Tailoring Bicomponent Supramolecular Nanoporous Networks: Phase Segregation, Polymorphism, and Glasses at the Solid−Liquid Interface
2009 (English)In: Journal of the American Chemical Society, ISSN 0002-7863, E-ISSN 1520-5126, Vol. 131, no 36, 13062-13071 p.Article in journal (Refereed) Published
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 R 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 one- dimensional (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.
Place, publisher, year, edition, pages
American Chemical Society (ACS), 2009. Vol. 131, no 36, 13062-13071 p.
Physical Chemistry Condensed Matter Physics
IdentifiersURN: urn:nbn:se:liu:diva-85265DOI: 10.1021/ja9032428OAI: oai:DiVA.org:liu-85265DiVA: diva2:567753