, program Elkartek)

Ionic liquids in the control of the poly(vinylidene fluoride-co-hexafluoropropylene) membranes morphology

Presentada en NALS 2017 Conference on Nanomaterials applied to Lifesciences in Gijón, Spain, 13-15 December 2017The development of polymer membranes with tailored micro-morphology and wettability are a demand in the areas of filtration, sensors or tissue engineering, among others. Poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) is a thermoplastic copolymer and one of the most interesting polymers to be used in these areas due to its good mechanical and thermal properties, biocompatibility and low density. The control of the morphology on this material is crucial for its performance [1]. However, for the moment this is a complicated task and is mostly restricted to the use of solvent evaporation (SE) and non-solvent-induced phase separation (NIPS) techniques. In this way, this work consists in a systematic study of the use of ionic liquids in the control of these membranes properties. Ionic liquids are molten salts with melting points lower than 100 °C, which stand out for their good properties, such as high good thermal stability, low vapor pressure, nonflammability and their ability to act as solvents of various materials and they have already been studied for the control of morphology in certain materials [2-3]. In this work, the production and the characterization of PVDF-HFP@ionic liquid composite membranes using different ionic liquids (Diethylmethylammonium trifluoromethanesulfonate, 1-Methylimidazolium bis(trifluoromethylsulfonyl)imide and 1-Methylimidazolium chloride) and methodologies (solvent evaporation temperature) are described in detail. The results demonstrate how aspects such as morphology, wettability or mechanical properties change depending on the production methodology employed and on the type of used ionic liquid. In view of the results, it is concluded that the morphology of a polymer composite can be tuned by use ILs and this control of the morphology could open up new possibilities for their use in different applications

Ionic liquids in the control of the poly(vinylidene fluoride-co- hexafluoropropylene) membranes morphology [Poster]

Poster presentado en: New Materials for a Better life! 2017 Workshop, 27/10/2017, Facultad de Ciencia y Tecnología, Universidad del País VascoThe development of polymer membranes with tailored micro-morphology and wettability are a demand in the areas of filtration, sensors or tissue engineering, among others. Poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) is a thermoplastic copolymer and one of the most interesting polymers to be used in these areas due to its good mechanical and thermal properties, biocompatibility and low density. The control of the morphology on this material is crucial for its performance. However, for the moment this is a complicated task and is mostly restricted to the use of solvent evaporation (SE) and non-solvent-induced phase separation (NIPS) techniques. In this way, this work consists in a systematic study of the use of ionic liquids in the control of these membranes properties. Ionic liquids are molten salts with melting points lower than 100 °C, which stand out for their good properties, such as high good thermal stability, low vapor pressure, nonflammability and their ability to act as solvents of various materials and they have already been studied for the control of morphology in certain materials. In this work, the production and the characterization of PVDF-HFP@ionic liquid composite membranes using different ionic liquids (Diethylmethylammonium trifluoromethanesulfonate, 1-Methylimidazolium bis(trifluoromethylsulfonyl)imide and 1-Methylimidazolium chloride) and methodologies (solvent evaporation temperature) are described in detail. The results demonstrate how aspects such as morphology, wettability or mechanical properties change depending on the production methodology employed and on the type of used ionic liquid. In view of the results, it is concluded that the morphology of a polymer composite can be tuned by use ILs and this control of the morphology could open up new possibilities for their use in different applications.“Ministerio de Economía, Industria y Competitividad” (MAT2016-76739-R(AEI/FEDER, UE)). “Gobierno Vasco” ( KK-2016/00095-LISOL, program Elkartek)

MOF@IL composite materials as Pd(II) supports for heterogeneous organocatalytic reactions

Comunicación Oral realizada en World Congress & Expo on Chemical Engineering & Catalysis (23-24 julio 2018, Osaka, Japón)Metal-Organic Frameworks (MOFs) have experienced a rapid emerge in the last two decades because they offer unique advantages for many applications due to their ordered structures, high thermal stability, tunable chemical functionality, ultra-high porosity and the availability of hundreds of well characterized structures.[1] Among the properties that they may present, they have shown interesting activity as heterogeneous catalysts.[2] Additionally, MOFs could be excellent supports for active catalytic species, due to their porous nature, in order to obtain heterogeneous and reusable catalysts,[3] providing superb opportunities to tackle with reactions that requires more than one type of active centre.[4] In order to obtain heterometallic catalyst we have immobilized Pd(II) into the pores of the well studied Cu3BTC2 MOF (BTC= benzene-1,3,5-tricarboxilate) with the help of imidazolium derivated ionic liquids (IL). The preparation of the catalyst was made in two steps. Firstly, the Cu3BTC2 was charged with [BMIM][BF4] ionic liquid (BMIM= 1-Butyl-3-methylimidazolium). Then, the insertion of palladium was made in basic media by the formation of a Pd organometallic complex with the N-heterocyclic carbine from the IL. The material was tested as heterogeneous catalyst for several organocatalytic reactions such as Suzuki-Miyaura and Sonogashira cross-coupling reactions, amine alkylation… The different conversion and selectivity results obtained for each type of reaction have allowed analyzing what is the role of each of the metals (Cu and Pd) in each reaction. References [1] H. Furukawa, K. E. Cordova, M. O’Keeffe, O. M. Yaghi, Science, 2013, 341(6149), 1230444-01–12; J. Adams, D. Pendlebury, Materials Science & Technology, Thomson Reuters, 2011. [2] P. García-García, M. Müller, A. Corma, Chem. Sci. 2014, 5, 2979–3007; J. Liu, L. Chen, H. Cui, J. Zhang, L. Zhang, C.-Y. Su, Chem. Soc. Rev. 2014, 43, 6011–6061. [3] P. Valvekens, F. Vermoortele, D. D. Vos, Catal. Sci. Technol. 2013, 3, 1435–1445; E. S. Larrea, R. Fernández de Luis, J. Orive, M. Iglesias, M. I. Arriortua, Eur. J. Inorg. Chem. 2015, 2015, 4699–4707. [4] D. Saha, R. Sen, T. Maity, S. Koner, Langmuir, 2013, 29, 3140–3151.Aknowledgements: This work has been financially supported by the “Ministerio de Economía, Industria y Competitividad” (MAT2016-76739-R (AEI/FEDER, UE)), the “Gobierno Vasco” (Basque University Research System Group, IT-630-13 and Dept. of Economic Development and Competitiveness, ELKARTEK program, LISOL (KK-2016/00095) projects), which we gratefully acknowledge. The authors thank the technicians of SGIker (UPV/EHU)