Self-Assembly of Semifluorinated Minidendrons Attached to Electron-Acceptor Groups into Pyramidal Columns

The synthesis and self‐assembly of twelve semifluorinated first‐generation dendrons or minidendrons attached to electron‐acceptor (n‐type) groups generated from various combinations of eight acceptors and three dendrons are reported. Dendrons attached to small electron‐acceptor molecules mediate their self‐assembly into π‐stacks located in the center of a supramolecular helical pyramidal column with the long axis of the acceptor perpendicular to the long axis of the column. Dendrons attached to large electron‐acceptor molecules, such as perylene bisimide, mediate the assembly of their acceptors in an unprecedented arrangement of π‐stacks that have the long axis of the acceptors parallel to the long axis of the supramolecular pyramidal column. All supramolecular columns self‐organize into various periodic columnar arrays that exhibit liquid‐crystalline phases, crystalline phases, or a liquid‐crystalline phase with enhanced intracolumnar order. The present study demonstrates the simplicity and the versatility of the concept of assembly of n‐type electroactive groups mediated by semifluorinated dendrons and assesses the scope and limitations of this supramolecular strategy. Supramolecular pyramidal columns mediate the π‐stacking of the electron‐acceptor groups attached to the apex of self‐assembling semifluorinated dendrons (see scheme). The synthesis and properties of the dendrons is also described.