Adsorption of alkanenitriles and alkanedinitriles on gold and copper

Abstract

Valeronitrile, heptadecanenitrile, nonadecanenitrile, heneicosanenitrile, malonodinitrile, succinodinitrile, glutarodinitrile, and tetradecanedinitrile adsorb on gold and copper from hexane or acetone solution or from the neat liquid. The adsorbed layers were analyzed by reflection infrared spectroscopy at grazing incidence, elUpsometry, contact angle measurements, surface profilometry, and X-ray photoelectron spectroscopy. The compounds with more than 10 methylene units form layers of a thickness of 6-8 A on copper and gold. The advancing contact angle of water on these layers is 90-94°; i.e. the wetting properties of these layers are very close to poly(ethylene) but different from poly(acrylonitrile) or monolayers of nitrile terminated alkanethiols. Valeronitrile behaves similar to long chain nitriles on gold, but on copper "multilayers" are formed (layer thickness up to ca. 1000 A). This is also observed for malonodinitrile and glutarodinitrile on copper. There is spectroscopic evidence for ^-bonded nitrile groups of some alkanenitriles and alkanedinitriles on copper.

Current–voltage characteristics of an LB monolayer of didecylammonium tricyanoquinodimethanide measured between macroscopic gold electrodes

“…The peak at 10 2927 cm -1 is due to CH 2 asymmetric stretch mode. In an all trans C-C alkane chain the CH 2 mode appears at 2920 cm -1 [21,22]. The higher frequency for CH 2 asymmetric stretch mode indicates that the decyl chains are in a liquid-like phase [21,22].…”

Self‐Assembled Monolayers on Electrodes

“…Less common are SAMs based on adsorption of isonitriles. 10,11 Chlorosilanes with long alkyl chains self-assemble on doped metal oxides such as SnO 2 , 12 silicon with a thin oxide coating 13 and even gold without any surface oxide. 14,15 Generation of alkane radicals near an oxide-free silicon surface results in the formation of a densely packed SAM in which a methylene carbon is directly bonded to a silicon surface atom.…”

Interaction between carboxylic modifiers and nanodispersed aluminium

“…The presence of nitrile groups in their chains can affect the value of chemisorption of rubbers on the aluminum surface. But according to Steiner et al [10], nitrile groups of macromolecules (in contrast to carboxyls) form predominantly coordination bonds with the metal surface.…”

“…According to Steiner et al [10], nitrile groups of macromolecules (in contrast to carboxyls) form predominantly coordination bonds with the metal surface. The absence of chemical interaction between the nitrile groups of rubber molecules and aluminum surface was confirmed by the reversible character of adsorption of butadiene-nitrile oligomer NR-1 (M n = 3000, acrylonitrile content is 18%) on the aluminium powder; unlike NR, molecules of this oligomer contain no end carboxyl groups.…”

“…The adsorption of electron-donor oxygen and nitrogen containing compounds is also accompanied by the formation of physical and chemical bonds with the surface [4][5][6]. Acetonitrile, long-chain alkane nitriles and alkane dinitriles are adsorbed on transition metals to form 2 -bonds thus being responsible for their horizontal surface coordination [9,10]. The character of polymer adsorption on the metal surface is also determined predominantly by the interaction between the active functional groups of macromolecules and adsorption sites of energetically heterogeneous surfaces of metals and their oxides [11].…”