Self-assembled monolayers chemical reactions

A second class of monolayers based on van der Waal s interactions within the monolayer and chemisorption (in contrast with physisorption in the case of LB films) on a soHd substrate are self-assembled monolayers (SAMs). SAMs are well-ordered layers, one molecule thick, that form spontaneously by the reaction of molecules, typically substituted-alkyl chains, with the surface of soHd materials (193—195). A wide variety of SAM-based supramolecular stmctures have been generated and used as functional components of materials systems in a wide range of technological appHcations ranging from nanoHthography (196,197) to chemical sensing (198—201). 

Molecular monolayers made via solution phase chemical reactions with H/Si( 111) are often referred to as self-assembled monolayers on silicon... 

HiPCO-SWCNTs were oxidized in a UV-03 gas-solid interface reaction and subsequently assembled on a rigid oligo(phenylenethynylene) self-assembled monolayer (SAM). In a chemical assembly , based on condensation between the carboxylic acid functionalities of the 03-oxidized SWNTs and the amine functionalities of the SAMs, SWCNT-amides were formed in ordered arrays [116]. 

Scanning probe lithography on metal or silicon substrates is a well known technique and can be supported by a self-assembled monolayer (SAM) [1,2], Such monolayers are of great interest e.g. for passivation of silicon surfaces [3]. Covalently bound monolayers by Si-C bonds that are formed by the reaction of 1-alkenes and a hydrogen terminated silicon surface [4,5], are known to show high thermal [6] as well as chemical stability [3,7]. 

One of the interesting things about the redox polymers is their use in the creation of the molecular electronic devices.3-5 Redox polymer films on electrodes have been fabricated using chemical modification, electrochemical polymerization, polymer coating, and so on.88 Recently, stepwise complexation methods have been employed to fabricate multiple complex layers.89,90,91 In this section, the stepwise preparation of bis(tpy)metal polymer chains by combining terpyridine (tpy) ligand self-assembled monolayer (SAM) formation and metal-tpy coordination reactions is described as an example. This method realized the formation of a desired number of polymer units and a desired sequence of Co-Fe heterometal structures in the polymer chain.92... 

It is known, however, that isothiocyanates on their own can form stable self-assembled monolayers on gold (Section V.E), and amine-terminated monolayers were reported to show unusually low reactivity towards electrophilic reagents329,330. It is therefore possible that the observed immobilization of eosin is due not to reaction with amino groups, but to either insertion of the eosin isothiocyanate into a disordered layer of cysteamine, or even replacement of cysteamine monolayer with the molecules of S=C=N—eosin. Because the experimental data on reactions in gold-thiol monolayers are scarce, chemical transformations described in this section should be interpreted with some caution. 

---