Rhodium and copper 6-methylpicolinate complexes. Structural diversity and supramolecular interaction study

Seven new coordination compounds with 6-methylpicolinic acid (6-HMepic) and rhodium(III) or copper(II) of formula [Rh(6-Mepic)3] (1), [Rh(6-Mepic)2(H2O)Cl] (2), [Rh(6-HMepic)(6-Mepic)Cl2]·3.5(H2O) (3), [Cu(6-Mepic)2(H2O)]·H2O (4), [Cu(6-Mepic)2]n, (5), [Cu(6-Mepic)(6-HMepic)I] (6) and [Cu(6-Mepic)(6-HMepic)Cl] (7) have been obtained. Their syntheses have been rationalized, and their structural and supramolecular characteristics have been studied and compared with other similar rhodium and copper picolinate complexes previously reported, in order to stablish structural correlations and analogies. The electrical properties of coordination polymer [Cu(6-Mepic)2]n (5) have been also analyzed and it has been found that it shows a moderated electrical transport along the chain.We thank the financial support from the Spanish Ministerio de Economía y Competitividad (MAT2013-46502-C2-2P and MAT2013-46753-C2-1P). Also the scientific computing center (CCC) of the Autonoma University of Madrid for their tim

MasterChem: Cooking 2D-polymers

2D-polymers are still dominated by graphene and closely related materials such as boron nitride, transition metal sulphides and oxides. However, the rational combination of molecules with suitable design is already showing the high potential of chemistry in this new research field. The aim of this feature article is to illustrate, and provide some perspectives, the current state-of-the-art in the field of synthetic 2D-polymers showing different alternatives to prepare this novel type of polymers based on the rational use of chemistry. This review comprises a brief revision of the essential concepts, the strategies of preparation following the two general approaches, bottom-up and top-down, and a revision of the promising seminal properties showed by some of these nanomaterials.Financial support from Spanish MINECO (MAT2013-46753-C2-1-P and MAT2013-46502-C2-2-P). D. R. thanks the Spanish MECD for a FPU gran

Luminescent Thermochromism of 2D Coordination Polymers Based on Copper(I) Halides with 4-Hydroxythiophenol

This is the peer-reviewed version of the following article: Troyano, J., Perles, J., Amo‐Ochoa, P., Martínez, J. I., Concepción Gimeno, M., Fernández‐Moreira, V., ... & Delgado, S. (2016). Luminescent Thermochromism of 2D Coordination Polymers Based on Copper (I) Halides with 4‐Hydroxythiophenol. Chemistry–A European Journal, 22(50), 18027-18035., which has been published in final form at https://doi.org/10.1002/chem.201603675. This article may be used for non-commercial purposes in accordance with Wiley-VCH Terms and Conditions for Self-ArchivingSolvothermal reactions between copper(I) halides and 4-mercaptophenol give rise to the formation of three coordination polymers with general formula [Cu3X(HT)2]n(X=Cl, 1; Br, 2; and I, 3). The structures of these coordination polymers have been determined by X-ray diffraction at both room- and low temperature (110 K), showing a general shortening in Cu−S, Cu−X and Cu−Cu bond lengths at low temperatures. 1 and 2 are isostructural, consisting of layers in which the halogen ligands act as μ3-bridges joining two Cu1 and one Cu2 atoms whereas in 3 the iodine ligands is as μ4-mode but the layers are quasi-isostructural with 1 or 2. These compounds show a reversible thermochromic luminescence, with strong orange emission for 1 and 2, but weaker for 3 at room temperature, whereas upon cooling at 77 K 1 and 2 show stronger yellow emission, and 3 displays stronger green emission. DFT calculations have been used to rationalize these observations. These results suggest a high potential for this novel and promising stimuli-responsive materialsThis work was supported by MICINN (MAT2013-46753-C2-1-P). JIM acknowledges funding from the ERC-Synergy Program (Grant ERC-2013-SYG-610256 NANOCOSMOS) and computing resources from CTI-CSIC

Fast and efficient direct formation of size-controlled nanostructures of coordination polymers based on copper(i)-iodine bearing functional pyridine terminal ligands

We report on the direct formation of 1D nanostructures of two coordination polymers based on copper(i)-iodine double chains decorated with ethyl isonicotinate or 2-amino-5-nitropyridine as terminal ligands. The use of different reaction conditions, e.g. energy of the formation process, solvents, and/or concentration of reactants, has allowed the control of the size of the fibres and ribbons directly formed in this process going from micron- to submicron- up to nano-size. We show experiments that direct the formation of materials kinetically versus thermodynamically controlled, adjusting simple experimental parameters. Finally, a morphological study on the Cu(i)-iodine bearing 2-amino-5-nitropyridine nanofibres has confirmed their reversible molecular recognition ability towards acetic acid vapoursWe are grateful for financial support from the Spanish Ministerio de Economía y Competitividad (MAT2013-46502-C2-2P, MAT2016-75883-C2-2-P, BES-2015-071534) and also to the scientific computing center (CCC) of the Autónoma University of Madrid for their tim

Structure and electrical properties of a one-dimensional polymeric silver thiosaccharinate complex with argentophilic interactions

Among the potential applications of coordination polymers, electrical con­ductivity ranks high in technological inter­est. We report the synthesis, crystal structure and spectroscopic analysis of an AgI–thio­saccharinate one-dimensional coordination polymer {systematic name: catena-poly[[[aqua­tetra­kis­(μ3-1,1-dioxo-1,2-benziso­thia­zole-3-thiol­ato-κ3N:S3:S3)tetra­silver(I)]-μ2-4,4′-(propane-1,3-di­yl)di­pyridine-κ2N:N′] dimethyl sulfoxide hemisolvate]}, {[Ag4(C7H4NO2S2)4(C13H14N2)(H2O)]·0.5C2H6OS}n, with the 4,4′-(propane-1,3-di­yl)di­pyridine ligand acting as a spacer. A relevant feature of the structure is the presence of an unusually short Ag...Ag distance of 2.8306 (9) Å, well within the range of argentophilic inter­actions, confirmed experimentally as such by a Raman study on the low-frequency spectrum, and corroborated theoretically by an Atoms in Mol­ecules (AIM) analysis of the calculated electron density. Electrical conductivity measurements show that this complex can act as a semiconductor with moderate conductivity.Fil: Dennehy, Mariana. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Química del Sur. Universidad Nacional del Sur. Departamento de Química. Instituto de Química del Sur; ArgentinaFil: Amo Ochoa, Pilar. Universidad Autónoma de Madrid; EspañaFil: Freire Espeleta, Eleonora. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad Nacional de San Martín. Escuela de Ciencia y Tecnología; Argentina. Comisión Nacional de Energía Atómica. Centro Atómico Constituyentes; ArgentinaFil: Suarez, Sebastian. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Química Inorgánica, Analítica y Química Física; ArgentinaFil: Halac, Emilia. Comisión Nacional de Energía Atómica. Centro Atómico Constituyentes; Argentina. Universidad Nacional de San Martín. Escuela de Ciencia y Tecnología; ArgentinaFil: Baggio, Ricardo. Comisión Nacional de Energía Atómica. Centro Atómico Constituyentes; Argentin

The flexibility of CuI chains and the functionality of pyrazine-2-thiocarboxamide keys to obtaining new Cu(I)-I coordination polymers with potential use as photocatalysts for organic dye degradation

This research focuses on two interesting aspects in the synthesis of new coordination polymers (CPs) taking advantage of the lability of coordination bonds. The first is the use of multifunctional and flexible building blocks, such as pyrazine-2-thiocarboxamide (Pyrtca) and CuI, and the second is the modification of the synthetic conditions to expand the amount of different crystalline phases. This means that starting from the same building blocks, we can increase the number of compounds obtained and diversify their final properties, as well as their possible applications. Furthermore, Cu(I)-halogen coordination polymers have been extensively studied for a long time due to their interesting optoelectronic properties. However, despite being usually semiconductors, research related to their possible behavior as photocatalysts is almost non-existent. In this work, we present five compounds, four coordination compounds with formulas [CuI(Pyrtca)]n (CP1), [Cu3I3(Pyrtca)7] (2) [Cu2I2(Pyrtca)]n (CP4 and CP4′) and a transformation of the starting ligand to a cationic imidazole derivative (compound 3) where copper iodine serves as a catalyst. All the compounds have been characterized by different techniques including single-crystal X-ray diffraction. The antibacterial behavior of CP1 against E. Coli DH5, E. Coli BL21, and C. glabrata (CECT 1448), as well as their optoelectronic properties, are also discussed in the work. The value of the band gap obtained (1.91 eV) for the two-dimensional coordination polymer of formula [Cu2I2(Pyrtca)]n (CP4) allows us to study its behavior as a photocatalyst in the degradation of persistent dyes in water with interesting results, achieving a total degradation of Methylene Blue and Rhodamine B in 40 min under UV–visible lightThis work was supported by the Spanish Ministerio de Ciencia e Innovación (Agencia Estatal de Investigación) (MCIN/AEI/10.13039/501100011033; PID2019- 108028GB-C22 and TED2021-131132B-C22

Structural and theoretical study of copper(ii)-5-fluoro uracil acetate coordination compounds: Single-crystal to single-crystal transformation as possible humidity sensor

This paper describes the synthesis and characterization of seven different copper(II) coordination compounds, as well as the formation of a protonated ligand involving all compounds from the same reaction. Their synthesis required hydrothermal conditions, causing the partial in situ transformation of 5-fluoro uracil-1-acetic acid (5-FUA) into an oxalate ion (ox), as well as the protonation of the 4,4′-bipyridine (bipy) ligand through a catalytic process resulting from the presence of Cu(II) within the reaction. These initial conditions allowed obtaining the new coordination compounds [Cu2(5-FUA)2(ox)(bipy)]n·2n H2O (CP2), [Cu(5-FUA)2(H2O)(bipy)]n·2n H2O (CP3), as well as the ionic pair [(H2bipy)+2 2NO3−] (1). The mother liquor evolved rapidly at room temperature and atmospheric pressure, due to the change in concentration of the initial reagents and the presence of the new chemical species generated in the reaction process, yielding CPs [Cu(5-FUA)2(bipy)]n·3.5n H2O, [Cu3(ox)3(bipy)4]n and [Cu(ox)(bipy)]n. The molecular compound [Cu(5-FUA)2(H2O)4]·4H2O (more thermodynamically stable) ended up in the mother liquor after filtration at longer reaction times at 25 °C and 1 atm., cohabiting in the medium with the other crystalline solids in different proportions. In addition, the evaporation of H2O caused the single-crystal to single-crystal transformation (SCSC) of [Cu(5-FUA)2(H2O)(bipy)]n·2n H2O (CP3) into [Cu(5-FUA)2(bipy)]n·2n H2O (CP4). A theoretical study was performed to analyze the thermodynamic stability of the phases. The observed SCSC transformation also involved a perceptible color change, highlighting this compound as a possible water sensorPID2019-108028GB-C22, TED2021-131132B-C2

¿Pueden las aplicaciones educativas de los dispositivos móviles ayudar al desarrollo de las inteligencias múltiples?

En este artículo presentamos una propuesta práctica y concreta para abordar el desarrollo y potenciación de las inteligencias múltiples mediante el uso de aplicaciones educativas diseñadas para dispositivos móviles. La primera parte consistirá en describir el concepto y relevancia educativa de las inteligencias múltiples para luego considerar las ventajas de la incorporación de los dispositivos móviles y realizar una propuesta concreta de tres apps por cada una de las nueve inteligencias

Multistimuli Response Micro- and Nanolayers of a Coordination Polymer Based on Cu2I2 Chains Linked by 2-Aminopyrazine

This is the peer reviewed version of the following article: Conesa‐Egea, J., Gallardo‐Martínez, J., Delgado, S., Martínez, J. I., Gonzalez‐Platas, J., Fernández‐Moreira, V., ... & Amo‐Ochoa, P. Multistimuli Response Micro‐and Nanolayers of a Coordination Polymer Based on Cu2I2 Chains Linked by 2‐Aminopyrazine. Small 13.33 (2017): 1700965 , which has been published in final form at https://doi.org/10.1002/smll.201700965. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Use of Self-Archived VersionA nonporous laminar coordination polymer of formula [Cu2I2(2-aminopyrazine)]n is prepared by direct reaction between CuI and 2-aminopyrazine, two industrially available building blocks. The fine tuning of the reaction conditions allows obtaining [Cu2I2(2-aminopyrazine)]n in micrometric and nanometric sizes with same structure and composition. Interestingly, both materials show similar reversible thermo- and pressure-luminescent response as well as reversible electrical response to volatile organic solvents such as acetic acid. X-ray diffraction studies under different conditions, temperatures and pressures, in combination with theoretical calculations allow rationalizing the physical properties of this compound and its changes under physical stimuli. Thus, the emission dramatically increases when lowering the temperature, while an enhancement of the pressure produces a decrease in the emission intensity. These observations emerge as a direct consequence of the high structural flexibility of the Cu2I2 chains which undergo a contraction in Cu-Cu distances as far as temperature decreases or pressure increases. However, the strong structural changes observed under high pressure lead to an unexpected effect that produces a less effective Cu-Cu orbital overlapping that justifies the decrease in the intensity emission. This work shows the high potential of materials based on Cu2I2 chains for new applicationsThe authors thank financial support from the Spanish Ministerio de Economía y Competitividad (MAT2013-46502-C2-2P, MAT2016-77608-C3-1-P, MAT2016-75883-C2-2-P, MAT2010-20843-C02-01, MAT2016-75586-C4-4-P, CTQ2016-75816-C2-1P), also thank the scientific computing center (CCC) of the Autonoma University of Madrid for their time. J.I.M. acknowledges the financial support by the Ramón y Cajal Program of MINECO (Grant RYC-2015-17730) and the EU via the ERC-Synergy Program (Grant ERC-2013-SYG-610256 NANOCOSMOS

Micro and nano smart composite films based on copper-iodine coordination polymer as thermochromic biocompatible sensors

Herein is presented the preparation and characterization of a composite material obtained by the combination of nanosheets of a coordination polymer (CP) based on the copper(I)-I double chain with response to temperature and pressure with polylactic acid (PLA) as biodegradable organic matrix. The new films of composite materials are generated using a simple and low-cost method and can be created with long lateral dimensions and thicknesses ranging from a few microns to a few nanometers. Studies show that the new material maintains the optical response versus the temperature, while the elasticity and flexibility of the PLA totally quenches the response to pressure previously observed for the CP. This new material can act as a reversible sensor at low temperatures, thanks to the flexibility of the copper(I)-iodine chain that conforms the CP. The addition of CP to the PLA matrix reduces the elastic modulus and ultimate elongation of the organic matrix, although it does not reduce its tensile strengthThis article has been funded by the Spanish Ministerio de Economía y Competitividad (and the current Ministerio de Ciencia, Innovación y Universidades) (MAT2016-77608-C3-1-P, MAT2016-75883-C2-2-P, MAT2016-75586-C4-4-P, CTQ2016-75816-C2-1P). J.C.-E. acknowledges the financial support by the “FPI-MINECO” Program of MINECO (Grant BES-2015-071534