Synthesis, Crystal Structure, and Selected Properties of [Au(S₂CNH₂)₂]SCN: A Precursor for Gold Macro‐Needles Consisting of Gold Nanoparticles Glued by Graphitic Carbon Nitride

Abstract

An ew preparation route is developed for the synthesis of needle-like crystals of [Au(S 2 CNH 2 ) 2 ]SCN, which avoids disproportionation of the Au I salt used as as tarting material. In the crystals tructure, the two crystallographically independent Au III centers are in as quare-planar environment of two S 2 CNH 2 ligands.T he Hirshfelds urface analysis reveals the presence of noncovalent intermolecular S···S interactions, which are essential for the spatiala rrangement of the molecules. Density functional theory (DFT) calculations including dispersion and dampingc orrections result in au nit cell volumev ery close to the value determined experimentally. Thermal decomposition in an inert atmosphere generates black needles with lengths of up to 500 mm. X-ray powder diffraction and pair distribution function analyses demonstrate that the needles are composedo fn anosizedcrystals with av olume-weighted average domain size of 20(1) nm. According to resultso fX -ray photoemission experiments, the black needles are covered by an itrogen-rich carbon nitride with composition near (CN) 2 N. 13 Cs olid-state NMR investigationsi ndicatet hat two different carbon species are present,w ith signals corresponding well to heptazine units as in melon and triazine units as in poly(triazin imide) type compounds. Scanning transmission electron microscopy tomography evidencest hat the needles are composed of slightly elongated nanoparticles.Supporting information and the ORCID identification number(s) for the author(s) of this article can be found under: https://doi.

Dithiocarbamate Complexes as Single Source Precursors to Nanoscale Binary, Ternary and Quaternary Metal Sulfides

“…210–240 °C. − The decomposition mechanism is not fully elucidated, but MeS 2 CNEt 2 is a major gas phase product, suggesting that a reductive-elimination process dominates . Decomposition of the Au­(I) complex, [Au­(S 2 CNH 2 ) 2 ]­[SCN], has recently been reported, occurring via a multistep process resulting in formation of macroneedles of gold nanoparticles glued together by graphitic carbon-nitride …”

Gold Microstructures by Thermolysis of Gold(III) Di‐isopropyldithiocarbamate Complexes

“…Existing SSPs for metallic gold materials include tetrachloroauric acid and complexes employing triphenylphosphine and trifluoromethyl stabilising ligands [31—38] . There are also examples of gold(III) dithiocarbamate complexes that have been used as SSPs for the growth of gold films using chemical vapour deposition [39—43] . The most established of these is dimethyl‐diethyldithiocarbamato gold(III), which is a volatile gold(III) complex used in the deposition of gold films by thermal decomposition on surfaces [39—41] .…”

“…[31][32][33][34][35][36][37][38] There are also examples of gold(III) dithiocarbamate complexes that have been used as SSPs for the growth of gold films using chemical vapour deposition. [39][40][41][42][43] The most established of these is dimethyl-diethyldithiocarbamato gold(III), which is a volatile gold(III) complex used in the deposition of gold films by thermal decomposition on surfaces. [39][40][41] However, some synthetic challenges include the use of dimethyl gold(III) iodide, which is typically a low yielding product of organometallic Grignard reactions, [44] and their volatility limits their use as solidstate SSPs for the formation of gold microstructures.…”

Binding of Gold(III) from Solutions by the [Ag6{S2CN(CH2)6}6] Cluster: Synthesis, Thermal Behavior, and Self-Organization of the Supramolecular Structure of the Double Complex [Au{S2CN(CH2)6}2]2[AgCl2]Cl·2CHCl3 (Role of Secondary Au⋅⋅⋅Cl, Ag⋅⋅⋅S, and Cl⋅⋅⋅Cl Interactions)

“…In addition, we have previously found the capability of silver(I) dialkyldithiocarbamates to bind gold(III) from solutions into the solid phase, forming pseudo-polymeric heterometallic Au(III)-Ag(I) compounds of the ionic type with the complicatedly organized supramolecular structures [10,11]. Compounds of this type can be of interest as precursors of gold nanoparticles and thin films, which are promising for practical use in diverse areas [12][13][14][15], and of Janus particles of the Ag 2 S/Au 0 type [16].…”