Silicon‑Noded Cross-Ligation Platform Enabled by Customizable and Moisture-Stable Bis(polyfluoroalkoxy)silanes

Connecting modules to central nodes is a powerful assembly strategy, as exemplified by DNA/RNA, MOFs, and SuFEx/PFEx chemistry. However, SuFEx and PFEx are largely confined to amine- and phenol-type modules and the alcohol modules could be problematic for SuFEx due to potential dehydroxylative reactions. Silicon‑noded cross-ligation offers an attractive alternative because both alcohols and phenols can serve as reliable modules to form stable silyl ethers, but lacks programmable stepwise ligation hubs comparable to those in SuFEx/PFEx. The most straightforward and common dichlorosilanes are not suitable for this purpose due to unpredictable over‑substitution and moisture‑sensitive intermediates. Herein, we develop moisture‑stable bis(polyfluoroalkoxy)silanes as customizable dichlorosilane surrogates for programmable silicon‑noded cross-ligations. Systematic comparisons established a nucleofugality order for silicon-bound polyfluoroalkoxy groups (perfluoro‑tert‑butoxy >> hexafluoroisopropoxy > trifluoroethoxy) and further demonstrated that polyfluoroalkoxysilanes outperformed chlorosilanes and silyl triflates in both handling and chemoselectivity. A general synthetic platform via dephenylative silyletherification enables efficient construction of symmetrical and unsymmetrical bis(polyfluoroalkoxy)silanes with gram‑scale scalability. The resulting hubs enabled predictable, stepwise cross-ligation of diverse functionalized alcohols and phenols under mild basic conditions with broad functionalgroup compatibility. Notably, streamlined, protecting-group-free iterative assembly of the same type of dihydroxy modules, such as 4-hydroxyphenethyl alcohol, at silicon nodes was further demonstrated, guided by the DNA node–module logic and the high chemoselectivity of polyfluoroalkoxysilanes. Collectively, this work overcomes the limitations of dichlorosilane chemistry and offers a versatile platform for silicon‑noded modular assembly.