Self-Assembled Multilayers of Transition-Metal−Terpyridinyl Complexes; Formation, and Characterization

Abstract

Layer-by-layer (LBL) growth of terpyridinyl ligands with a range of metal ions is reported. Monolayers of mercaptophenyl terpyridine on gold were used to initiate LBL assembly by complexing the first layer of metal ions. Tetra-2-pyridinylpyrazine was used as a linking ligand between subsequent metal ion layers. The assembly of the terpyridines with 21 different metals was evaluated using UV absorbance spectroscopy, variable-angle spectroscopic ellipsometry, and atomic force microscopy. Successful LBL growth appears to depend on the ionic radius of the metal ion. Metals that formed multilayered LBL structures were primarily limited to a small range of effective ionic radii between 66 and 73 pm. Metal ions with smaller ionic radii usually formed initial layers but seldom exhibited consistent LBL growth, while ions with radii larger than 73 nm generally did not demonstrate any evidence of LBL growth.

Interfacial Behavior and Film Patterning of Redox‐Active Cationic Copper(II)‐Containing Surfactants

“…This interaction leads to redox, [4] optical, [5,6] and magnetic [7] behavior and distinctive order, and has been explored thus far in thixotropic, [8] mesogenic, [9] and micellar [10] design. Although self-assembly remains the chief approach for film formation, [11][12][13] isothermal compression [14] allows for greater control over the final morphology. [15,16] This characteristic is fundamental for device nanofabrication, but only in the recent past has the design of amphiphilic precursors departed from lipids to encompass alkylamines, [17] polymers and copolymers, [18] and dendrimers [19] within its subjects.…”

Ruthenium–amine complexation for constructing self-assembled molecular films

“…This approach can be conducted in the reversal manner as well: A metal ion layer is first deposited on a substrate, and then ligand molecules are coordinated onto the substrate. In these processes, surface-coordination chemistry is an effective principle to promote self-assembling monolayers and multilayers, and a number of reports have been published in this field regarding, for example, phosphonic acid-metal ion [15][16][17][18][19][20][21][22], carboxylic acid-metal ion [23,24], and 3 amine-metal ion [25][26][27] systems.…”

The first complex of 4′-(4-methylthiophenyl)-2,2′:6′,2″-terpyridine – A model for terpylated self-assembled monolayers

“…The {M(tpy) 2 } n+ motif (tpy = 2,2 0 :6 0 ,2 00 -terpyridine) is one of the most popular metallosupramolecular strategies for the specific introduction of metal centres into supramolecular assemblies and devices and numerous examples of structural motifs functionalised with tpy (terpylation) have been reported [3][4][5][6]. We recently described the preparation and coordination behaviour of 2,2 0 :6 0 ,2 00 -terpyridine-4 0 (1 0 H)-thione (1) [7] and the formation of self-assembled monolayers of 1 and the related compounds 2 and 3 (Scheme 1) on gold has been reported [8][9][10][11][12]. Although the complexation of 3 on gold surfaces or gold nanoparticles has been reported, no complexes of 2 or 3 have been characterised.…”