Supramolecular Template-Directed Synthesis of Perfect Phenelenediimino-Bridged Ladderlike Polyphenylsiloxanes

A template synthesis of the soluble, high molecular weight (Mw), and perfect p‐phenylenediimino (p‐PDA)‐bridged ladderlike polyphenylsiloxane (PLPS) is reported. First, N,N′‐bis(phenyldichlorosilyl)‐p‐PDA monomers were self‐assembled into a perfect ladder superstructure (LS) by concerted interaction of aromatic π–π stacking and hydrogen bonding. Then the LS underwent a novel stoichiometric hydrolysis/dehydrochlorination–condensation reaction instead of the usual hydrolysis/dehydration–condensation reaction, leading to the PLPS. The perfect ladder structures of both the PLPS and, in particular, the unstable supramolecular LS were confirmed as follows. 1) There are two Bragg peaks in solid and/or solution X‐ray diffraction (XRD) spectra representing the ladder width (w) and ladder thickness (t); these peaks were consistent with those calculated by molecular simulation. 2) Both the PLPS and LS have extremely sharp absorption peaks with small half‐peak widths (Δ1/2