Supramolecular effects in self-assembled monolayers: general discussion

Amabilino, David B.; Bâldea, Ioan; Batteas, James D.; Besenius, Pol; Beton, Peter H.; Buck, Manfred; Chi, Lifeng; Costantini, Giovanni; Davies, Philip R.; Feyter, Steven De; Fernandez, Yuri Diaz; Dwivedi, Deepak; Ernst, Karl‐Heinz; Flood, Amar H.; Hirsch, Brandon E.; Humblot, Vincent; Jones, Robert G.; Kühnle, Angelika; Lackinger, Markus; Lin, Nian; Linderoth, Trolle R.; Pradier, Claire‐Marie; Rahman, Talat S.; Raval, Rasmita; Robinson, Neil; Sacchi, Marco; Schwaminger, Sebastian P.; Tait, Steven L.; Woodruff, D.P.; Zuilhof, Han

doi:10.1039/c7fd90073b

Cited by 2 publications

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“…Disordered structures have been given little attention at the solution/solid interface. 33,34 With few exceptions, 35−40 macromolecular systems (e.g., proteins or polymers) and thin films, disordered packing and disorder/order transitions are essential for proper function. 41−49 In proteins, proper function depends on transitions between ordered/disordered structures and interactions between ordered/disordered domains.…”

Section: ■ Introductionmentioning

confidence: 99%

“…Disordered structures have been given little attention at the solution/solid interface. , With few exceptions, − the majority of systems studied to date have concentrated on neatly ordered structures and transitions between them. For macromolecular systems (e.g., proteins or polymers) and thin films, disordered packing and disorder/order transitions are essential for proper function. − In proteins, proper function depends on transitions between ordered/disordered structures and interactions between ordered/disordered domains. − In organic thin films, order/disorder transitions are observed with increasing dopant concentration .…”

Section: Introductionmentioning

confidence: 99%

“…To a lesser extent, molecular simulations have been used to gain novel molecular-level insights into solvent–adsorbate–surface interactions and processes that are not observable with experiment alone. Expanding our understanding of nanoscale supramolecular interactions and processes is essential in developing a deeper understanding of self-assembly. ,− …”

Section: Introductionmentioning

confidence: 99%

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Solution-Mediated Annealing Pathways Are Critical for Supramolecular Ordering of Complex Macrocycles at Surfaces

et al. 2020

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Self-organizations of supramolecular assemblies at surfaces typically achieve highly ordered two-dimensional packing structures due to the negotiation of various intermolecular interactions into a minimum free energy configuration. As we advance these systems toward the long-term goal of achieving programmable surface functionality, however, we consider systems of greater complexity in molecular building-block architecture and in growth conditions. Here, we study the polymorphic selfassembly of tricarbazolo triazolophane macrocycles (tricarb) at the solution/solid interface to determine the underlying pathway that tricarb follows when it transitions between two structures. Tricarb species, depending on peripheral functionalization, self-assemble into kinetically trapped disordered structures or thermodynamically favored ordered honeycomb structures. Experiments varying pre-and post-deposition conditions (solubility, concentration, and temperature) suggest that a solution-mediated annealing pathway, as opposed to an on-surface rearrangement, is key to a transition from disordered structures to honeycomb. Molecular dynamic simulations provide nanoscale insights into the roles of peripheral groups and solvent molecules in self-assembly. Substituents on the exterior of the molecule not only affect solubility but also stabilize tricarb−tricarb hydrogen-bonded structures. Peripheral groups influence the formation/re-formation and strength of adsorbate−adsorbate contacts and also limit solvent interactions about a macrocyclic core. The combination of simulation and experiment demonstrates the role of the solutionmediated annealing pathway in the self-assembly of complex supramolecular systems.

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Section: ■ Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Solution-Mediated Annealing Pathways Are Critical for Supramolecular Ordering of Complex Macrocycles at Surfaces

et al. 2020

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A sui generis electrode-driven spatial confinement effect responsible for strong twisting enhancement of floppy molecules in closely packed self-assembled monolayers

Bâldea

2018

Phys. Chem. Chem. Phys.

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At present, it is widely accepted that properties (e.g., molecular conformation) of molecules adsorbed to form self-assembled monolayers (SAMs) on electrodes can be very different from isolated species because of a substantial charge transfer or specific chemical bonding at the interface. Contrary to this view, the theoretical results presented here predict that the strong twisting angle (φ) enhancement of floppy molecules adsorbed to form densely packed SAMs on most common electrodes (Pt, Au, Ag, and Cu) is neither due to charge transfer nor to specific bonding but rather to a sui generis electrode-driven spatial confinement effect that can be quantitatively described within an electrode-free two-dimensional model. We predict a logistic ("Fermi-Dirac") growth pattern of φ as the coverage approaches the value characteristic of a herringbone arrangement, which is twice the value for isolated molecules or low-coverage SAMs.

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Supramolecular effects in self-assembled monolayers: general discussion

Cited by 2 publications

References 0 publications

Solution-Mediated Annealing Pathways Are Critical for Supramolecular Ordering of Complex Macrocycles at Surfaces

Solution-Mediated Annealing Pathways Are Critical for Supramolecular Ordering of Complex Macrocycles at Surfaces

A sui generis electrode-driven spatial confinement effect responsible for strong twisting enhancement of floppy molecules in closely packed self-assembled monolayers

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