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

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1701790

2017-08-25

2017-10-20

16136810

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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. Show less

Wiley-VCH Verlag

Small

ACL

Labex projects CSC (ANR-10-LABX-0026 CSC)

EC/H2020/642196///iSwitch

Chimie/Matériaux

density functional theory (DFT)
functional surfaces
metallopolymers
photoswitches
scanning tunneling microscopy (STM)

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

E4 - DMO : Département des matériaux organiques

aut
crp

International