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RESEARCH FRONT

The Nature of Hydrogen Bonding Involving the Siloxane Group

Simon Grabowsky A B D , Jens Beckmann A C and Peter Luger A
+ Author Affiliations
- Author Affiliations

A Freie Universität Berlin, Institut für Chemie und Biochemie/Anorganische Chemie, 14195 Berlin, Germany.

B Current address: The University of Western Australia, School of Chemistry and Biochemistry, M313, Crawley WA 6009, Australia.

C Current address: Universität Bremen, Institut für Anorganische und Physikalische Chemie, 28359 Bremen, Germany.

D Corresponding author. Email: simon.grabowsky@uwa.edu.au

Australian Journal of Chemistry 65(7) 785-795 https://doi.org/10.1071/CH11468
Submitted: 9 December 2011  Accepted: 6 February 2012   Published: 27 April 2012

Abstract

Variation of the Si–O–Si angle in siloxane compounds is a way to tune their basicity from highly hydrophobic systems at linear geometry to hydrophilic systems at small angles. This has great potential in the design of new siloxane materials with properties distinct from those of known silicones. We investigate hydrogen bonds with the siloxane linkage as an acceptor in a large range of Si–O–Si angles for the two hydrogen-bonded complexes disiloxane⋯silanol [(H3Si)2O⋯HOSiH3] and disiloxane⋯water [(H3Si)2O⋯HOH] with free disiloxane [H3SiOSiH3] as reference in a quantum-mechanical ab-initio study. Geometry, electron density, and the electron localizability indicator provide several complementary indicators of hydrogen bonding which show how Si–O–Si angle variation affects the nature and strength of these unusual hydrogen bonds.


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