Synthesis and Characterization of Thiolate-Oxo Ligated Zinc Alkyl Derivatives for Production of Zn-Based Nanoparticles.
A series of mercapto-oxo containing reagents [3-mercaptopropionic acid (H2-3MPA), 4-mercaptophenol (H2-4MP), 2-mercaptopyridine-N-oxide (H-2MPO)] was reacted with diethyl zinc (ZnEt2) in hexanes/pyridine (py) to yield {(μ4-3MPA)[Zn(Et)(py)]4}∞(1), [(py)2(Et)Zn(μ3-4MP)Zn(Et)(py)]2(2), and (2MPO)Zn(Et)py (3). For polymeric1, each of the functional sites of the 3MPA was bound to four tetrahedral (Td) coordinated Zn(Et)(py) subunits. The sulfur of the 3MPA bridges two of the 'Zn(Et)(py)' subunits, which are also bridged by the two carboxylate oxygens of another 3MPA to propagate the chain. In contrast,2forms a discrete tetranuclear species consisting of two Zn(Et)(py) moieties bridged by the oxygens of two 4MP ligands with the thiolate sites of each terminated by Zn(Et)(py)2moieties. Compound3adopts a monomeric species using a chelating 2MPO, a terminal Et, and a bound py to fill the Td coordination of the Zn metal center. Compounds1 - 3were then used to generate nanoparticles via solution precipitation and solvothermal routes to determine the effect these precursors have on the morphology and composition of the final materials produced. Compounds1 - 3were found to form zincite, zinc metal, or mixed zincite/wurtzite phases from solution precipitation or solvothermal routes; however, no routes yielded the mixed anion (i.e., ZnOxSy) materials.
Sandia National Laboratories, Advanced Materials Laboratory, 1001 University Boulevard, SE, Albuquerque, New Mexico 87106.
Timothy J
TJ
Boyle
Harry D
HD
Pratt
Todd M
TM
Alam
Thomas
T
Headley
Mark A
MA
Rodriguez
O,S ligands; ceramics; nanomaterials; wurtzite; zinc; zincite