Light-Induced Contraction/Expansion of 1D Photoswitchable Metallopolymer Monitored at the Solid-Liquid Interface

EL GARAH, Mohamed, BORRE, Etienne, CIESIELSKI, Artur, DIANAT, Arezoo, GUTIERREZ, Rafael, CUNIBERTI, Gianaurelio, BELLEMIN-LAPONNAZ, Stephane, MAURO, Matteo et SAMORI, Paolo, 2017. Light-Induced Contraction/Expansion of 1D Photoswitchable Metallopolymer Monitored at the Solid-Liquid Interface. Small [en ligne]. 20 octobre 2017. Vol. 13, n° 40pp. 1701790. [Consultésans date]. DOI 10.1002/smll.201701790. Consulté de : http://onlinelibrary.wiley.com.scd-rproxy.u-strasbg.fr/doi/10.1002/smll.201701790/fullThe use of a bottom-up approach to the fabrication of nanopatterned functional surfaces, which are capable to respond to external stimuli, is of great current interest. Herein, the preparation of light-responsive, linear supramolecular metallopolymers constituted by the ideally infinite repetition of a ditopic ligand bearing an azoaryl moiety and Co(II) coordination nodes is described. The supramolecular polymerization process is followed by optical spectroscopy in dimethylformamide solution. Noteworthy, a submolecularly resolved scanning tunneling microscopy (STM) study of the in situ reversible trans-to-cis photoisomerization of a photoswitchable metallopolymer that self-assembles into 2D crystalline patterns onto a highly oriented pyrolytic graphite surface is achieved for the first time. The STM analysis of the nanopatterned surfaces is corroborated by modeling the physisorbed species onto a graphene slab before and after irradiation by means of density functional theory calculation. Significantly, switching of the monolayers consisting of supramolecular Co(II) metallopolymer bearing trans-azoaryl units to a novel pattern based on cis isomers can be triggered by UV light and reversed back to the trans conformer by using visible light, thereby restoring the trans-based supramolecular 2D packing. These findings represent a step forward toward the design and preparation of photoresponsive “smart” surfaces organized with an atomic precision.1. .
Accès libre Peer reviewed
Version acceptée pour publication (post-print auteur)
Paternité - Pas d'utilisation commerciale [CC] [BY] [NC]
Auteurs Mohamed El Garah
Etienne Borre
Artur Ciesielski
Arezoo Dianat
Rafael Gutierrez
Gianaurelio Cuniberti
Stephane Bellemin-Laponnaz
Matteo Mauro
Paolo Samori
Unité de recherche du site

Institut de Science et d'Ingénierie Supramoléculaires - ISIS - UMR7006
Institut de Physique et Chimie des Matériaux de Strasbourg - IPCMS - UMR7504
URL éditeur http://onlinelibrary.wiley.com.scd-rproxy.u-strasbg.fr/doi/10.1002/smll.201701790/full
Langue

en
Volume

13
Numéro

40
Page de début

1701790
Date de première publication

2017-08-25
Date de parution

2017-10-20
ISSN

16136810
Titre de la source (revue, livre…)

Small
Résumé

The use of a bottom-up approach to the fabrication of nanopatterned functional surfaces, which are capable to respond to external stimuli, is of great current interest. Herein, the preparation of light-responsive, linear supramolecular
Show moreThe use of a bottom-up approach to the fabrication of nanopatterned functional surfaces, which are capable to respond to external stimuli, is of great current interest. Herein, the preparation of light-responsive, linear supramolecular metallopolymers constituted by the ideally infinite repetition of a ditopic ligand bearing an azoaryl moiety and Co(II) coordination nodes is described. The supramolecular polymerization process is followed by optical spectroscopy in dimethylformamide solution. Noteworthy, a submolecularly resolved scanning tunneling microscopy (STM) study of the in situ reversible trans-to-cis photoisomerization of a photoswitchable metallopolymer that self-assembles into 2D crystalline patterns onto a highly oriented pyrolytic graphite surface is achieved for the first time. The STM analysis of the nanopatterned surfaces is corroborated by modeling the physisorbed species onto a graphene slab before and after irradiation by means of density functional theory calculation. Significantly, switching of the monolayers consisting of supramolecular Co(II) metallopolymer bearing trans-azoaryl units to a novel pattern based on cis isomers can be triggered by UV light and reversed back to the trans conformer by using visible light, thereby restoring the trans-based supramolecular 2D packing. These findings represent a step forward toward the design and preparation of photoresponsive “smart” surfaces organized with an atomic precision.
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DOI 10.1002/smll.201701790
Éditeur

Wiley-VCH Verlag
Titre abrégé de la source

Small
Type de publication

ACL
Projet(s) de recherche ANR

Labex projects CSC (ANR-10-LABX-0026 CSC)
Projet(s) de recherche européen(s)

Marie Sklodowska-Curie project ITN project iSwitch (GA-642196)
Domaine

Chimie/Matériaux
Mots-clés

density functional theory (DFT)
functional surfaces
metallopolymers
photoswitches
scanning tunneling microscopy (STM)
Unité de recherche extérieure au site

Institute for Materials Science and Max Bergmann Center of Biomaterials; Dresden University of Technology; 01062 Dresden Germany
Fonction

aut
crp
Identifiant ORCID orcid.org/0000-0001-6256-8281
Audience

International