Dipolar Control of Monolayer Morphology:  Spontaneous SAM Patterning

Abstract

A strategy for controlling relative placements of molecules within multicomponent monolayers at the solution-HOPG interface is demonstrated. The monolayers assemble from complementary pairs of 1,5-bis-alkyldiether-anthracenes bearing self-repelling side chains. Each diether side chain suffers repulsive dipolar interactions if it adsorbs next to an identical side chain in the morphology normally assumed by 1,5-bis-substituted-anthracene monolayers. Complementary side-chain pairs experience attractive dipolar interactions when adsorbed as neighbors in the normal morphology monolayer. The repulsive and attractive forces spontaneously drive formation of a patterned monolayer at the solution-HOPG interface. Each molecule adsorbs in its own row, sandwiched between two rows of the complementary anthracene. These studies demonstrate the viability of using weak dipolar interactions to control molecular placement and monolayer morphology and to pattern multicomponent monolayers.

Oligomeric Tectonics: Supramolecular Assembly of Double‐Stranded Oligobisnorbornene through π–π Stacking

“…The fact that, even in the high resolution images of Figure 4, no interstices can be found to pinpoint the termini of 1 in the assembly suggests a conformal contact through multiple interactions of p-p stacking and/or dipole-dipole attractions. This rationale is supported by recent studies by Wei et al [71][72][73][74] and Tahara and co-workers, [75] who showed that dipolar interactions provide directionality and stabilize a two-dimensional molecular pattern on a solid surface.…”

Living on the edge: Tuning supramolecular interactions to design two-dimensional organic crystals near the boundary of two stable structural phases

“…18 For example, alkyl chains play an important role in self-assembly at the solution-solid interface in assisting adsorption and by directing assembly. [19][20][21][22] The role of dipolar functional groups positioned at the periphery of a molecule, [23][24][25][26][27][28] the anti-parallel alignment of zwitterions on surfaces, [29][30][31] and the impact of molecular dipoles 32,33 in supramolecular self-assembly at surfaces have been studied. While these types of contacts have been extensively examined in surface-adsorbed crystals, [34][35][36] the challenge now lies in balancing the weights of their relative contributions to generate bi-phasic systems.…”

Reactive capture of gold nanoparticles by strongly physisorbed monolayers on graphite

“…Thus, key challenges to reliable AuNP capture by physisorbed monolayers include (i) ensuring monolayer molecules adhere sufficiently tightly to preclude dissociation during AuNP incubation, sample drying and processing and (ii) forming strong, selective links to capture and hold NP. Anthracenes and their Diels-Alder adducts (DAa) bearing aliphatic side chains at the 1-and 5-positions (Chart 1) form crystalline and co-crystalline monolayers at the solution -HOPG interface [43][44][45][46][47][48][49]. The DAa and anthracene cores assemble in linear columns that alternate with alkyl columns assembled from tightly packed, aliphatic side chains (Scheme 1).…”