3.9 Article

Self-Assembled Structures from Solid Cadmium(II) Acetate in Thiol/Ethanol Solutions: A Novel Type of Organic Chemical Garden

Journal

CHEMSYSTEMSCHEM
Volume 3, Issue 2, Pages -

Publisher

WILEY
DOI: 10.1002/syst.202000048

Keywords

biomimetic structures; cadmium; chemical gardens; crystalline membranes; self-assembly

Funding

  1. EU [CA17120]
  2. PRIN2017 Mineral Reactivity, a Key to Understand Large-Scale Processes: from Rock Forming Environments to Solid Waste Recovering/Lithification [2017L83S77]

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Research has shown that cadmium(II) acetate in tablet form can form unique self-assembled structures in high concentration heptanethiol solutions, representing a distinctive case in organic Chemical Gardens. The study further investigates the properties and structures of the self-assembled products, revealing the critical role of formation conditions in determining the nature and structure of the precipitating phase.
Cadmium(II) acetate in tablet form, immersed in ethanol solutions with a high concentration of heptanethiol (30-80 mM), was able to develop self-assembled sail-shaped structures. The solution in which the self-assembled structure is formed is totally organic (both solute and solvent), thus representing a unique case among organic Chemical Gardens. The constituting material for this new Chemical Garden (CG) is made of a single phase, namely a cadmium heptanethiolate with a microcrystalline structure consisting of a central cluster [CdnSn]. The morphological and structural features were studied using different techniques (SEM-EDS, elemental analysis, ATR-FTIR, Cd-113 MAS NMR, XRPD). A crystalline cell for the Cd(II) heptanethiolate cluster was obtained that completely differs from that of the solid phase precipitated by mixing an ethanol solution of Cd(II) acetate with heptanethiol. It follows that the conditions under which the formation of Cd(II) heptanethiolate occurs (slowly from solid, quickly from solution) play a critical role in determining the nature and structure of the precipitating phase.

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