Coordination-Driven Ambient Infiltration of Silicon and Germanium Precursors for the Synthesis of Polymer–Inorganic Hybrid Materials

Polymer–inorganic hybrids (PIH) merge the functionality of the inorganic phase and processability in polymeric materials. Their synthesis is nontrivial and largely limited to aqueous solution or highly reactive precursors in the gas phase. Here, we present an ambient-condition, organic-compatible, coordination-driven route for synthesizing PIHs through hypervalency using the strong Lewis basicity of poly(4-vinylpyridine) (P4VP). Volatile chlorosilanes and chlorogermanes react spontaneously with P4VP to form cross-linked P4VP–M (M = Si, Ge) complexes. Complexation occurs rapidly in homogeneous polymer solutions, and heterogeneous vapor phase infiltration of solid films. Complementary techniques including solid-state 29 Si NMR, FTIR, and Raman spectroscopy support the formation of a six-coordinate silicon complex in the reaction between trichlorosilane and P4VP. The chemistry is general, enabling the formation of diverse complexes by careful selection of polymer–precursor pairs. In situ swelling studies reveal rapid, uniform infiltration into P4VP, slower sterically hindered uptake in P2VP, and no infiltration in PS, demonstrating clear coordination-driven selectivity. Leveraging spatial selectivity, silane infiltration into PS- b -P4VP produces silicon-based inorganic hard masks after polymer removal, providing a facile alternative that avoids the high temperatures and vacuum requirements of atomic layer deposition (ALD)-based infiltration.