Tailoring bicomponent supramolecular nanoporous networks: Phase segregation, polymorphism, and glasses at the solid-liquid interface

C.-A. Palma, P. Samorí, J. Bjork, M.S. Dyer, M. Persson, M. Bonini, A. Llanes-Pallas, D. Bonifazi

Research output: Contribution to journalArticlepeer-review

Abstract

We study the formation of four supramolecular bicomponent networks based on four linear modules (linkers) bridging melamine via triple hydrogen-bonds. We explore at the nanoscale level the phenomena of polymorphism and phase segregation which rule the generation of highly crystalline nanoporous patterns self-assembled at the solid-liquid interface. The investigated linkers include two systems exposing diuracil groups in the α and ω position, naphthalene tetracarboxylic diimide and pyromellitic diimide. In situ scanning tunneling microscopy (STM) investigations revealed that, when blended with melamine, out of the four systems, three are able to form two-dimensional (2D) porous architectures, two of which exhibit highly ordered hexagonal structures, while pyromellitic diimide assembles only into onedimensional (1D) supramolecular arrays. These bicomponent self-assembled monolayers are used as a test bed to gain detailed insight into phase segregation and polymorphism in 2D supramolecular systems by exploring the contribution of hydrogen-bond energy and periodicity, molecular flexibility, concentration and ratio of the components in solution as well as the effect of annealing via time-dependent and temperature-modulated experiments. These comparative studies, obtained through a joint experimental and computational analysis, offer new insights into strategies toward the bottom-up fabrication of highly ordered tunable nanopatterning at interfaces mediated by hydrogen bonds. © 2009 American Chemical Society.
Original languageEnglish
Pages (from-to)13062-13071
Number of pages10
JournalJournal of the American Chemical Society
Volume131
DOIs
Publication statusPublished - 16 Sep 2009

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