Tris(ß-ketoiminate) Aluminium(III) Compounds as Aluminium Oxide Precursors.

Precursor design is the crucial step in tailoring the deposition profile towards a multitude of functional materials. Most commercially available aluminium oxide precursors require high processing temperatures (>500 °C). Herein, we report the tuning of the decomposition profile (200-350 °C) of a range of octahedrally coordinated tris(ß-ketoiminate) aluminium complexes of the type [Al(MeCN(R)CHC=OMe)3 ], by varying the R substituents in the ligands. The complexes are derived from the reaction of trimethylamine alane (TMAA) and a series of N-substituted ß-ketoiminate ligands (R-acnacH, R=Me, Et, i Pr, Ph) with varying R-substituents sizes. When the more sterically encumbered ligand (R=Mes) was used, the Al atom became five-coordinate, therefore representing the threshold to octahedral coordination around the metal in these type of compounds, which, consequently, lead to a change of decomposition profile. The resulting compounds have been characterised by NMR spectroscopy, mass spectrometry, elemental analysis and single crystal X-ray diffraction. [Al(MeCN(Me)CHC=OMe)3 ] has been used as a single source precursor for the deposition of Al2 O3 . Thin films were deposited via aerosol assisted chemical vapour deposition (AACVD), with toluene as the solvent, and were analysed using SEM, EDX and XPS.

Phosphinecarboxamide based InZnP QDs - an air tolerant route to luminescent III-V semiconductors.

We describe a new synthetic methodology for the preparation of high quality, emission tuneable InP-based quantum dots (QDs) using a solid, air- and moisture-tolerant primary phosphine as a group-V precursor. This presents a significantly simpler synthetic pathway compared to the state-of-the-art precursors currently employed in phosphide quantum dot synthesis which are volatile, dangerous and air-sensitive, e.g. P(Si(CH3)3)3.

Novel primary phosphinecarboxamides derived from diamines.

We describe the synthesis of N-functionalised phosphinecarboxamides obtained by reaction of the 2-phosphaethynolate anion (PCO-) with diamines, specifically hydrazine, methylenediamine and ethylenediamine, in the presence of acid. The resulting neutral compounds can be deprotonated to generate phosphide anions that, when further reacted with electrophiles, form secondary phosphines.

Novel ferrocenyl functionalised phosphinecarboxamides: synthesis, characterisation and coordination.

The synthesis of two novel ferrocenyl-substituted phosphinecarboxamides, FcNHC(O)PH2 (1; Fc = ferrocenyl) and FcCH2NHC(O)PH2 (2), is reported. These two primary phosphines were obtained by the reaction of aminoferrocene with sodium 2-phosphaethynolate in the presence of a proton source or, directly, from aminomethylferrocene hydrochloride and sodium 2-phosphaethynolate. Their ability to act as ligands was probed via reactions of 1 with rhodium(iii) and ruthenium(ii) precursors. The isoelectronic metal complexes [(η5-C5Me5)RhCl2(1-κP)] and [(η6-mes)RuCl2(1-κP)] were obtained. Treatment of these compounds with a base resulted in HCl elimination to afford phosphide-bridged dirhodium and diruthenium complexes highlighting that on coordination to a metal, the P-H bonds of these phosphinecarboxamides become increasingly protic.

A heterobimetallic [Mn5(II)Cu5(II)] nanowheel modulated by a flexible bis-oxamate type ligand.

The synthesis, crystal structure and preliminary magnetic characterization of a new heterobimetallic [Mn5(II)Cu5(II)] wheel containing a flexible bis-oxamate type ligand are described. This decanuclear compound exhibits a relatively strong intra-wheel antiferromagnetic interaction leading to a ground spin state S = 10.

A pH-triggered bistable copper(II) metallacycle as a reversible emulsion switch for biphasic processes.

A unique bistable copper-metallacyclic complex is used as an elegant molecular switch for the reversible formation of emulsions by simple pH variation. This switch may have several exciting applications in biphasic processes such as catalysis and separation science technologies.