Synthesis of zirconium(IV) and hafnium(IV) isopropoxide, sec-butoxide and tert-butoxide.

We revisited the synthesis of zirconium(IV) and hafnium(IV) alkoxides, namely the metal isopropoxide isopropanol complex (M(OiPr)4·iPrOH, M = Zr, Hf) and the metal sec- and tert-butoxide (M(OsBu)4 and M(OtBu)4, M = Zr, Hf). We optimized the most convenient synthesis methods and compared the products with commercial sources. En route to the metal sec- and tert-butoxides, we synthesized the metal diethylamido complex (M(NEt2)4, M = Zr, Hf).

Complexation and disproportionation of group 4 metal (alkoxy) halides with phosphine oxides.

Group 4 Lewis acids are well-known catalysts and precursors for (non-aqueous) sol-gel chemistry. Titanium, zirconium and hafnium halides, and alkoxy halides are precursors for the controlled synthesis of nanocrystals, often in the presence of Lewis base. Here, we investigate the interaction of Lewis bases with the tetrahalides (MX4, X = Cl, Br) and metal alkoxy halides (MXx(OR)4-x, x = 1-3, R = OiPr, OtBu). The tetrahalides yield the expected Lewis acid-base adducts MX4L2 (L = tetrahydrofuran or phosphine oxide). The mixed alkoxy halides react with Lewis bases in a more complex way. 31P NMR spectroscopy reveals that excess of phosphine oxide yields predominantly the complexation product, while a (sub)stoichiometric amount of phosphine oxide causes disproportionation of the MXx(OR)4-x species into MXx+1(OR)3-x and MXx-1(OR)5-x. The combination of complexation and disproportionation yields an atypical Job plot. In the case of zirconium isopropoxy chlorides, we fitted the concentration of all observed species and extracted thermodynamic descriptors from the Job plot. The complexation equilibrium constant decreases in the series: ZrCl3(OiPr) > ZrCl2(OiPr)2 ≫ ZrCl(OiPr)3, while the disproportionation equilibrium constant follows the opposite trend. Using calculations at the DFT level of theory, we show that disproportionation is driven by the more energetically favorable Lewis acid-base complex formed with the more acidic species. We also gain more insight into the isomerism of the complexes. The disproportionation reaction turns out to be a general phenomenon, for titanium, zirconium and hafnium, for chlorides and bromides, and for isopropoxides and tert-butoxides.

Monoalkyl Phosphinic Acids as Ligands in Nanocrystal Synthesis.

Ligands play a crucial role in the synthesis of colloidal nanocrystals. Nevertheless, only a handful molecules are currently used, oleic acid being the most typical example. Here, we show that monoalkyl phosphinic acids are another interesting ligand class, forming metal complexes with a reactivity that is intermediate between the traditional carboxylates and phosphonates. We first present the synthesis of n-hexyl, 2-ethylhexyl, n-tetradecyl, n-octadecyl, and oleylphosphinic acid. These compounds are suitable ligands for high-temperature nanocrystal synthesis (240-300 °C) since, in contrast to phosphonic acids, they do not form anhydride oligomers. Consequently, CdSe quantum dots synthesized with octadecylphosphinic acid are conveniently purified, and their UV-vis spectrum is free from background scattering. The CdSe nanocrystals have a low polydispersity and a photoluminescence quantum yield up to 18% (without shell). Furthermore, we could synthesize CdSe and CdS nanorods using phosphinic acid ligands with high shape purity. We conclude that the reactivity toward TOP-S and TOP-Se precursors decreases in the following series: cadmium carboxylate > cadmium phosphinate > cadmium phosphonate. By introducing a third and intermediate class of surfactants, we enhance the versatility of surfactant-assisted syntheses.

Crystal structures of three N,N,N'-tris-ubstituted thio-ureas for reactivity-controlled nanocrystal synthesis.

The synthesis and single-crystal X-ray structures of three N,N,N'-tris-ubstituted thio-ureas are reported, namely N,N,N'-tri-benzyl-thio-urea, C22H22N2S (1), N-methyl-N,N'-di-phenyl-thio-urea, C14H14N2S (2), and N,N-di-n-butyl-N'-phenylthio-urea, C15H24N2S (3). The influence of the different substituents on the thio-ureas is clear from the delocalization of the thio-urea C-N and C=S bonds, while the crystal structures show infinite chains of N,N,N'-tri-benzyl-thio-urea (1), hydrogen-bonded pairs of N-methyl-N,N'-di-phenyl-thio-urea (2) and hexa-mer ring assemblies of N,N-di-n-butyl-N'-phenylthio-urea (3) mol-ecules. The above-mentioned compounds were synthesized via a mild, general procedure, readily accessible precursors and with a high yield, providing straightforward access to a whole library of thio-ureas.

Silica@zirconia Core@shell Nanoparticles for Nucleic Acid Building Block Sorption.

The development of delivery systems for the immobilization of nucleic acid cargo molecules is of prime importance due to the need for safe administration of DNA or RNA type of antigens and adjuvants in vaccines. Nanoparticles (NP) in the size range of 20-200 nm have attractive properties as vaccine carriers because they achieve passive targeting of immune cells and can enhance the immune response of a weakly immunogenic antigen via their size. We prepared high capacity 50 nm diameter silica@zirconia NPs with monoclinic/cubic zirconia shell by a green, cheap and up-scalable sol-gel method. We studied the behavior of the particles upon water dialysis and found that the ageing of the zirconia shell is a major determinant of the colloidal stability after transfer into the water due to physisorption of the zirconia starting material on the surface. We determined the optimum conditions for adsorption of DNA building blocks, deoxynucleoside monophosphates (dNMP), the colloidal stability of the resulting NPs and its time dependence. The ligand adsorption was favored by acidic pH, while colloidal stability required neutral-alkaline pH; thus, the optimal pH for the preparation of nucleic acid-modified particles is between 7.0-7.5. The developed silica@zirconia NPs bind as high as 207 mg dNMPs on 1 g of nanocarrier at neutral-physiological pH while maintaining good colloidal stability. We studied the influence of biological buffers and found that while phosphate buffers decrease the loading dramatically, other commonly used buffers, such as HEPES, are compatible with the nanoplatform. We propose the prepared silica@zirconia NPs as promising carriers for nucleic acid-type drug cargos.

The Trouble with ODE: Polymerization during Nanocrystal Synthesis.

1-Octadecene is a widely used solvent for high-temperature nanocrystal synthesis (120-320 °C). Here, we show that 1-octadecene spontaneously polymerizes under these conditions, and the resulting poly(1-octadecene) has a comparable solubility and size to nanocrystals stabilized by hydrophobic ligands. Typical purification procedures (precipitation/redispersion cycles or size exclusion chromatography) fail to separate the poly(1-octadecene) impurity from the nanocrystal product. To avoid formation of poly(1-octadecene), we replace 1-octadecene with saturated, aliphatic solvents. Alternatively, the nanocrystals' native ligands are exchanged for polar ligands, leading to significant solubility differences between nanocrystals and poly(1-octadecene), therefore allowing isolation of pure nanocrystals, free from polymer impurities. These results will help design superior syntheses and improve nanocrystal purity, an important factor in many applications.