This work develops an iterative growth approach to synthesize
discrete
oligo lactic acids with exactly defined stereoconfiguration by connecting
enantiomeric monomers (i.e., L- and D-lactic acid) following a predesigned
sequence. A library of diblock copolymers with uniform chain length
was modularly prepared by conjugating the stereoisomeric blocks with
a chemically incompatible chain. The precise chemical structure eliminates
all molecular uncertainties associated with statistical distribution
and decouples the intertwined variables. A rich collection of ordered
structures, including unconventional Frank–Kasper A15 and σ
phases, was captured. The stereoconfiguration exerts pronounced impacts
on chain conformation, leading to appreciable variations of lattice
dimension and phase stability. This study quantitatively assessed
the critical contribution of stereoconfiguration on packing behaviors,
calling for particular attention to this essential molecular parameter
as an effective handle for rational structural engineering