Multiple Ordering Transitions: Hierarchical Self‐Assembly of Rod–Coil Block Copolymers

Organized structures over length scales differing by 10³ are reported, i.e., crystals of rod block (unit cell ∼ 1 nm), block copolymer microdomains (layer periodicity ∼ 50 nm), and Néel domain walls (wall periodicity ∼ 1000 nm)—see Figure and inside front cover. The result is an example of combined dynamic and static self‐ assembly, which creates an unconventional morphology with multiple length scales in a single‐step process.