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A Rotaxane Scaffold Bearing Multiple Redox Centers: Synthesis, Surface Modification and Electrochemical Properties
Author(s) -
Steffenhagen Marie,
Latus Alina,
Trinh Thi Minh Nguyet,
Nierengarten Iwona,
Lucas Ivan T.,
Joiret Suzanne,
Landoulsi Jessem,
DelavauxNicot Béatrice,
Nierengarten JeanFrançois,
Maisonhaute Emmanuel
Publication year - 2018
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201705245
Subject(s) - rotaxane , ferrocene , scanning tunneling microscope , cyclic voltammetry , surface modification , redox , chemistry , intramolecular force , electrochemistry , raman spectroscopy , molecule , materials science , nanotechnology , crystallography , photochemistry , electrode , stereochemistry , supramolecular chemistry , inorganic chemistry , organic chemistry , physics , optics
A rotaxane scaffold incorporating two dithiolane anchoring units for the modification of gold surfaces has been functionalized with multiple copies of a redox unit, namely ferrocene. Surface modification has been first assessed at the single molecule level by atomic force microscopy (AFM) and scanning tunneling microscopy (STM) imaging, while tip enhanced Raman spectroscopy (TERS) provided the local vibrational signature of the ferrocenyl subunits of the rotaxanes grafted onto the gold surface. Finally, oxidation of the redox moieties within a rotaxane scaffold grafted onto gold microelectrodes has been investigated by ultrafast cyclic voltammetry. Intramolecular electron hopping is indeed extremely fast in this system. Moreover, the kinetics of charge injection depends on the molecular coverage due to the influence of intermolecular contacts on molecular motions.