Symmetry and spacing controls in periodic covalent functionalization of graphite surfaces templated by self-assembled molecular networks

Abstract

We herein present the periodic covalent functionalization of graphite surfaces, creating a range of patterns of different symmetries and pitches at the nanoscale. Self-assembled molecular networks (SAMNs) of rhombic-shaped bis(dehydrobenzo[12]annulene)...

Spatially Controlled Aryl Radical Grafting of Graphite Surfaces Guided by Self-Assembled Molecular Networks of Linear Alkane Derivatives: The Importance of Conformational Dynamics

“…All STM observations were performed at 20–25 °C using Nanoscope IIID or V (Bruker AXS) with an external pulse/function generator (Agilent 33220A), or PicoSPM (Agilent Technologies) with negative sample bias. − STM tips were mechanically cut from Pt/Ir wire (80/20%, diameter 0.25 mm). All STM images were taken in a quasi-constant current mode.…”

“…OA was used as the solvent after distillation. The sample solution (20–40 μL) was added to a homemade liquid cell placed on a highly oriented pyrolytic graphite surface (HOPG, grade ZYB, Momentive Performance Material Quartz, Inc., Strongsville, OH). − We employed a liquid cell to minimize the effect of solvent evaporation. After annealing treatment at 80 °C for 3 h, the substrate was naturally cooled to room temperature.…”

“…Electrochemical treatments were performed using a homemade electrochemical (EC) Teflon cell and HZ-7000 (Hokuto DENKO). ,− Pt wire was used as the counter electrode, which was heated by a butane gas burner before use. Ag/AgCl (in 3 M NaCl aq.)…”

“…Raman spectra of the dried surfaces were measured using an XploRA PLUS Confocal Raman Microscope (HORIBA). A green ND:YAG laser beam (532 nm, 100 W) was irradiated to the sample surface through an objective lens (×50), − and the Raman scattering was corrected by the same objective and detected using a Peltier-type CCD detector (−60 °C, Syncerity, HORIBA Scientific). The measurement points (16 points) were located at 13.3 μm intervals in the x - and y -directions.…”

“…We recently reported a new concept for the spatio-controlled covalent modification of graphitic surfaces. In this approach, we use self-assembled molecular networks (SAMNs) at the interface between an organic liquid and the carbon surface as templating masks in the electrochemical grafting of aryldiazonium salts. − The advantage of this approach is the versatility in template symmetry, spacing, and chirality because of the large library of SAMNs. − While from a conceptual point of view, porous SAMNs are the natural choice, we discovered that high-density SAMNs also act as templates . Lamellar structures formed by linear alkanes ( n -C 30 H 62 , n -C 40 H 82 , and n -C 50 H 102 ) guide the aryl radical addition to the alkane terminal area producing linear rows of grafted molecules.…”