Odd or even? Monolayer domain size depends on diyne position in alkadiynylanthracenes.
1,5-(Alkadiynyl)anthracenes self-assemble single component and multicomponent monolayers at the solution-HOPG interface. An alkadiynyl chain's kinked shape constrains the molecular structures with which it can close-pack. This affords rudimentary molecular recognition that has been used to direct self-assembly of 1-D patterned, multicomponent monolayers. The unit cell building blocks of single- and multicomponent alkadiynylanthracene monolayers repeat with high fidelity for 100s of nanometers along the side chain direction. Unit cell repeat fidelity along the orthogonal, anthracene column direction of the monolayer depends on diyne location within the side chain; even-position diyne side chains produce high fidelity of unit cell repeats and wider domain widths along the anthracene columns, whereas odd-position diyne side chains produce more frequent domain interfaces that disrupt the anthracene columns. Alkadiynylanthracene monolayers may be viewed as stacks of 1-D molecular tapes. 1-D tape molecular composition, sequence, and intratape side chain alignment are dictated by shape complementarity of the kinked alkadiynyl side chains. Stacking alignments of adjacent 1-D tapes are controlled by shape matching of tape peripheries and determine repeat fidelity along the anthracene columns. Tapes stacked with a constant intertape alignment comprise crystalline domains that repeat along the anthracene columns. The 1-D tapes formed by anthracenes with odd-position diynes have triangle wave peripheries that close-pack in multiple stacking alignments. This reduces unit cell repeat fidelity and decreases the widths of crystalline domains along the anthracene columns. Even-position diyne side chains form 1-D tapes with trapezoid wave peripheries that close-pack in only one stacking alignment. This generates higher stacking fidelity, larger domain widths, and fewer domain interfaces along the anthracene columns of even-position diyne monolayers. Even- and odd-position diyne monolayers exhibit comparable densities of interfaces between enantiotopic domains and between domains aligned along different graphite symmetry axes. These interfaces likely arise through collisions of independently nucleated/growing domains and persist for lack of kinetically competent pathways that interconvert or merge the domains.
Department of Chemistry, Brown University , Providence, Rhode Island 02912, United States.
Yi
Y
Xue
Min Kyoung
MK
Kim
Tereza
T
Pašková
Matthew B
MB
Zimmt