Dimethylmalonato Zinc Complexes as Molecular Precursors for Electronic Grade Zinc Oxide: Towards a Systematic Ligand Design by Understanding Molecular Decomposition Mechanisms

Abstract

Zinc complexes with dimethyl 2-hydroxyimino-and 2-nitromalonate (dmm-NOH and Hdmm-NO 2 , respectively) were synthesized and examined as potential precursors for nanocrystalline zinc oxide. The functionalised 1,3-diketones are sufficiently acidic to allow direct synthesis from hydrozincite or zinc 2-propoxide as well as their full spectroscopic and analytical characterization. Their nominal elemental compositions of [Zn 4 O(dmm-NO) 6 ] and [Zn 3 (OH) 4 (dmm-NO 2 ) 2 ] suggest the presence of multinuclear cage structures with oxo-or hydroxo-bridging ligands. This assumption is in ac-

Molecular Precursors for ZnO Nanoparticles: Field-Assisted Synthesis, Electrophoretic Deposition, and Field-Effect Transistor Device Performance

“…Further contributions exist between 1700 and 1400 cm –1 which hint at further products, but could not be attributed. In the case of 2 (corresponding to IVa,b and V in Figure b), dimethyl carbonate (1290, 1432, and 1780 cm –1 ) and methanol (1030 cm –1 ) , were present (Figure S4a–d). At higher temperatures (i.e., III in Figure a and VI in Figure b), only carbon dioxide and carbon monoxide (2220 cm –1 ), as well as methane (3010 cm –1 ) and ammonia, could be detected for both 1 and 2 (Figure b,d).…”

Zinc diketonates as single source precursors for ZnO nanoparticles: microwave-assisted synthesis, electrophoretic deposition and field-effect transistor device properties

“…The latter corresponds to our earlier investigations on the decomposition of metal complexes with 1,3-diketones with ester functionalities, in which similar rearrangements occurred. 16,17 The synthesis of spherical zinc oxide nanoparticles besides a number of platelet-shaped crystallites from the decomposition of (1) in acetonitrile in an autoclave at 100 1C over a period of two days was reported by Niederberger. 18 Since acetonitrile possesses a dielectric constant k of 37.5, 7 a microwave-assisted route can be employed alternatively, which has the advantage of a drastic decrease in reaction time.…”

Synergistic and Antagonistic Ligand Effects in the Transformation of Silver Compounds of Keto‐ and Cyano‐Functionalised Oximates and Nitronates: A Systematic Study Using Thermal Analysis

“…This surprising finding corresponds to earlier investigations of our group dealing with the decomposition of zinc complexes with dialkyl malonates, which were functionalised in 2-position. [23] Thereby the formation of dialkyl carbonates was observed likewise. In the case of the zinc complexes of functionalised dialkyl malonates the exact mechanism is not clear and could proceed by various routes.…”

“…[21,22] The thermal decomposition of the family of title compounds was studied in detail by means of thermogravimetry coupled with mass spectrometry as well as Fourier transform infrared spectroscopy (TG/MS-FTIR). The combination of FTIR and MS for the evolving gases is advantageous as organic molecules and cumulenes can be easily deteced by IR spectroscopy, whereas smaller molecules such as nitrous oxides or hydrogen cyanide might need additional confirmation by MS. [23] In that way, both techniques are nicely complementary. Solid materials obtained after decomposition were typically characterised by means of X-ray diffraction (XRD).…”