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dc.contributor.authorGodlewski, Szymon
dc.contributor.authorEngelund, Mads
dc.contributor.authorPeña Gil, Diego
dc.contributor.authorZuzak, Rafał
dc.contributor.authorKawai, Hiroyo
dc.contributor.authorKolmer, Marek
dc.contributor.authorCaeiro Rodríguez, Jorge
dc.contributor.authorGuitián Rivera, Enrique
dc.contributor.authorVollhardt, K. Peter C.
dc.contributor.authorSánchez-Portal, Daniel
dc.contributor.authorSzymonski, Marek
dc.contributor.authorPérez Meirás, María Dolores
dc.identifier.citationGodlewski, S., Engelund, M., Peña, D., Zuzak, R., Kawai, H., & Kolmer, M. et al. (2018). Site-selective reversible Diels–Alder reaction between a biphenylene-based polyarene and a semiconductor surface. Physical Chemistry Chemical Physics, 20(16), 11037-11046. doi: 10.1039/c8cp01094c
dc.description.abstractUnderstanding the mechanisms involved in the covalent attachment of organic molecules to surfaces is a major challenge for nanotechnology and surface science. On the basis of classical organic chemistry mechanistic considerations, key issues such as selectivity and reactivity of the organic adsorbates could be rationalized and exploited for the design of molecular-scale circuits and devices. Here we use tris(benzocyclobutadieno)triphenylene, a singular Y-shaped hydrocarbon containing antiaromatic cyclobutadienoid rings, as a molecular probe to study the reaction of polycyclic conjugated molecules with atomic scale moieties, dangling-bond (DB) dimers on a hydrogen-passivated Ge(001):H surface. By combining molecular design, synthesis, scanning tunneling microscopy and spectroscopy (STM/STS) and computational modeling, we show that the attachment involves a concerted [4+2] cycloaddition reaction that is completely site-selective and fully reversible. This selectivity, governed by the bond alternation induced by the presence of the cyclobutadienoid rings, allows for the control of the orientation of the molecules with respect to the surface DB-patterning. We also demonstrate that by judicious modification of the electronic levels of the polycyclic benzenoid through substituents, the reaction barrier height can be modified. Finally, we show that after deliberate tip-induced covalent bond cleavage, adsorbed molecules can be used to fine tune the electronic states of the DB dimer. This power to engineer deliberately the bonding configuration and electronic properties opens new perspectives for creating prototypical nanoscale circuitry
dc.description.sponsorshipThis work was supported by the FP7 FET-ICT ‘‘Planar Atomic and Molecular Scale devices’’ (PAMS) project (funded by the European Commission under contract no. 610446), by the Polish Ministry for Science and Higher Education from financial resources for science in 2013–2017 granted for an international co-financed project (contract no. 2913/7.PR/2013/2) and by projects CTQ2016-78157-R, MAT2016-78293-C6-3R and MAT2016-78293- C6-4R (AEI/FEDER, UE). EG, DP and DP are grateful for financial support from the Xunta de Galicia (Centro singular de investigacio´n de Galicia accreditation 2016–2019, ED431G/09) and the European Union (European Regional Development Fund-ERDF). The STM experiments were carried out using equipment purchased with funding from the European Regional Development Fund within the framework of the Polish Innovation Economy Operational Program (contract no. POIG.02.01.00-12-023/08). MK acknowledges financial backing from the Foundation for Polish Science (FNP). HK is indebted to the A*STAR Computational Resource Centre (A*CRC) for computational resources and backing. RZ appreciates the support received from KNOW (scholarship KNOW/59/SS/RZ/2016)
dc.publisherRoyal Society of Chemistry
dc.relationinfo:eu-repo/grantAgreement/MINECO/Plan Estatal de Investigación Científica y Técnica y de Innovación 2013-2016/CTQ2016-78157-R/ES
dc.rights© The Royal Society of Chemistry 2018
dc.titleSite-selective reversible Diels–Alder reaction between a biphenylene-based polyarene and a semiconductor surface
dc.contributor.affiliationUniversidade de Santiago de Compostela. Centro de Investigación en Química Biolóxica e Materiais Moleculares
dc.contributor.affiliationUniversidade de Santiago de Compostela. Departamento de Química Orgánica

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