Bhide, MA;
Mears, KL;
Carmalt, CJ;
Knapp, CE;
(2021)
Synthesis, solution dynamics and chemical vapour deposition of heteroleptic zinc complexes via ethyl and amide zinc thioureides.
Chemical Science
10.1039/d1sc01846a.
(In press).
Preview |
Text
d1sc01846a.pdf - Published Version Download (1MB) | Preview |
Abstract
Ethyl and amide zinc thioureides [L^{1}ZnEt]_{2} (1), [L^{1*}ZnEt]_{2} (2) and [L^{1}Zn(N(SiMe_{3})_{2})]_{2} (3) have been synthesised from the equimolar reaction of thiourea ligands (HL^{1} = iPrN(H)CSNMe2 and HL^{1*} = PhN(H)CSNMe_{2}) with diethyl zinc and zinc bis[bis(trimethylsilyl)amide] respectively. New routes towards heteroleptic complexes have been investigated through reactions of 1, 2 and 3 with β-ketoiminates (HL^{2} = [(Me)CN(H){iPr}–CHC(Me)[double bond, length as m-dash]O]), bulky aryl substituted β-diiminates (HL3 = [(Me)CN(H){Dipp}–CHC(Me)[double bond, length as m-dash]N{Dipp}] (Dipp = diisopropylphenyl) and HL3* = [(Me)CN(H){Dep}–CHC(Me)[double bond, length as m-dash]N{Dep}] (Dep = diethylphenyl)) and donor-functionalised alcohols (HL^{4} = Et_{2}N(CH_{2})_{3}OH and HL4* = Me_{2}N(CH_{2}){3}_OH) and have led to the formation of the heteroleptic complexes [L^{1*}ZnL^{3*}] (5), [L^{1}ZnL^{4}]_{2} (6), [L^{1}ZnL^{4*}]_{2} (7), [L^{1*}ZnL^{4}] (8) and [L^{1*}ZnL^{4*}] (9). All complexes have been characterised by {1}^H and 1{3}^C NMR, elemental analysis, and the X-ray structures of HL^{1*}, 1, 2, 6 and 7 have been determined via single crystal X-ray diffraction. Variable temperature 1H, COSY and NOESY NMR experiments investigating the dynamic behaviour of 5, 6 and 7 have shown these molecules to be fluxional. On the basis of solution state fluxionality and thermogravimetric analysis (TGA), alkoxyzinc thioureides 6 and 7 were investigated as single-source precursors for the deposition of the ternary material zinc oxysulfide, Zn(O,S), a buffer layer used in thin film photovoltaic devices. The aerosol-assisted chemical vapour deposition (AACVD) reaction of 7 at 400 °C led to the deposition of the heterodichalcogenide material Zn(O,S), which was confirmed by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and energy dispersive X-ray analysis (EDX), with optical properties investigated using UV/vis spectroscopy, and surface morphology and film thickness examined using scanning electron microscopy (SEM).
Type: | Article |
---|---|
Title: | Synthesis, solution dynamics and chemical vapour deposition of heteroleptic zinc complexes via ethyl and amide zinc thioureides |
Open access status: | An open access version is available from UCL Discovery |
DOI: | 10.1039/d1sc01846a |
Publisher version: | https://doi.org/10.1039/D1SC01846A |
Language: | English |
Additional information: | © 2021 The Author(s). Published by the Royal Society of Chemistry. This article is licensed under a Creative Commons Attribution 3.0 Unported Licence (http://creativecommons.org/licenses/by/3.0/). |
UCL classification: | UCL UCL > Provost and Vice Provost Offices > UCL BEAMS UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Maths and Physical Sciences UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Maths and Physical Sciences > Dept of Chemistry |
URI: | https://discovery-pp.ucl.ac.uk/id/eprint/10129239 |
Archive Staff Only
![]() |
View Item |