Correction: Atomic layer deposition of Cu(i) oxide films using Cu(ii) bis(dimethylamino-2-propoxide) and water.

Correction for 'Atomic layer deposition of Cu(i) oxide films using Cu(ii) bis(dimethylamino-2-propoxide) and water' by J. R. Avila, et al., Dalton Trans., 2017, DOI: .

Second-generation hexavalent molybdenum oxo-amidinate precursors for atomic layer deposition.

The synthesis of molybdenum oxo-amidinate complexes MoO2(R2AMD)2 [AMD = N,N'-di-R-acetamidinate; R = Cy (2; cyclohexyl) and iPr (3)], and their characterization by 1H, 13C NMR, X-ray diffraction, and thermogravimetric analysis is reported. Quartz-crystal microbalance and X-ray photoelectron spectroscopic studies confirm that 3 is an improved ALD precursor versus the R = t-butyl derivative for MoO3 film growth. Complex 3 is accessible in higher yields (80%+), is easier to handle without mass loss, and in conjunction with O3 as the second ALD reagent, yields nitride-free MoO3 films.

Functionalised cyclodextrin-based metal-organic frameworks.

CD-MOF, an extended framework incorporating the C8 symmetric cyclic oligosaccharide, γ-cyclodextrin (γ-CD), is based on the coordination of alkali metal cations to alternating α-1,4-linked d-glucopyranosyl units on the primary and secondary faces of the γ-CD tori. Here, we report the synthesis and characterisation of an amino-functionalised CD-MOF that is isostructural with pristine CD-MOF and adsorbs CO2 permanently.

Atomic layer deposition of Cu(i) oxide films using Cu(ii) bis(dimethylamino-2-propoxide) and water.

To grow films of Cu2O, bis-(dimethylamino-2-propoxide)Cu(ii), or Cu(dmap), is used as an atomic layer deposition precursor using only water vapor as a co-reactant. Between 110 and 175 °C, a growth rate of 0.12 ± 0.02 Å per cycle was measured using an in situ quartz crystal microbalance (QCM). X-ray photoelectron spectroscopy (XPS) confirms the growth of metal-oxide films featuring Cu(i).

Using resonance Raman spectroscopy to examine vibrational barriers to electron transfer and electronic delocalization.

A time-dependent approach to the interpretation of resonance Raman scattering intensities has been used to obtain quantitative vibrational mode displacement information from scattering intensities associated with charge-transfer excitation. The displacements and associated frequencies are the key parameters needed to understand Franck-Condon effects in electron-transfer kinetics, and to delineate in a mode-specific way the composition of vibrational reorganization energies. Application of the approach to a number of types of electron-transfer reactions is described, including symmetrical and unsymmetrical intervalence electron transfers in inorganic and organic redox systems, metal-to-ligand charge-transfer reactions, and interfacial electron-transfer reactions. Also described is how the approach can be used to elucidate mechanisms for valence delocalization in strongly interacting redox systems.

How far do electrons move? A semiempirical investigation of thermal electron-transfer distances in cationic bis(hydrazine) and bis(hydrazyl) mixed-valence compounds.

A computational approach for estimating thermal electron-transfer reaction distances in symmetrical mixed-valence compounds is described and applied to a series of bis(hydrazine) and bis(hydrazyl) radical cations and derivatives, some of which have been investigated experimentally by Nelsen and co-workers. Ground-state semiempirical charge distributions are obtained by using optimized reactant geometries. Advantage is then taken of the approximate C(2) symmetry, or the approximate mirror symmetry, of each of the targeted compounds, and the inherent degeneracy of the corresponding electron-transfer reactions, such that the change in dipole moment (Delta-mu) upon charge transfer can be estimated from an appropriately distance-weighted sum of charge differences between approximately symmetry-equivalent atoms found on the donor and acceptor sides of the molecule. Delta-mu can then be related directly to the effective one-electron-transfer distance. We find that calculated adiabatic electron-transfer distances can differ appreciably from the geometric donor-site/acceptor-site separation distances. Furthermore, for a fixed geometric separation distance, the effective electron-transfer distance can vary considerably, depending on chemical substituent composition and/or isomeric configuration. Further advantage is taken of the approximate donor-site/acceptor-site symmetry, in the context of a Newton-Cave type analysis, to establish the relative importance of electronic delocalization effects versus self-polarization and inductive effects in diminishing or enhancing effective one-electron-transfer distances.

Resonance Raman and semiempirical electronic structure studies of an odd-electron dinickel tetraiminoethylenedimacrocycle complex.

Resonance Raman studies of Ni2TIED3+ (TIED = tetraiminoethylenedimacrocycle) reveal that many modes couple to the intense electronic transition centered at 725 nm, a feature that is nominally similar to the intense delocalized intervalence absorption bands observed in the same region for Fe2(TIED)L4(5+) and Ru2(TIED)L4(5+) (L is any of several axial ligands). Time-dependent spectral modeling of the Raman and absorption spectra for the nickel compound was undertaken to understand the electronic transition. We were unable to model the Raman and absorption spectra successfully with a single electronic transition, suggesting that the absorption band is made up of two overlapping transitions. Semiempirical electronic structure calculations corroborate the suggestion. Additionally, these calculations indicate that the transitions are in fact ligand-localized transitions, with little metal involvement and no charge-transfer character. Furthermore, the ground-state electronic structure is best described as an identical pair of NiII centers bridged by a radical anion rather than a three-site mixed-valence assembly. Previous EPR studies (McAuley and Xu, Inorg. Chem. 1992, 31, 5549) had indicated primarily ligand character for the radical. The assignments are consistent with the resonance Raman results where the dominant modes coupled to the transitions are assigned as totally symmetric bridge vibrations.

Supramolecular chemistry: functional structures on the mesoscale.

Supramolecular chemistry deals with the chemistry and collective behavior of organized ensembles of molecules. In this so-called mesoscale regime, molecular building blocks are organized into longer-range order and higher-order functional structures via comparatively weak forces. As one of the modern frontiers in chemistry, supramolecular chemistry heralds many promises that range from biocompatible materials and biomimetic catalysts to sensors and nanoscale fabrication of electronic devices.