Person: Cortijo Montes, Miguel
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First Name
Miguel
Last Name
Cortijo Montes
Affiliation
Universidad Complutense de Madrid
Faculty / Institute
Ciencias Químicas
Department
Química Inorgánica
Area
Química Inorgánica
Identifiers
14 results
Search Results
Now showing 1 - 10 of 14
Item Tetracarbonatodiruthenium Fragments and Lanthanide(III) Ions as Building Blocks to Construct 2D Coordination Polymers(Polymers, 2019) Gutiérrez Martín, Daniel; Cortijo Montes, Miguel; Martín Humanes, Álvaro; González Prieto, Rodrigo; Delgado Martínez, Patricia; Herrero Domínguez, Santiago; Priego Bermejo, José Luis; Jiménez Aparicio, ReyesTwo-dimensional coordination polymers of [Pr(DMSO)2(OH2)3][Ru2(CO3)4(DMSO)(OH2)]·5H2O (Prα) and [Ln(OH2)5][Ru2(CO3)4(DMSO)]·xH2O (Ln = Sm (Smβ), Gd (Gdβ)) formulae have been obtained by reaction of the corresponding Ln(NO3)3·6H2O dissolved in dimethyl sulphoxide (DMSO) and K3[Ru2(CO3)4]·4H2O dissolved in water. Some DMSO molecules are coordinated to the metal atoms reducing the possibilities of connection between the [Ru2(CO3)4]3− and Ln3+ building blocks giving rise to the formation of two-dimensional networks. The size of the Ln3+ ion and the synthetic method seem to have an important influence in the type of two-dimensional structure obtained. Slow diffusion of the reagents gives rise to Prα that forms a 2D net that is built by Ln3+ ions as triconnected nodes and two types of Ru25+ units as bi- and tetraconnected nodes with (2-c)(3-c)2(4-c) stoichiometry (α structure). An analogous synthetic procedure gives Smβ and Gdβ that display a grid-like structure, (2-c)2(4-c)2, formed by biconnected Ln3+ ions and two types of tetraconnected Ru25+ fragments (β structure). The magnetic properties of these compounds are basically explained as the sum of the individual contributions of diruthenium and lanthanide species, although canted ferrimagnetism or weak ferromagnetism are observed at low temperature.Item Linear One-Dimensional Coordination Polymers Constructed by Dirhodium Paddlewheel and Tetracyanido-Metallate Building Blocks(Crystals, 2019) Prior, David; Cortijo Montes, Miguel; González Prieto, Rodrigo; Herrero Domínguez, Santiago; Jiménez Aparicio, Reyes; Perles Hernáez, Josefina; Priego Bermejo, José LuisIn this article, we describe the preparation of anionic heteronuclear one-dimensional coordination polymers made by dirhodium paddlewheels and tetracyanido-metallatate building blocks. A series of complexes of (PPh4)2n[{Rh2(µ-O2CCH3)4}{M(CN)4}]n (M = Ni (1), Pd (2), Pt (3)) formulae were obtained by reaction of [Rh2(μ-O2CCH3)4] with (PPh4)2[M(CN)4] in a 1:1 or 2:1 ratio. Crystals of 1−3 suitable for single crystal X-ray diffraction were grown by slow diffusion of a dichloromethane solution of the dirhodium complex into a chloroform solution of the corresponding tetracyanido–metallatate salt. Compounds 1 and 2 are isostructural and crystallize in the triclinic P-1 space group, while compound 3 crystallizes in the monoclinic P21/n space group. A detailed description of the structures is presented, including the analysis of the packing of anionic chains and PPh4+ cations.Item Synthesis and Structural Characterization of a Series of One-Dimensional Heteronuclear Dirhodium-Silver Coordination Polymers(Polymers, 2019) Cruz Franch, Paula; Fernández Bartolomé, Estefanía; Cortijo Montes, Miguel; Delgado Martínez, Patricia; González Prieto, Rodrigo; Priego Bermejo, José Luis; Torres, María del Rosario; Jiménez Aparicio, ReyesHerein, we describe the preparation of heteronuclear dirhodium-silver complexes by reaction between molecular Rh(II)-Rh(II) compounds [Rh2(μ-O2CR)4L2] (R = Me, Ph (1), CH2OEt (2); L = solvent molecules) with paddlewheel structure and PPh4[Ag(CN)2]. One-dimensional coordination polymers of (PPh4)n[Rh2(μ-O2CR)4Ag(CN)2]n (R = Me (3), Ph (4), CH2OEt (5)) formula have been obtained by replacement of the two labile molecules in the axial positions of the paddlewheel structures by a [Ag(CN)2]− bridging unit. The crystal structures of 3–5 display a similar arrangement, having anionic chains with a wavy structure and bulky (PPh4)+ cations placed between the chains. The presence of the (PPh4)+ cations hinders the existence of intermolecular Ag-Ag interactions although several C-H····π interactions have been observed. A similar reaction between [Rh2(μ-O2CCMe3)4(HO2CCMe3)2] and PPh4[Ag(CN)2] led to the molecular compound (PPh4)2{Rh2(μ-O2CCMe3)4[Ag(CN)2]2} (6) by replacement of the axial HO2CCMe3 ligands by two [Ag(CN)2]− units. The trimethylacetate ligand increases the solubility of the complex during the crystallization favouring the formation of discrete heteronuclear species.Item Magnetostructural Studies on Zigzag One-Dimensional Coordination Polymers Formed by Tetraamidatodiruthenium(II,III) Paddlewheel Units Bridged by SCN Ligands(Magnetochemistry, 2019) Moreno da Silva, Sara; Delgado Martínez, Patricia; Cortijo Montes, Miguel; González Prieto, Rodrigo; Priego Bermejo, José Luis; Herrero Domínguez, Santiago; Jiménez Aparicio, ReyesWe report herein on three zigzag one-dimensional coordination polymers of {[Ru2(μ-NHOCR)4](μ-SCN)}n (R = o-Me-C6H4 (2), m-Me-C6H4 (3), p-Me-C6H4 (4)) formula. These new compounds have been obtained by reaction of the corresponding [Ru2(μ-NHOR)4(THF)2](BF4) complex with (NBu4)(SCN) under different synthetic conditions. The crystal structure of [Ru2(μ-NHOCC6H4-o-Me)4(THF)2](BF4) (1), 2 and 3 are presented. A cis-(2,2) arrangement of the amidate ligands of the [Ru2(μ-NHOCR)4]+ units is observed in all cases. Interestingly, the structures of 2 and 3 show linkage isomerism in alternated tetraamidatodiruthenium units whose axial positions are occupied by the same type of donor atom of the SCN ligands. This results in zigzag chains with a Ru-S-C angle of 98.97° and Ru-N-C angle of 169.36° in the case of 2 and 97.99° and 159.26°, respectively, in the case of 3. The magnetic data obtained for 2–4 are indicative of a σ2π4δ2(π*δ*)3 ground state (S = 3/2) and a large zero-field splitting (ZFS) in all cases (D = 54.57, 62.72 and 43.00 cm−1 for 2–4, respectively). Similar small antiferromagnetic interactions between diruthenium units (zJ = −0.93, −0.79 and −1.11 cm−1 for 2–4, respectively) are estimated for all the polymers, suggesting an analogous zigzag arrangement of the chains for 4.Item Microwave and solvothermal methods for the synthesis of nickel and ruthenium complexes with 9-anthracene carboxylate ligand(Inorganica Chimica Acta, 2015) Cortijo Montes, Miguel; Delgado-Martínez, Patricia; González Prieto, Rodrigo; Herrero Domínguez, Santiago; Jiménez Aparicio, Reyes; Perles Hernáez, Josefina; Priego Bermejo, José Luis; Torres, Marisa RosarioMicrowave and solvothermal activation processes have been explored as tools for the preparation of various nickel and ruthenium complexes. Different reaction conditions are tested using ethanol or water as solvents. Three nickel derivatives, [Ni(9-atc)2(OH2)2(py)2]·2EtOH (1), [Ni2(9-atc)4(OH2)(py)4]·2H2O (2·2H2O), and [Ni2(9-atc)4(py)2] (3), and two diruthenium compounds, {[Ru2Cl(9-atc)4]·2H2O}n (4) and [Ru2(9-atc)4(EtOH)2]·2EtOH (5), are obtained. The crystal structure determination of complexes 1-3 and 5 is also described. Compound 1 displays a 1D extended supramolecular structure with hydrogen bonds involving crystallization solvent molecules. Compound 2 is dimetallic, and both nickel centers show an octahedral coordination environment, whereas complexes 3 and 5 display a typical carboxylate-bridged paddlewheel-type structure with two metal atoms connected by four bridging carboxylate ligands. All compounds show weak antiferromagnetic interactions except 3, where a strong intra-dimer antiferromagnetic coupling is observed. Compound 4 also shows a strong zero field splitting.Item Hybrid Polyfunctional Systems Based on Nickel(II) Isonicotinate(European Journal of Inorganic Chemistry, 2013) Cortijo Montes, Miguel; Herrero Domínguez, Santiago; Jiménez Aparicio, Reyes; Perles Hernáez, Josefina; Priego Bermejo, José Luis; Torralvo, Maria José; Torroba, JavierSeveral metal–organic frameworks of nickel(II) were obtained starting from the molecular complex 1, [Ni(OH2)4(4-pyc)2] (4-pyc = 4-pyridinecarboxylate or isonicotinate). By using different reaction conditions, two polymorphs of the anhydrous complex [Ni(4-pyc)2]n (2a and 2b) and the polynuclear compound [Ni5(OH2)3(4-pyc)10]n (3) were obtained in very high yield. All of the compounds were characterized by elemental analysis and spectroscopic data. The crystal structure determination of compounds 2b and 3 was also carried out. Structural and topological analysis of these new structural types and other related ones were performed. It was found that compounds 2a and 2b are a rare case of coordination framework isomers. Thermogravimetric studies indicate that compounds 2b and 3 lose the pore-allocated solvent molecules at moderate temperatures without any significant structural change, and at higher temperatures, compounds 1 and 3 are transformed into 2a. Textural parameters that characterize the microporous networks for 2b and 3 were obtained by nitrogen-adsorption measurements. For both samples, the micropore size distribution indicates cylindrical pores with diameters of 0.85 (2b) and 0.90 nm (3). The values of Brunauer–Emmett–Teller and Langmuir surface areas are 178 and 185 m2 g–1 for compound 2b, and 995 and 982 m2 g–1 for compound 3. Micropore volumes are 0.065 and 0.350 cm3 g–1 for 2b and 3, respectively. The magnetic properties of compounds 1, 2a, and 2b are consistent with the presence of zero-field splitting and a small antiferromagnetic coupling between the metal atoms. The magnetic properties of the pentanuclear compound 3 were analyzed by considering one monomer with zero-field splitting caused by axially distorted NiII octahedral compounds, and two dimeric fragments with magnetic interactions within each dimetallic unit.Item Trapping Ag(I) ions by a Pd8 metallacrown molecule to form an unusual nonanuclear AgPd8 cation(Inorganica Chimica Acta, 2019) Calleja, Fernando ; Cortijo Montes, Miguel; Perles Hernáez, Josefina; Herrero Domínguez, Santiago; Jiménez Aparicio, ReyesThe {[Pd(µ-SC6F5)(µ-dppm)Pd](µ-SC6F5)}4 (dppm = methanediylbis(diphenylphosphane)) (Pd8) metallacrown traps Ag(I) cations giving {Ag[Pd(µ3-SC6F5)(µ-dppm)Pd]4(µ-SC6F5)4}(X) (X = SO3CF3− (AgPd8a), SbF6− (AgPd8b) and ClO4− (AgPd8c)) and {Ag[Pd(µ3-SC6F5)(µ-dppm)Pd]4(µ-SC6F5)4}2[Pt(C6F5)4] (AgPd8d). The insertion of silver increases significantly the stability of the cluster that is stable in solution even in the presence of light, because of the macrocyclic effect.Item The use of amidinate ligands in paddlewheel diruthenium chemistry(Coordination Chemistry Reviews, 2019) Cortijo Montes, Miguel; González Prieto, Rodrigo; Herrero Domínguez, Santiago; Priego Bermejo, José Luis; Jiménez Aparicio, ReyesThe amidinate anions have been widely used in the formation of dinuclear complexes with paddlewheel structure. The higher donor character of this type of ligands, compared to carboxylate ligands, increases the electronic density of the dimetallic units giving, in the case of ruthenium, stable complexes with a large variety of oxidation states containing Ru24+, Ru25+ and Ru26+ units. Even complexes with Ru22+, Ru23+ and Ru27+ cores have been detected in electrochemical measurements and isolated in some cases. The influence of formamidinate and benzamidinate ligands in the synthesis, characterization, properties and reactivity of metal-metal bonded diruthenium complexes with paddlewheel structure in several oxidation states is considered. A revision of the electronic and magnetic properties of diruthenium complexes and their relationship with the different electronic configurations found in this type of complexes is broadly documented. Additionally, the switching between oxidation states is considered through the discussion of the results obtained by electrochemical measurements. Finally, the most relevant applications of the amidinatodiruthenium complexes are also reviewed.Item Ferromagnetic Interactions through Hydrogen Bonds in a One‐Dimensional NiII Coordination Polymer(European Journal of Inorganic Chemistry, 2013) Cortijo Montes, Miguel; González Prieto, Rodrigo; Herrero Domínguez, Santiago; Jiménez Aparicio, Reyes; Sánchez-Rivera, PaulaA one-dimensional coordination polymer [Ni(tp)(OH2)4] (1) (tp = –O2CC6H4CO2–; terephthalate) has been synthesized under environmentally friendly conditions. It has been characterized by elemental analysis, infrared spectroscopy, thermogravimetry, single-crystal and powder X-ray diffraction, and magnetic measurements. Compound 1 is a rare example of 1D polymeric NiII dicarboxylate that shows ferromagnetic interactions through hydrogen bonds. The zigzag arrangement of the NiII octahedral units connected by hydrogen bonds distinguishes compound 1 from other [Ni(dicarboxylate)(OH2)4] compounds, in which the interactions are antiferromagnetic.Item One‐Dimensional [Ni(O2CR)2(NN)x] Polymers: Structural, Magnetic, and Density Functional Theory Studies(ChemPlusChem, 2014) Cortijo Montes, Miguel; Herrero Domínguez, Santiago; Jerez, Belén; Jiménez Aparicio, Reyes; Perles Hernáez, Josefina; Priego Bermejo, José Luis; Tortajada Pérez, JoséFive nickel complexes, [Ni2(3,4,5-tmb)4(4,4 ′-bpy)] (1), [Ni2(2-ntc)4(4,4 ′-bpy)] (2), [Ni(9-atc)2(4,4 ′-bpy)] (3), [Ni(3,4,5-tmb)2(t-bpee) ] (4), and [Ni2(2-ntc)4(t-bpee)2] (5) (3,4,5-tmb=3,4,5-trimethoxybenzoate; 2-ntc=2-naphthalenecarboxylate; 9-atc=9-anthracenecarboxylate; 4,4 ′-bpy=4,4 ′-bipyridine; t-bpee=trans-1,2-bis(4-pyridyl)ethylene), are prepared. They are characterized by elemental analysis, IR spectroscopy, thermogravimetric analysis, and single-crystal and powder X-ray diffraction. 1 and 2 form linear chains of paddlewheel units joined by 4,4 ′-bpy ligands; 3 and 4 display zigzag chains formed by cis-bis(chelate) Ni(O2CR)2 units joined by 4,4 ′-bpy and t-bpee, respectively; and the structure of 5 consists of double chains. The magnetic behavior of the compounds is also studied, and DFT calculations using the broken-symmetry approximation are performed to gain a better understanding of the strong antiferromagnetism found in 1. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.