Synthesis and Hydrolysis–Condensation Study
of Water-Soluble Self-Assembled Pentacoordinate Polysilylamides
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Abstract
Polysilylamides
(<i>n</i> = 1–8) with a Si–Cl functionality
containing pentacoordinate silicon in the backbone were produced in
high yield by transsilylation of bis(chloromethyl)methylchlorosilane
and the trimethylsilyl derivative of diketopiperazine. Pentacoordinate
polysilylamides were highly soluble in water as a result of silicon
water coordination (Si←OH<sub>2</sub>) from hydrolysis of the
Si–Cl group in each repeat unit. Interestingly, the water silicon
coordination in polysilanolamides was stable toward self-condensation
and found to contain pentacoordinate silicon even in water, thus avoiding
siloxane (Si–O–Si) bond formation. In the gas phase
the polysilanolamides underwent intramolecular stepwise hydrolysis–condensation
possibly as a result of CC double-bond formation at each monomer
unit, as observed by MALDI-TOF MS. Low-intensity peaks of macrocyclic
polysilanolamides (<i>n</i> = 2–5) were also observed
that contain water molecules. For a better understanding of the hydrolysis–condensation
process of the polysilylamide, new model compounds of pentacoordinated
silicon derivatives of pyridones were synthesized, characterized,
and compared with the polysilanolamides using NMR and X-ray crystallography.
X-ray analysis of the model compounds revealed insight into the silicon
water coordination in each repeat unit and the mode of packing within
the polymers that contain these monomer units. It is found that the
partial hydrolysis of the model pentacoordinate chlorosilanes gives
water-coordinated pentacoordinate silicon species that resemble an
intermediate in the aqueous hydrolysis of pentacoordinate polysilylamides