Staff View: 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

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

The crystallographic structures of 12 palladium xanthates, PdĲS2COR)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...

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Main Authors:	Tan, Yee Seng , Siti Nadiah Abdul Halim,, Molloy, Kieran C., Sudlow, Anna L., Otero-de-la-Roza, Alberto, Tiekink, Edward R. T.
Format:	Article
Published:	Royal Society of Chemistry 2016
Subjects:	QD Chemistry
Online Access:	http://eprints.sunway.edu.my/615/ http://dx.doi.org/10.1039/c5ce02126j
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spelling	my.sunway.eprints.6152020-10-07T10:01:41Z http://eprints.sunway.edu.my/615/ 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 Tan, Yee Seng * Siti Nadiah Abdul Halim, Molloy, Kieran C. Sudlow, Anna L. Otero-de-la-Roza, Alberto Tiekink, Edward R. T. * QD Chemistry The crystallographic structures of 12 palladium xanthates, PdĲS2COR)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 PdĲS2COR)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. Royal Society of Chemistry 2016 Article PeerReviewed Tan, Yee Seng * and Siti Nadiah Abdul Halim, and Molloy, Kieran C. and Sudlow, Anna L. and Otero-de-la-Roza, Alberto and Tiekink, Edward R. T. * (2016) 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. CrystEngComm, 18 (7). pp. 1105-1117. ISSN 1466-8033 http://dx.doi.org/10.1039/c5ce02126j doi:10.1039/c5ce02126j
institution	Sunway University
building	Sunway Campus Library
collection	Institutional Repository
continent	Asia
country	Malaysia
content_provider	Sunway University
content_source	Sunway Institutional Repository
url_provider	http://eprints.sunway.edu.my/
topic	QD Chemistry
spellingShingle	QD Chemistry Tan, Yee Seng * Siti Nadiah Abdul Halim, Molloy, Kieran C. Sudlow, Anna L. Otero-de-la-Roza, Alberto Tiekink, Edward R. T. * 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
description	The crystallographic structures of 12 palladium xanthates, PdĲS2COR)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 PdĲS2COR)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.
format	Article
author	Tan, Yee Seng * Siti Nadiah Abdul Halim, Molloy, Kieran C. Sudlow, Anna L. Otero-de-la-Roza, Alberto Tiekink, Edward R. T. *
author_facet	Tan, Yee Seng * Siti Nadiah Abdul Halim, Molloy, Kieran C. Sudlow, Anna L. Otero-de-la-Roza, Alberto Tiekink, Edward R. T. *
author_sort	Tan, Yee Seng *
title	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
title_short	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
title_full	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
title_fullStr	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
title_full_unstemmed	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
title_sort	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
publisher	Royal Society of Chemistry
publishDate	2016
url	http://eprints.sunway.edu.my/615/ http://dx.doi.org/10.1039/c5ce02126j
_version_	1680323387804614656
score	13.211869

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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