TY - JOUR
T1 - Synthesis of diaryl dithiocarbamate complexes of zinc and their uses as single source precursors for nanoscale ZnS
AU - Sarker, Jagodish C.
AU - Alam, Firoz
AU - McNaughter, Paul
AU - Pugh, David
AU - Cockcroft, Jeremy K.
AU - Lewis, David J.
AU - Hogarth, Graeme
N1 - Funding Information:
We thank the Commonwealth Scholarship commission for a PhD studentship (JCS) and the EPSRC for grants EP/R020590/1 (DJL, FA) and EP/R022518/1 (DJL, P.McN).
Publisher Copyright:
© 2023 The Authors
PY - 2023/10/1
Y1 - 2023/10/1
N2 - Diaryldithiocarbamate complexes, [Zn(S2CNAr2)2], have been prepared with a view to comparing their structures, reactivity and thermally-promoted degradation with respect to the well-studied dialkyl-derivatives. In the solid-state both [Zn{S2CN(p-tol)2}2] and [Zn{S2CN(p-anisyl)2}2] are monomeric with a distorted tetrahedral Zn(II) centre, but somewhat unexpectedly, the bulkier naphthyl-derivative [Zn{S2CN(2-nap)2}2]2 forms dimeric pairs with five-coordinate Zn(II) centres. Preliminary reactivity studies on [Zn{S2CN(p-tol)2}2] suggests that it binds amines and cyclic amines in a similar fashion to the dialkyl complexes and can achieve six-coordination as shown in the molecular structure of [Zn{S2CN(p-tol)2}2(2,2′-bipy)]. The thermal decomposition of [Zn{S2CN(p-tol)2}2] was studied in oleylamine solution by both heat-up and hot-injection methods. Nanorods of ZnS were produced in both cases with average dimensions of 17 × 2.1 nm and 11 × 3.5 nm respectively, being significantly shorter than those produced from [Zn(S2CNiBu2)2] under similar conditions. This is tentatively attributed to the differing rates of amine-exchange between diaryl- and dialkyl dithiocarbamate (DTC) complexes and/or their differing rates of DTC loss following amine-exchange. The solid-state decomposition of [Zn{S2CN(p-tol)2}2] has also been studied at 450 °C under argon affording irregular and large (10–300 µm) sheet-like particles of wurtzite.
AB - Diaryldithiocarbamate complexes, [Zn(S2CNAr2)2], have been prepared with a view to comparing their structures, reactivity and thermally-promoted degradation with respect to the well-studied dialkyl-derivatives. In the solid-state both [Zn{S2CN(p-tol)2}2] and [Zn{S2CN(p-anisyl)2}2] are monomeric with a distorted tetrahedral Zn(II) centre, but somewhat unexpectedly, the bulkier naphthyl-derivative [Zn{S2CN(2-nap)2}2]2 forms dimeric pairs with five-coordinate Zn(II) centres. Preliminary reactivity studies on [Zn{S2CN(p-tol)2}2] suggests that it binds amines and cyclic amines in a similar fashion to the dialkyl complexes and can achieve six-coordination as shown in the molecular structure of [Zn{S2CN(p-tol)2}2(2,2′-bipy)]. The thermal decomposition of [Zn{S2CN(p-tol)2}2] was studied in oleylamine solution by both heat-up and hot-injection methods. Nanorods of ZnS were produced in both cases with average dimensions of 17 × 2.1 nm and 11 × 3.5 nm respectively, being significantly shorter than those produced from [Zn(S2CNiBu2)2] under similar conditions. This is tentatively attributed to the differing rates of amine-exchange between diaryl- and dialkyl dithiocarbamate (DTC) complexes and/or their differing rates of DTC loss following amine-exchange. The solid-state decomposition of [Zn{S2CN(p-tol)2}2] has also been studied at 450 °C under argon affording irregular and large (10–300 µm) sheet-like particles of wurtzite.
KW - Amine-exchange
KW - Diaryl dithiocarbamate
KW - Single source precursors
KW - Zinc complexes
UR - http://www.scopus.com/inward/record.url?scp=85163828147&partnerID=8YFLogxK
U2 - 10.1016/j.ica.2023.121663
DO - 10.1016/j.ica.2023.121663
M3 - Article
AN - SCOPUS:85163828147
SN - 0020-1693
VL - 556
JO - INORGANICA CHIMICA ACTA
JF - INORGANICA CHIMICA ACTA
M1 - 121663
ER -