How Equilibrium Gets Mimicked during Kinetic and Thermodynamic Control in Porphyrin and Phthalocyanine Self-Assembled Monolayers

Publication Type:
Journal Article
Langmuir, 2018, 34 (1), pp. 18 - 22
Issue Date:
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© 2017 American Chemical Society. The recent review of Hipps and Mazur is extended to consider the origins and significance of their conclusion that "surface structures vary with relative component concentration in a way that may mimic equilibria but is not". How this situation can arise during self-assembly is discussed, as well as a range of qualitative and quantitative observations and high-level free-energy calculations that document the effect for meso-tetraalkylporphyrins self-assembled monolayer (SAM) polymorphs. This leads to a discussion of modern challenges facing quantification of the effects caused by kinetic control, as well as to the usefulness of equilibrium mimicking in the design and synthesis of SAMs.
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