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The tetrameric hydrolysis products of zirconium(IV) and hafnium(IV), the zirconyl(IV) and hafnyl(IV) ions, [M(4)(OH)(8)(OH(2))(16)(8+)], often labelled MO(2+).5H(2)O, are in principle the only zirconium(IV) and hafnium(IV) species present in aqueous solution without stabilising ligands and pH larger than zero. These complexes are furthermore kinetically very stable and do not become protonated even after refluxing in concentrated acid for at least a week. The structures of these complexes have been determined in both solid state and aqueous solution by means of crystallography, EXAFS and large angle X-ray scattering (LAXS). Each metal ion in the [M(4)(OH)(8)(OH(2))(16)](8+) complex binds four hydroxide ions in double hydroxo bridges, and four water molecules terminally. The M-O bond distance to the hydroxide ions are markedly shorter, ca. 0.12 A, than to the water molecules. The hydrated zirconium(IV) and hafnium(IV) ions only exist in extremely acidic aqueous solution due to their very strong tendency to hydrolyse. The structure of the hydrated zirconium(IV) and hafnium(IV) ions has been determined in concentrated aqueous perchloric acid by means of EXAFS, with both ions being eight-coordinated, most probably in square antiprismatic fashion, with mean Zr-O and Hf-O bond distances of 2.187(3) and 2.160(12) A, respectively. The dimethyl sulfoxide solvated zirconium(IV) and hafnium(IV) ions are square antiprismatic in both solid state and solution, with mean Zr-O and Hf-O bond distances of 2.193(1) and 2.181(6) A, respectively, in the solid state. Hafnium(IV) chloride does not dissociate in N,N'-dimethylpropyleneurea, dmpu, a solvent with good solvating properties but with a somewhat lower permittivity (epsilon= 36.1) than dimethyl sulfoxide (epsilon= 46.4), and an octahedral HfCl(4)(dmpu)(2) complex is formed.

An ordered network of interconnected tin oxide (SnO2) nanoparticles with a unique 3D architecture and an excellent lithium‐ion (Li‐ion) storage performance is derived for the first time through hydrolysis and thermal self‐assembly of the solid alkoxide precursor. Mesoporous anodes composed of these ≈9 nm‐sized SnO2 particles exhibit substantially higher specific capacities, rate performance, coulombic efficiency, and cycling stabilities compared with disordered nanoparticles and commercial SnO2. A discharge capacity of 778 mAh g–1, which is very close to the theoretical limit of 781 mAh g–1, is achieved at a current density of 0.1 C. Even at high rates of 2 C (1.5 A g–1) and 6 C (4.7 A g–1), these ordered SnO2 nanoparticles retain stable specific capacities of 430 and 300 mAh g–1, respectively, after 100 cycles. Interconnection between individual nanoparticles and structural integrity of the SnO2 electrodes are preserved through numerous charge–discharge process cycles. The significantly better electrochemical performance of ordered SnO2 nanoparticles with a tap density of 1.60 g cm–3 is attributed to the superior electrode/electrolyte contact, Li‐ion diffusion, absence of particle agglomeration, and improved strain relaxation (due to tiny space available for the local expansion). This comprehensive study demonstrates the necessity of mesoporosity and interconnection between individual nanoparticles for improving the Li‐ion storage electrochemical performance of SnO2 anodes.

This review provides an insight into the common reaction mechanisms in Soft Chemistry processes involved in nucleation, growth and aggregation of metal, metal oxide and chalcogenide nanoparticles starting from metal-organic precursors such as metal alkoxides, beta-diketonates, carboxylates and their chalcogene analogues and demonstrates how mastering the precursor chemistry permits us to control the chemical and phase composition, crystallinity, morphology, porosity and surface characteristics of produced nanomaterials.