Persistence of C-H⋯π(chelate ring) interactions in the crystal structures of Pd(S2COR)2. the utility of Pd(S2COR)2 as precursors for palladium sulphide materials

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DOIResolve DOI: http://doi.org/10.1039/c5ce02126j
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TypeArticle
Journal titleCrystEngComm
ISSN1466-8033
Volume18
Issue7
Pages11051117; # of pages: 13
AbstractThe crystallographic structures of 12 palladium xanthates, Pd(S2COR)2 (R = alkyl) show a uniform adoption of square-planar PdS4 geometries. Supramolecular aggregation in 1 (R = Me), 2 (Et) and 3 (n-Pr) is based on secondary Pd⋯S interactions, which are "turned off" when the bulk of R increases. In 4 (i-Pr), C-H⋯S hydrogen bonding is present. In each of 2-4, C-H⋯π(PdS2C) interactions are incorporated within the architecture, stabilised by Pd⋯S secondary- or C-H⋯S hydrogen-bonding. In 5-12 (R = n-Bu, i-Bu, n-Pent, i-Pent, neoPent, n-Hex, i-Hex, neoHex), varying numbers of stand-alone C-H⋯π(PdS2C) interactions involving different hydrogen donors uniformly stabilise supramolecular chains in their crystal structures. In order to determine the relative importance of the various intermolecular interactions and packing effects, a computational study using dispersion-corrected density-functional theory was performed on 3 (R = n-Pr). The results showed that the most significant contributors to the stability of the crystal structure are Pd⋯S interactions followed closely by C-H⋯π(PdS2C) interactions. Two non-specific hydrophobic interactions also contribute to the overall packing to a lesser extent. The utility of Pd(S2COR)2 to function as synthetic precursors for PdS nanoparticles and thin films was also investigated. Aerosol-assisted-CVD on representative examples generated PdS films with either matted, needle-like or granular morphologies depending on temperature and substrate. Solvothermal (ethylene glycol) decomposition generated sulphur-rich PdS nanoparticles with diameters 120 nm (7 and 10)-400 nm (8). When dodecanethiol was employed as a capping agent, PdS1.75 nanoparticles <10 nm were generated from 1.
Publication date
PublisherRoyal Society of Chemistry
LanguageEnglish
AffiliationNational Research Council Canada (NRC-CNRC)
Peer reviewedYes
NPARC number21277493
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Record identifiere264b219-9092-4936-8fb5-4ebb2f766507
Record created2016-03-09
Record modified2016-05-09
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