Engineering 2D spin networks by on-surface encapsulation of azafullerene radicals in nanotemplates

Abstract We present an efficient strategy for on-surface engineering of organic metal-free supramolecular complexes with long-term spin protection. By vacuum deposition of azafullerene (C59N•) monomers on a pre-deposited template layer of [10]cycloparaphenylene ([10]CPP) nanohoops on Au(111) surface...

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Main Authors: Gregor Kladnik, Luca Schio, Gregor Bavdek, Yuri Tanuma, Marion van Midden Mavrič, Erik Zupanič, Bastien Anézo, Ioanna K. Sideri, Nikos Tagmatarchis, Jannis Volkmann, Hermann A. Wegner, Andrea Goldoni, Christopher P. Ewels, Alberto Morgante, Luca Floreano, Denis Arčon, Dean Cvetko
Format: Article
Language:English
Published: Nature Portfolio 2025-01-01
Series:Nature Communications
Online Access:https://doi.org/10.1038/s41467-024-55521-2
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author Gregor Kladnik
Luca Schio
Gregor Bavdek
Yuri Tanuma
Marion van Midden Mavrič
Erik Zupanič
Bastien Anézo
Ioanna K. Sideri
Nikos Tagmatarchis
Jannis Volkmann
Hermann A. Wegner
Andrea Goldoni
Christopher P. Ewels
Alberto Morgante
Luca Floreano
Denis Arčon
Dean Cvetko
author_facet Gregor Kladnik
Luca Schio
Gregor Bavdek
Yuri Tanuma
Marion van Midden Mavrič
Erik Zupanič
Bastien Anézo
Ioanna K. Sideri
Nikos Tagmatarchis
Jannis Volkmann
Hermann A. Wegner
Andrea Goldoni
Christopher P. Ewels
Alberto Morgante
Luca Floreano
Denis Arčon
Dean Cvetko
author_sort Gregor Kladnik
collection DOAJ
description Abstract We present an efficient strategy for on-surface engineering of organic metal-free supramolecular complexes with long-term spin protection. By vacuum deposition of azafullerene (C59N•) monomers on a pre-deposited template layer of [10]cycloparaphenylene ([10]CPP) nanohoops on Au(111) surface we exploit the molecular shape matching between the C59N• and [10]CPP for the azafullerene encapsulation with nanohoops in a guest-host complexation geometry. C59N•⊂[10]CPP supramolecular complexes self-assemble into an extended two-dimensional hexagonal lattice yielding a high density network of stable spin-1/2 radicals. We find compelling evidence for electronic coupling between the guest C59N• and the host [10]CPP in supramolecular species. At the same time, [10]CPP effectively protects the radical state of encapsulated azafullerenes against dimerization and inhibits C59N• coupling to the Au substrate. Azafullerene encapsulation by nanohoops represents a viable realization of molecular spin protection while simultaneously demonstrating exceptional self-assembling properties by which large-scale 2D architectures of molecular spins can be realized.
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spelling doaj-art-8d7b16f2600c444abc6fe2e8b224d9ac2025-01-05T12:41:11ZengNature PortfolioNature Communications2041-17232025-01-0116111010.1038/s41467-024-55521-2Engineering 2D spin networks by on-surface encapsulation of azafullerene radicals in nanotemplatesGregor Kladnik0Luca Schio1Gregor Bavdek2Yuri Tanuma3Marion van Midden Mavrič4Erik Zupanič5Bastien Anézo6Ioanna K. Sideri7Nikos Tagmatarchis8Jannis Volkmann9Hermann A. Wegner10Andrea Goldoni11Christopher P. Ewels12Alberto Morgante13Luca Floreano14Denis Arčon15Dean Cvetko16Faculty of Mathematics and Physics, University of LjubljanaCNR-IOM, Istituto Officina dei Materiali, Basovizza Area Science ParkCNR-IOM, Istituto Officina dei Materiali, Basovizza Area Science ParkJožef Stefan InstituteJožef Stefan InstituteJožef Stefan InstituteJožef Stefan InstituteTheoretical and Physical Chemistry Institute, National Hellenic Research FoundationTheoretical and Physical Chemistry Institute, National Hellenic Research FoundationInstitute of Organic Chemistry, Justus Liebig University GiessenInstitute of Organic Chemistry, Justus Liebig University GiessenElettra Sincrotrone Trieste S.C.p.A.Institut des Matériaux de Nantes Jean Rouxel (IMN), UMR 6502 CNRS, Nantes UniversityCNR-IOM, Istituto Officina dei Materiali, Basovizza Area Science ParkCNR-IOM, Istituto Officina dei Materiali, Basovizza Area Science ParkFaculty of Mathematics and Physics, University of LjubljanaFaculty of Mathematics and Physics, University of LjubljanaAbstract We present an efficient strategy for on-surface engineering of organic metal-free supramolecular complexes with long-term spin protection. By vacuum deposition of azafullerene (C59N•) monomers on a pre-deposited template layer of [10]cycloparaphenylene ([10]CPP) nanohoops on Au(111) surface we exploit the molecular shape matching between the C59N• and [10]CPP for the azafullerene encapsulation with nanohoops in a guest-host complexation geometry. C59N•⊂[10]CPP supramolecular complexes self-assemble into an extended two-dimensional hexagonal lattice yielding a high density network of stable spin-1/2 radicals. We find compelling evidence for electronic coupling between the guest C59N• and the host [10]CPP in supramolecular species. At the same time, [10]CPP effectively protects the radical state of encapsulated azafullerenes against dimerization and inhibits C59N• coupling to the Au substrate. Azafullerene encapsulation by nanohoops represents a viable realization of molecular spin protection while simultaneously demonstrating exceptional self-assembling properties by which large-scale 2D architectures of molecular spins can be realized.https://doi.org/10.1038/s41467-024-55521-2
spellingShingle Gregor Kladnik
Luca Schio
Gregor Bavdek
Yuri Tanuma
Marion van Midden Mavrič
Erik Zupanič
Bastien Anézo
Ioanna K. Sideri
Nikos Tagmatarchis
Jannis Volkmann
Hermann A. Wegner
Andrea Goldoni
Christopher P. Ewels
Alberto Morgante
Luca Floreano
Denis Arčon
Dean Cvetko
Engineering 2D spin networks by on-surface encapsulation of azafullerene radicals in nanotemplates
Nature Communications
title Engineering 2D spin networks by on-surface encapsulation of azafullerene radicals in nanotemplates
title_full Engineering 2D spin networks by on-surface encapsulation of azafullerene radicals in nanotemplates
title_fullStr Engineering 2D spin networks by on-surface encapsulation of azafullerene radicals in nanotemplates
title_full_unstemmed Engineering 2D spin networks by on-surface encapsulation of azafullerene radicals in nanotemplates
title_short Engineering 2D spin networks by on-surface encapsulation of azafullerene radicals in nanotemplates
title_sort engineering 2d spin networks by on surface encapsulation of azafullerene radicals in nanotemplates
url https://doi.org/10.1038/s41467-024-55521-2
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