Chemical Engineering of Photoactivity in Heterometallic Titanium-Organic Frameworks by Metal Doping

[EN] We report a new family of titanium-organic frameworks that enlarges the limited number of crystalline, porous materials available for this metal. They are chemically robust and can be prepared as single crystals at multi-gram scale from multiple precursors. Their heterometallic structure enables engineering of their photoactivity by metal doping rather than by linker functionalization. Compared to other methodologies based on the post-synthetic metallation of MOFs, our approach is well-fitted for controlling the positioning of dopants at an atomic level to gain more precise control over the band-gap and electronic properties of the porous solid. Changes in the band-gap are also rationalized with computational modelling and experimentally confirmed by photocatalytic H-2 production.This work was supported by the EU (ERC Stg Chem-fs-MOF 714122) and Spanish MINECO (MDM-2015-0538, MAT2016-75586-C4-4-P & CTQ2017-83486-P). C.M.-G. and J.C.-G. thank the Spanish MINECO for a Ramon y Cajal Fellowship and FPI Scholarship (CTQ2014-59209-P), respectively. N.M.P. thanks the Junta de Andalucia for post-doctoral fellowship (P10-FQM-6050). BSC-RES and UG-Alhambra are acknowledged for the computational resources and F. Lloret for helpful discussions.Castells-Gil, J.; Padial, NM.; Almora-Barrios, N.; Albero-Sancho, J.; Ruiz-Salvador, AR.; Gonzalez-Platas, J.; García Gómez, H.... (2018). Chemical Engineering of Photoactivity in Heterometallic Titanium-Organic Frameworks by Metal Doping. Angewandte Chemie International Edition. 57(28):8453-8457. https://doi.org/10.1002/anie.201802089S845384575728Furukawa, H., Cordova, K. E., O’Keeffe, M., & Yaghi, O. M. (2013). The Chemistry and Applications of Metal-Organic Frameworks. Science, 341(6149), 1230444-1230444. doi:10.1126/science.1230444Adil, K., Belmabkhout, Y., Pillai, R. S., Cadiau, A., Bhatt, P. M., Assen, A. H., … Eddaoudi, M. (2017). 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2D Cu(I)‑I Coordination Polymer with Smart Optoelectronic Properties and Photocatalytic Activity as a Versatile Multifunctional Material

This work presents two isostructural Cu(I)-I 2-fluoropyrazine (Fpyz) luminescent and semiconducting 2D coordination polymers (CPs). Hydrothermal synthesis allows the growth of P-1 space group single crystals, whereas solvent-free synthesis produces polycrystals. Via recrystallization in acetonitrile, P21 space group single crystals are obtained. Both show a reversible luminescent response to temperature and pressure. Structure determination by single-crystal X-ray diffraction at 200 and 100 K allows us to understand their response as a function of temperature. Applying hydrostatic/uniaxial pressure or grinding also generates significant variations in their emission. The high structural flexibility of the Cu(I)-I chain is significantly linked to the corresponding alterations in structure. Remarkably, pressure can increase the conductivity by up to 3 orders of magnitude. Variations in resistivity are consistent with changes in the band gap energy. The experimental results are in agreement with the DFT calculations. These properties may allow the use of these CPs as optical pressure or temperature sensors. In addition, their behavior as a heterogeneous photocatalyst of persistent organic dyes has also been investigatedThanks to Micro and Nanotechnology Institute CNM-CSIC for SEM images. Thanks to the SCXRD laboratory of the Interdepartmental Research Service and to Servicios Generales de Apoyo a la Investigación (SEGAI) at La Laguna University. This work has been supported by MCINN/AEI/ 10.13039/ 5011000011033 under the National Program of Sciences and Technological Materials, PID2019-108028GB-C22, PID2019- 106383GB-C41/C44, and TED2021-131132B-C22. Thanks to Gobierno d e Canarias and EU-FEDER (grant: ProID2020010067). This study forms part of the Advanced Materials program and was supported by MCIN with funding from European Union Next Generation EU (PRTR-C17.I1) and by Generalitat Valenciana (grant MFA/2022/007 and PROMETEO CIPROM/2021/075-GREENMAT). A.L. (R.T.) and D.E. thank the Generalitat Valenciana for the Ph.D. (Postdoctoral) Fellowship No. GRISOLIAP/2019/025 (CIAPOS/2021/20). J.C.G. and R. W. acknowledge the support from the Spanish Ministry of Science and Innovation (RTI2018-097508-B-I00, PID2021-128313OB-I00, TED2021- 131018B-C22) and the Regional Government of Madrid through projects NMAT2D-CM (S2018/NMT-4511). J.C.G. acknowledges support from the Regional Government of Madrid through “Proyectos Sinérgicos de I + D” (grant Y2018/NMT-5028 FULMATEN-CM) and NANOCOV-CM (REACT-UE). IMDEA Nanociencia acknowledges support from the Severo Ochoa Programme for Centres of Excellence in R&D (MINECO, grant CEX2020-001039-S

Structural behaviour of copper(I) iodine compounds under high pressure

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Ab initio crystal structure determination of two chain functionalized pyrroles from synchrotron X-ray powder diffraction data

The crystal structure of two chain functionalized pyrroles, methyl 1-benzyl-5-(1-(4-chlorobenzoyloxy)-2-methoxy-2-oxoethyl)-4-(4-chlorophenyl)-1H-pyrrole-2-carboxylate and methyl 1-benzy1-4-(biphenyl-4-yl)-5-(1-(4-biphenylcarbonyloxy)-2-methoxy-2-oxoethyl)-1H-pyrrole-2-carboxylate, which are both important active candidates as antitumoral agents, have been obtained ab initio from synchrotron X-ray powder diffraction data. Both compounds crystallize in the monoclinic system (space group P2(1)/c), with a = 20.2544(3) angstrom, b = 6.80442(9) angstrom, c = 21.1981(3) angstrom, beta = 111.6388(9)degrees and a = 29.7747(6) angstrom, b = 6.27495(14) angstrom, c= 18.8525(3) angstrom, beta = 107.053(2)degrees, respectively. These structures were determined using a direct space approach, by means of Monte Carlo technique, followed by Rietveld refinement.The financial support from the Spanish Ministerio de Ciencia e Innovación (PI201060E013) is also acknowledged.Peer Reviewe

Equation of state and structural characterization of Cu 4 I 4 {PPh 2 (CH 2 CH = CH 2 )} 4 under pressure

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Effect of linker distribution in the photocatalytic activity of multivariate mesoporous crystals

The use of Metal–Organic Frameworks as crystalline matrices for the synthesis of multiple component or multivariate solids by the combination of different linkers into a single material has emerged as a versatile route to tailor the properties of single-component phases or even access new functions. This approach is particularly relevant for Zr6-MOFs due to the synthetic flexibility of this inorganic node. However, the majority of materials are isolated as polycrystalline solids, which are not ideal to decipher the spatial arrangement of parent and exchanged linkers for the formation of homogeneous structures or heterogeneous domains across the solid. Here we use high-throughput methodologies to optimize the synthesis of single crystals of UiO-68 and UiO-68-TZDC, a photoactive analogue based on a tetrazine dicarboxylic derivative. The analysis of the single linker phases reveals the necessity of combining both linkers to produce multivariate frameworks that combine efficient light sensitization, chemical stability, and porosity, all relevant to photocatalysis. We use solvent-assisted linker exchange reactions to produce a family of UiO-68-TZDC% binary frameworks, which respect the integrity and morphology of the original crystals. Our results suggest that the concentration of TZDC in solution and the reaction time control the distribution of this linker in the sibling crystals for a uniform mixture or the formation of core–shell domains. We also demonstrate how the possibility of generating an asymmetric distribution of both linkers has a negligible effect on the electronic structure and optical band gap of the solids but controls their performance for drastic changes in the photocatalytic activity toward proton or methyl viologen reduction.Financial support for this work was provided by the Marie Skłodowska-Curie Global Fellowships (749359-EnanSET, N.M.P) within the European Union research and innovation framework programme (2014-2020

Structural and Luminescence Properties of Cu(I)X-Quinoxaline under High Pressure (X = Br, I)

A study of high-pressure single-crystal X-ray diffraction and luminescence experiments together with ab initio simulations based on the density functional theory has been performed for two isomorphous copper(I) halide compounds with the empirical formula [C8H6Cu2X2N2] (X = Br, I) up to 4.62(4) and 7.00(4) GPa for X-ray diffraction and 6.3(4) and 11.6(4) GPa for luminescence, respectively. An exhaustive study of compressibility has been completed by means of determination of the isothermal equations of state and structural changes with pressure at room temperature, giving bulk moduli of K0 = 14.4(5) GPa and K′0 = 7.7(6) for the bromide compound and K0 = 13.0(2) GPa and K′0 = 7.4(2) for the iodide compound. Both cases exhibited a phase transition of second order around 3.3 GPa that was also detected in luminescence experiments under the same high-pressure conditions, wherein redshifts of the emission bands with increasing pressure were observed due to shortening of the Cu–Cu distances. Additionally, ab initio studies were carried out which confirmed the results obtained experimentally, although unfortunately, the phase transition was not predicted

Ethical leadership within health care : health care leader’s perceptions of the preservation of ethics in their professional role

Syftet med denna magisteravhandling är att nå en djupare förståelse av vad ett etiskt ledarskap inom hälso- och sjukvården innebär. Strävan är att belysa hur vårdledare kan slå vakt om etiken som en del av sin yrkesroll och bana väg för ett etiskt ledarskap. Magisteravhandlingens frågeställningar är: 1. Vad innebär ett etiskt ledarskap inom hälso- och sjukvården? 2. Hur kan ledaren inom hälso- och sjukvården slå vakt om etiken och försvara den som en del av sin yrkesroll och värdegrund? Centrala begrepp för avhandlingen är etik, ledarskap, människan och hermeneutik. Magisteravhandlingen baserar sig på den caring science-tradition som utvecklats vid enheten för vårdvetenskap på Åbo Akademi i Vasa. Närmelsesättet är kvalitativt och avhandlingen är hermeneutisk till sin natur. Materialet består av intervjuer med ledare inom hälso- och sjukvården och intervjutexterna har tolkats genom en kvalitativ innehållsanalys, inspirerad av hermeneutisk läsning. Analysen av intervjutexterna resulterade i ett huvudtema med sex underteman. En central tanke för alla dessa är att etisk kompetens och etiskt kunnande hos ledaren är en förutsättning för att man skall kunna upprätthålla en god etik i verksamheten. Upprätthållandet av etiken ses som ett kontinuerligt arbete som kräver tid och satsning, men medför mycket gott för såväl patienter som personal. Huvudtemat representeras av tanken att en äkta medmänsklighet hos en närvarande ledare synliggör etiken och lyfter upp medarbetarna och deras integritet. Ett etiskt helhetstänkande från ledaren inbjuder till etisk reflektion och samtal kring etiken i arbetet. Denna öppenhet stärker såväl arbetsklimat som etiken i sig. Vikten av stöd och tilltro stiger fram som centrala för att de anställda skall förmå tillämpa etiken i vardagen, vilket ses som avgörande för att ge etiken fotfäste och genomslagskraft