18 research outputs found
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.; GarcĂa GĂłmez, 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., OâKeeffe, 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). Gas/vapour separation using ultra-microporous metalâorganic frameworks: insights into the structure/separation relationship. Chemical Society Reviews, 46(11), 3402-3430. doi:10.1039/c7cs00153cHowarth, A. J., Liu, Y., Li, P., Li, Z., Wang, T. C., Hupp, J. T., & Farha, O. K. (2016). Chemical, thermal and mechanical stabilities of metalâorganic frameworks. Nature Reviews Materials, 1(3). doi:10.1038/natrevmats.2015.18Colombo, V., Galli, S., Choi, H. J., Han, G. D., Maspero, A., Palmisano, G., ⊠Long, J. R. (2011). High thermal and chemical stability in pyrazolate-bridged metalâorganic frameworks with exposed metal sites. Chemical Science, 2(7), 1311. doi:10.1039/c1sc00136aPark, K. S., Ni, Z., Cote, A. P., Choi, J. Y., Huang, R., Uribe-Romo, F. J., ⊠Yaghi, O. M. (2006). Exceptional chemical and thermal stability of zeolitic imidazolate frameworks. Proceedings of the National Academy of Sciences, 103(27), 10186-10191. doi:10.1073/pnas.0602439103Cavka, J. H., Jakobsen, S., Olsbye, U., Guillou, N., Lamberti, C., Bordiga, S., & Lillerud, K. P. (2008). A New Zirconium Inorganic Building Brick Forming Metal Organic Frameworks with Exceptional Stability. Journal of the American Chemical Society, 130(42), 13850-13851. doi:10.1021/ja8057953Devic, T., & Serre, C. (2014). High valence 3p and transition metal based MOFs. Chem. Soc. Rev., 43(16), 6097-6115. doi:10.1039/c4cs00081aBai, Y., Dou, Y., Xie, L.-H., Rutledge, W., Li, J.-R., & Zhou, H.-C. (2016). Zr-based metalâorganic frameworks: design, synthesis, structure, and applications. Chemical Society Reviews, 45(8), 2327-2367. doi:10.1039/c5cs00837aAssi, H., Mouchaham, G., Steunou, N., Devic, T., & Serre, C. (2017). Titanium coordination compounds: from discrete metal complexes to metalâorganic frameworks. Chemical Society Reviews, 46(11), 3431-3452. doi:10.1039/c7cs00001dDan-Hardi, M., Serre, C., Frot, T., Rozes, L., Maurin, G., Sanchez, C., & FeÌrey, G. (2009). A New Photoactive Crystalline Highly Porous Titanium(IV) Dicarboxylate. Journal of the American Chemical Society, 131(31), 10857-10859. doi:10.1021/ja903726mGao, J., Miao, J., Li, P.-Z., Teng, W. Y., Yang, L., Zhao, Y., ⊠Zhang, Q. (2014). A p-type Ti(iv)-based metalâorganic framework with visible-light photo-response. Chem. Commun., 50(29), 3786-3788. doi:10.1039/c3cc49440cBueken, B., Vermoortele, F., Vanpoucke, D. E. P., Reinsch, H., Tsou, C.-C., Valvekens, P., ⊠De Vos, D. (2015). A Flexible Photoactive Titanium Metal-Organic Framework Based on a [TiIV3(ÎŒ3-O)(O)2(COO)6] Cluster. Angewandte Chemie International Edition, 54(47), 13912-13917. doi:10.1002/anie.201505512Bueken, B., Vermoortele, F., Vanpoucke, D. E. P., Reinsch, H., Tsou, C.-C., Valvekens, P., ⊠De Vos, D. (2015). A Flexible Photoactive Titanium Metal-Organic Framework Based on a [TiIV3(ÎŒ3-O)(O)2(COO)6] Cluster. Angewandte Chemie, 127(47), 14118-14123. doi:10.1002/ange.201505512Yuan, S., Liu, T.-F., Feng, D., Tian, J., Wang, K., Qin, J., ⊠Zhou, H.-C. (2015). A single crystalline porphyrinic titanium metalâorganic framework. Chemical Science, 6(7), 3926-3930. doi:10.1039/c5sc00916bYuan, S., Qin, J.-S., Xu, H.-Q., Su, J., Rossi, D., Chen, Y., ⊠Zhou, H.-C. (2017). [Ti8Zr2O12(COO)16] Cluster: An Ideal Inorganic Building Unit for Photoactive MetalâOrganic Frameworks. ACS Central Science, 4(1), 105-111. doi:10.1021/acscentsci.7b00497Dhakshinamoorthy, A., Asiri, A. M., & GarcĂa, H. (2016). Metal-Organic Framework (MOF) Compounds: Photocatalysts for Redox Reactions and Solar Fuel Production. Angewandte Chemie International Edition, 55(18), 5414-5445. doi:10.1002/anie.201505581Dhakshinamoorthy, A., Asiri, A. M., & Garcia, H. (2016). Metall-organische GerĂŒstverbindungen: Photokatalysatoren fĂŒr Redoxreaktion und die Produktion von Solarbrennstoffen. Angewandte Chemie, 128(18), 5504-5535. doi:10.1002/ange.201505581Deng, X., Li, Z., & GarcĂa, H. (2017). Visible Light Induced Organic Transformations Using Metal-Organic-Frameworks (MOFs). Chemistry - A European Journal, 23(47), 11189-11209. doi:10.1002/chem.201701460Horiuchi, Y., Toyao, T., Saito, M., Mochizuki, K., Iwata, M., Higashimura, H., ⊠Matsuoka, M. (2012). Visible-Light-Promoted Photocatalytic Hydrogen Production by Using an Amino-Functionalized Ti(IV) MetalâOrganic Framework. The Journal of Physical Chemistry C, 116(39), 20848-20853. doi:10.1021/jp3046005Hendon, C. H., Tiana, D., Fontecave, M., Sanchez, C., Dâarras, L., Sassoye, C., ⊠Walsh, A. (2013). Engineering the Optical Response of the Titanium-MIL-125 MetalâOrganic Framework through Ligand Functionalization. Journal of the American Chemical Society, 135(30), 10942-10945. doi:10.1021/ja405350uChambers, M. B., Wang, X., Ellezam, L., Ersen, O., Fontecave, M., Sanchez, C., ⊠Mellot-Draznieks, C. (2017). Maximizing the Photocatalytic Activity of MetalâOrganic Frameworks with Aminated-Functionalized Linkers: Substoichiometric Effects in MIL-125-NH2. Journal of the American Chemical Society, 139(24), 8222-8228. doi:10.1021/jacs.7b02186Blatov, V. A., Shevchenko, A. P., & Proserpio, D. M. (2014). Applied Topological Analysis of Crystal Structures with the Program Package ToposPro. Crystal Growth & Design, 14(7), 3576-3586. doi:10.1021/cg500498kDelgado-Friedrichs, O., & OâKeeffe, M. (2003). Identification of and symmetry computation for crystal nets. Acta Crystallographica Section A Foundations of Crystallography, 59(4), 351-360. doi:10.1107/s0108767303012017DincÄ, M., Han, W. S., Liu, Y., Dailly, A., Brown, C. M., & Long, J. R. (2007). Observation of Cu2+âH2 Interactions in a Fully Desolvated Sodalite-Type MetalâOrganic Framework. Angewandte Chemie International Edition, 46(9), 1419-1422. doi:10.1002/anie.200604362DincÄ, M., Han, W. S., Liu, Y., Dailly, A., Brown, C. M., & Long, J. R. (2007). Observation of Cu2+âH2 Interactions in a Fully Desolvated Sodalite-Type MetalâOrganic Framework. Angewandte Chemie, 119(9), 1441-1444. doi:10.1002/ange.200604362Liu, T.-F., Vermeulen, N. A., Howarth, A. J., Li, P., Sarjeant, A. A., Hupp, J. T., & Farha, O. K. (2016). Adding to the Arsenal of Zirconium-Based Metal-Organic Frameworks: the
Topology as a Platform for Solvent-Assisted Metal Incorporation. European Journal of Inorganic Chemistry, 2016(27), 4349-4352. doi:10.1002/ejic.201600627Wang, B., Lv, X.-L., Feng, D., Xie, L.-H., Zhang, J., Li, M., ⊠Zhou, H.-C. (2016). Highly Stable Zr(IV)-Based MetalâOrganic Frameworks for the Detection and Removal of Antibiotics and Organic Explosives in Water. Journal of the American Chemical Society, 138(19), 6204-6216. doi:10.1021/jacs.6b01663Tan, Y.-X., He, Y.-P., & Zhang, J. (2011). Pore partition effect on gas sorption properties of an anionic metalâorganic framework with exposed Cu2+ coordination sites. Chemical Communications, 47(38), 10647. doi:10.1039/c1cc14118jZou, L., Feng, D., Liu, T.-F., Chen, Y.-P., Yuan, S., Wang, K., ⊠Zhou, H.-C. (2016). A versatile synthetic route for the preparation of titanium metalâorganic frameworks. Chem. Sci., 7(2), 1063-1069. doi:10.1039/c5sc03620hSantaclara, J. G., Kapteijn, F., Gascon, J., & van der Veen, M. A. (2017). Understanding metalâorganic frameworks for photocatalytic solar fuel production. CrystEngComm, 19(29), 4118-4125. doi:10.1039/c7ce00006eCremades, E., EcheverrĂa, J., & Alvarez, S. (2010). The Trigonal Prism in Coordination Chemistry. Chemistry - A European Journal, 16(34), 10380-10396. doi:10.1002/chem.200903032Brozek, C. K., & DincÄ, M. (2013). Ti3+-, V2+/3+-, Cr2+/3+-, Mn2+-, and Fe2+-Substituted MOF-5 and Redox Reactivity in Cr- and Fe-MOF-5. Journal of the American Chemical Society, 135(34), 12886-12891. doi:10.1021/ja406447
2D Cu(I)âI 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 InvestigaciĂłn (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 âProyectos SinĂ©rgicos de I + Dâ (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
International audienc
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 InnovaciĂłn (PI201060E013) is also acknowledged.Peer Reviewe
Equation of state and structural characterization of Cu 4 I 4 {PPh 2 (CH 2 CHâ=âCH 2 )} 4 under pressure
International audienc
Effect of linker distribution in the photocatalytic activity of multivariate mesoporous crystals
The use of MetalâOrganic 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 coreâshell 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 SkĆodowska-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 KâČ0 = 7.7(6) for the bromide compound and K0 = 13.0(2) GPa and KâČ0 = 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 CuâCu 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 leaderâs perceptions of the preservation of ethics in their professional role
Syftet med denna magisteravhandling Àr att nÄ en djupare förstÄelse av vad ett etiskt ledarskap inom hÀlso- och sjukvÄrden innebÀr. StrÀvan Àr att belysa hur vÄrdledare kan slÄ vakt om etiken som en del av sin yrkesroll och bana vÀg för ett etiskt ledarskap. Magisteravhandlingens frÄgestÀllningar Àr: 1. Vad innebÀr ett etiskt ledarskap inom hÀlso- och sjukvÄrden? 2. Hur kan ledaren inom hÀlso- och sjukvÄrden slÄ vakt om etiken och försvara den som en del av sin yrkesroll och vÀrdegrund? Centrala begrepp för avhandlingen Àr etik, ledarskap, mÀnniskan och hermeneutik.
Magisteravhandlingen baserar sig pĂ„ den caring science-tradition som utvecklats vid enheten för vĂ„rdvetenskap pĂ„ Ă
bo Akademi i Vasa. NÀrmelsesÀttet Àr kvalitativt och avhandlingen Àr hermeneutisk till sin natur. Materialet bestÄr av intervjuer med ledare inom hÀlso- och sjukvÄrden och intervjutexterna har tolkats genom en kvalitativ innehÄllsanalys, inspirerad av hermeneutisk lÀsning.
Analysen av intervjutexterna resulterade i ett huvudtema med sex underteman. En central tanke för alla dessa Àr att etisk kompetens och etiskt kunnande hos ledaren Àr en förutsÀttning för att man skall kunna upprÀtthÄlla en god etik i verksamheten. UpprÀtthÄllandet av etiken ses som ett kontinuerligt arbete som krÀver tid och satsning, men medför mycket gott för sÄvÀl patienter som personal. Huvudtemat representeras av tanken att en Àkta medmÀnsklighet hos en nÀrvarande ledare synliggör etiken och lyfter upp medarbetarna och deras integritet. Ett etiskt helhetstÀnkande frÄn ledaren inbjuder till etisk reflektion och samtal kring etiken i arbetet. Denna öppenhet stÀrker sÄvÀl arbetsklimat som etiken i sig. Vikten av stöd och tilltro stiger fram som centrala för att de anstÀllda skall förmÄ tillÀmpa etiken i vardagen, vilket ses som avgörande för att ge etiken fotfÀste och genomslagskraft