TY - JOUR
T1 - Tailoring bicomponent supramolecular nanoporous networks
T2 - Phase segregation, polymorphism, and glasses at the solid-liquid interface
AU - Palma, C.-A.
AU - Samorí, P.
AU - Bjork, J.
AU - Dyer, M.S.
AU - Persson, M.
AU - Bonini, M.
AU - Llanes-Pallas, A.
AU - Bonifazi, D.
N1 - Publication code : RES. ACAD.
PY - 2009/9/16
Y1 - 2009/9/16
N2 - 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.
AB - 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.
UR - http://www.scopus.com/inward/record.url?scp=70349150982&partnerID=8YFLogxK
U2 - 10.1021/ja9032428
DO - 10.1021/ja9032428
M3 - Article
SN - 1520-5126
VL - 131
SP - 13062
EP - 13071
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
ER -