The ladder polyvinylsilsesquioxane (Vi-LPSQ) with high regularity was successfully synthesized via supramolecular architecture-directed stepwise coupling and polymerization:“synchronous growth polymerization

synchronous bridge-cleaving followed by in situ condensation”.Formation with branches or cross-linking is unavoidable if the effective template is absent.Here

it is necessaryly emphasized that ladder superstructure (Vi-LS) and hydrogen-bonding adduct (HBA) are two imperative supramolecular architectures determining the ladder regularity of Vi-LPSQ.The ladder-rung

diaminophenylenes

can self-assemble into real ladder superstructures (Vi-LS) as template by π-interaction-aided N—H’s hydrogenbonding.And when converting the real Vi-DLPS to the desired Vi-LPSQ

oxalyl chloride can initially form a stable hydrogen-bonded adduct (HBA) with the diaminophenylenes-bridge of Vi-DLPS by a synergy of hydrogen bonding between carbonyl and amino groups and dπ-pπ interaction of p-electrons of Cl-atom and d-orbital of Si-atom.As a result

the reactive Vi-LPSQ is obtained based-on this supramolecular architecturesdirected approach.The ladder regularities for either the Vi-DLPS or Vi-LPSQ are confirmed by the strong-diffraction peaks at small angle range of XRD patterns.Especially

29Si-NMR measurement gives the sharp peak with extremely narrow baselinewidth

Δca. 1

of the repeat moieties:Vi—Si(O2/2)—NH—Ph—NH—Si(O2/2)—Vi and Vi—Si(O2/2)—O—Si(O2/2)—Vi.Moreover

The target polymer Vi-LPSQ is a premising precursor for preparation of number of advanced functional materials due to a possibility of functionalization for the reactive vinyl group.