Gelation Mechanism Revealed in Organometallic Gels: Prevalence of van der Waals Interactions on Oligomerization by Coordination Chemistry

Chemphyschem. 2023 Jul 17;24(14):e202300077. doi: 10.1002/cphc.202300077. Epub 2023 May 25.

Abstract

Shaping of nanomaterials is a necessary step for their inclusion in electronic devices and batteries. For this purpose, the formulation of a moldable material including these nanomaterials is desirable. Organomineral gels are a very interesting option, since the components of the nanomaterial itself form a gel without the help of a binder. As a consequence, the properties of the nanomaterial are not diluted by the binder. In this article we studied organometallic gels based on a [ZnCy2 ] organometallic precursor and a primary alkyl amine which together forms spontaneously gels after few hours. We identified the main parameters controlling the gel properties monitored by rheology and NMR measurements The experiments demonstrate that the gelation time depends on the length of the alkyl chain of the amine and that the gelation mechanism derived firstly from the rigidification of the aliphatic chains of the amine, which takes precedence over the oligomerization of the inorganic backbone. This result highlights that the control of the rheological properties of organometallic gels remains mainly governed by the choice of the amine.

Keywords: NMR spectroscopy; gels; nanomaterials; organometallic chemistry; rheology.