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).

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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).

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