Multi-Step Nucleation of a Crystalline Silicate Framework via a Structurally Precise Prenucleation Cluster

Hierarchical nucleation pathways are ubiquitous in the synthesis of minerals and materials. In the case of zeolites and metal-organic frameworks, pre-organized multi-ion "secondary building units" (SBUs) have been proposed as fundamental building blocks. However, detailing the progress of multi-step reaction mechanisms from monomeric species to stable crystals and defining the structures of the SBUs remains an unmet challenge. Combining in situ nuclear magnetic resonance, small-angle X-ray scattering, and atomic force microscopy, we show that crystallization of the framework silicate, cyclosilicate hydrate, occurs through an assembly of cubic octameric Q³ ₈ polyanions formed through cross-linking and polymerization of smaller silicate monomers and other oligomers. These Q³ ₈ are stabilized by hydrogen bonds with surrounding H₂ O and tetramethylammonium ions (TMA⁺ ). When Q³ ₈ levels reach a threshold of ≈32 % of the total silicate species, nucleation occurs. Further growth proceeds through the incorporation of [(TMA)_x (Q³ ₈ )⋅n H₂ O]^(x-8) clathrate complexes into step edges on the crystals.