Suchergebnisse

A new compound (1) formed by two antiparallelly disposed tetracyano thienoquinoidal units has been synthesized and studied by electrochemistry, UV/Vis-NIR, IR, EPR, and transient spectroscopy. Self-assembly of 1 on a Au(111) surface has been investigated by scanning tunneling microscopy. Experiments have been rationalized by quantum chemical calculations. 1 exhibits a unique charge distribution in its anionic form, with a gradient of charge yielding a neat molecular in-plane electric dipole momentum, which transforms out-of-plane after surface deposition due to twisted→folded conformational change and to partial charge transfer from Au(111). Intermolecular van der Waals interactions and antiparallel trapezoidal shape fitting lead to the formation of an optimal dense on Au(111) two-dimensional assembly of 1. ; The authors thank the Spanish Ministry of Science, Innovation and Universities MCIU (projects CTQ2017-83531-R, RED2018-102815-T, MAT2017-85089-C2-1-R), Centro de Excelencia Severo Ochoa grants (SEV-2016-0686, SEV-2015-0496 and FUNFUTURE CEX2019-000917-S) and the CAM (QUIMTRONIC-CM project Y2018/NMT-4783). We thank MINECO/FEDER of the Spanish Government (projects PGC2018-098533-B-100 and PID2019-109555GB-I00), the Eusko Jaurlaritza (Basque Government, project PIBA19-0004) and the Junta de Andalucía, Spain (UMA18FEDERJA057). We also thank the Research Central Services (SCAI) of the University of Málaga and the Donostia International Physics Center (DIPC) Computer Center. We thank Dr. Juwon Oh and Prof. Donhgo Kim from the Spectroscopy Laboratory for Functional π-electronic Systems and Department of Chemistry, Yonsei University in Korea for the generous gift of the TRIR and UV/Vis transient absorption spectroscopy data. ; Peer reviewed

Taming the magnetic anisotropy of lanthanides through coordination environments is crucial to take advantage of the lanthanides properties in thermally robust nanomaterials. In this work, the electronic and magnetic properties of Dy-carboxylate metal–organic networks on Cu(111) based on an eightfold coordination between Dy and ditopic linkers are inspected. This surface science study based on scanning probe microscopy and X-ray magnetic circular dichroism, complemented with density functional theory and multiplet calculations, reveals that the magnetic anisotropy landscape of the system is complex. Surface-supported metal–organic coordination is able to induce a change in the orientation of the easy magnetization axis of the Dy coordinative centers as compared to isolated Dy atoms and Dy clusters, and significantly increases the magnetic anisotropy. Surprisingly, Dy atoms coordinated in the metallosupramolecular networks display a nearly in-plane easy magnetization axis despite the out-of-plane symmetry axis of the coordinative molecular lattice. Multiplet calculations highlight the decisive role of the metal–organic coordination, revealing that the tilted orientation is the result of a very delicate balance between the interaction of Dy with O atoms and the precise geometry of the crystal field. This study opens new avenues to tailor the magnetic anisotropy and magnetic moments of lanthanide elements on surfaces. ; The ALBA synchrotron is acknowledged for providing beam time at BOREAS beamline (proposal number 2015091454). This project has received funding from the European Research Council (ERC, grant 766555) and Marie Sklodowska-Curie Actions (MSCA, project 894924) under the European Union's Horizon 2020 research and innovation programme. This work has been financed by the Spanish Ministerio de Economía, Industria y Competitividad (projects FIS2016-78591-C3-1-R, RTI2018-097895-B-C42, MAT2016-78293-C6-2-R, MAT2017-85089-C2-1-R, and PID2019-107338RB-C65); the Comunidad de Madrid (Projects S2013/MIT-2850, P2018/NMT4321, and S2018/NMT-4367); the European Regional Development Fund (ERDF) under the program Interreg V-A España-Francia-Andorra (Contract No. EFA 194/16 TNSI); and "Severo Ochoa" Programme for Centres of Excellence in R&D (grants SEV-2016-0686, and SEV-2017-0706).