RT Journal Article
T1 Site-selective reversible Diels–Alder reaction between a biphenylene-based polyarene and a semiconductor surface
A1 Godlewski, Szymon
A1 Engelund, Mads
A1 Peña Gil, Diego
A1 Zuzak, Rafał
A1 Kawai, Hiroyo
A1 Kolmer, Marek
A1 Caeiro Rodríguez, Jorge
A1 Guitián Rivera, Enrique
A1 Vollhardt, K. Peter C.
A1 Sánchez-Portal, Daniel
A1 Szymonski, Marek
A1 Pérez Meirás, María Dolores
AB Understanding 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
PB Royal Society of Chemistry
SN 1463-9076
YR 2018
FD 2018-04-28
LK http://hdl.handle.net/10347/16994
UL http://hdl.handle.net/10347/16994
LA eng
NO Godlewski, 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
NO This work was supported by the FP7 FET-ICT ‘‘Planar Atomicand Molecular Scale devices’’ (PAMS) project (funded by theEuropean Commission under contract no. 610446), by thePolish Ministry for Science and Higher Education from financialresources for science in 2013–2017 granted for an internationalco-financed project (contract no. 2913/7.PR/2013/2) and by projectsCTQ2016-78157-R, MAT2016-78293-C6-3R and MAT2016-78293-C6-4R (AEI/FEDER, UE). EG, DP and DP are grateful for financialsupport from the Xunta de Galicia (Centro singular de investigacio´nde Galicia accreditation 2016–2019, ED431G/09) and theEuropean Union (European Regional Development Fund-ERDF).The STM experiments were carried out using equipment purchasedwith funding from the European Regional DevelopmentFund within the framework of the Polish Innovation EconomyOperational Program (contract no. POIG.02.01.00-12-023/08).MK acknowledges financial backing from the Foundation forPolish Science (FNP). HK is indebted to the A*STAR ComputationalResource Centre (A*CRC) for computational resourcesand backing. RZ appreciates the support received from KNOW (scholarship KNOW/59/SS/RZ/2016)
DS Minerva
RD 27 abr 2026