Probing Absolute Electronic Energy Levels in Hg‐Doped CdTe Semiconductor Nanocrystals by Electrochemistry and Density Functional Theory

The absolute electronic energy levels in Hg‐doped CdTe semiconductor nanocrystals (CdHgTe NCs) with varying sizes/volumes and Hg contents are determined by using cyclic voltammetry (CV) measurements and density functional theory (DFT) ‐based calculations. The electrochemical measurements demonstrate several distinct characteristic features in the form of oxidation and reduction peaks in the voltammograms, where the peak positions are dependent on the volume of CdHgTe NCs as well as on their composition. The estimated absolute electronic energy levels for three different volumes, namely 22, 119 and 187 nm³ with 2.7±0.3 % of Hg content, show strong volume dependence. The volume‐dependent shift in the characteristic reduction and oxidation peak potential scan can be attributed to the alteration in the energetic band positions owing to the quantum confinement effect. Moreover, the composition (Cd/Hg=98.3/1.7 and 97.0/3.0) ‐dependent alteration in the electronic energy levels of CdHgTe NCs for two different samples with similar volumes (ca. 124±5 nm³) are shown. Thus obtained electronic energy level values of CdHgTe NCs as a function of volume and composition demonstrate good congruence with the corresponding absorption and emission spectral data, as well as with DFT‐based calculations. DFT calculations reveal that incorporation of Hg into CdTe NCs mostly affects the energy levels of conduction band edge, whereas the valence band edge remains almost unaltered.     

Effect of included guest molecules on the normal state conductivity and superconductivity of beta''-(ET)(4)[(H(3)O)Ga(C(2)O(4))(3)].G (G = pyridine,nitrobenzene)

Normal state conductivity and superconductivity together with bulk magnetic susceptibility and magnetization measurements have been measured for two molecular charge-transfer salts: beta' '-(ET)4[(H3O)Ga(C2O4)3]G (ET = bis(ethylenedithio)tetrathiafulvalene, G = pyridine for compound I and nitrobenzene for compound II). With the exception of the included guest molecules (G) the crystal structures are almost identical. Both show minima in their electrical transport at 130 K for I and at 160 K for II, but at lower temperatures their behaviors differ markedly. The resistance of I reaches a maximum at 50 K with a further small peak at 2 K and possible superconductivity only below 2 K, whereas that of II increases continuously down to 7.5 K, where an abrupt transition to a superconducting state occurs.     

Structure activity relationship by NMR and by computer: a comparative study

There has recently been considerable interest in using NMR spectroscopy to identify ligand binding sites of macromolecules. In particular, a modular approach has been put forward by Fesik et al. (Shuker, S. B.; Hajduk, P. J.; Meadows, R. P.; Fesik, S. W. Science 1996, 274, 1531-1534) in which small ligands that bind to a particular target are identified in a first round of screening and subsequently linked together to form ligands of higher affinity. Similar strategies have also been proposed for in silico drug design, where the binding sites of small chemical groups are identified, and complete ligands are subsequently assembled from different groups that have favorable interactions with the macromolecular target. In this paper, we compare experimental and computational results on a selected target (FKBP12). The binding sites of three small ligands ((2S)1-acetylprolinemethylester, 1-formylpiperidine, 1-piperidinecarboxamide) in FKBP12 were identified independently by NMR and by computational methods. The subsequent comparison of the experimental and computational data showed that the computational method identified and ranked favorably ligand positions that satisfy the experimental NOE constraints.     

Data quality assurance for thermophysical property databases--applications to the TRC SOURCE data system

To a significant degree processes of database development are based upon human activities, which are susceptible to various errors. Propagation of errors in the processing leads to a decrease in the value of original data as well as that of any database products. Data quality is a critical issue that every database producer must handle as an inseparable part of the database management. Within the Thermodynamics Research Center (TRC), a systematic approach to implement database integrity rules was established through the use of modern database technology, statistical methods, and thermodynamic principles. The four major functions of the system--error prevention, database integrity enforcement, scientific data integrity protection, and database traceability--are detailed in this paper.     

Characterising lone-pair activity of lead(II) by 207Pb solid-state NMR spectroscopy: coordination polymers of [N(CN)2]- and [Au(CN)2]- with terpyridine ancillary ligands

A series of lead(II) coordination polymers containing [N(CN)₂]^? (DCA) or [Au(CN)₂]^? bridging ligands and substituted terpyridine (terpy) ancillary ligands ([Pb(DCA)₂] ( 1 ), [Pb(terpy)(DCA)₂] ( 2 ), [Pb(terpy){Au(CN)₂}₂] ( 3 ), [Pb(4′‐chloro‐terpy){Au(CN)₂}₂] ( 4 ) and [Pb(4′‐bromo‐terpy)(μ‐OH₂)_0.5{Au(CN)₂}₂] ( 5 )) was spectroscopically examined by solid‐state ²⁰⁷Pb MAS NMR spectroscopy in order to characterise the structural and electronic changes associated with lead(II) lone‐pair activity. Two new compounds, 2 and [Pb(4′‐hydroxy‐terpy){Au(CN)₂}₂] ( 6 ), were prepared and structurally characterised. The series displays contrasting coordination environments, bridging ligands with differing basicities and structural and electronic effects that occur with various substitutions on the terpyridine ligand (for the [Au(CN)₂]^? polymers). ²⁰⁷Pb NMR spectra show an increase in both isotropic chemical shift and span (Ω) with increasing ligand basicity (from δ_iso=?3090 ppm and Ω=389 ppm for 1 (the least basic) to δ_iso=?1553 ppm and Ω=2238 ppm for 3 (the most basic)). The trends observed in ²⁰⁷Pb NMR data correlate with the coordination sphere anisotropy through comparison and quantification of the Pb? N bond lengths about the lead centre. Density functional theory calculations confirm that the more basic ligands result in greater p‐orbital character and show a strong correlation to the ²⁰⁷Pb NMR chemical shift parameters. Preliminary trends suggest that ²⁰⁷Pb NMR chemical shift anisotropy relates to the measured birefringence, given the established correlations with structure and lone‐pair activity.     

Reactivity of 3d transition metal cations in diethylene glycol solutions. Synthesis of transition metal ferrites with the structure of discrete nanoparticles complexed with long-chain carboxylate anions

Study of the reactivity of 3d transition metal cations in diethylene glycol solutions revealed several key features that made it possible to develop a new method for synthesis of the nanocrystalline transition metal ferrites. The 3-7 nm particles of [MFe2O4]n[O2CR]m, where M = Mn, Fe, Co, Ni, and Zn, ligated on their surface with long-chain carboxylate anions, have been obtained in an isolated yield of 75-90%. The key features are the following. Complexation of the first-row transition metal cations with diethylene glycol at a presence of alkaline hydroxide is sufficient to enable control over the rate of their hydrolysis. The reaction of hydrolysis leads to the formation of metal oxide nanocrystals in colloidal solution. The nanoparticles growth is terminated by an added long-chain carboxylic acid, which binds to their surface and acts as a capping ligand. The isolated nanocrystalline powders are stable against agglomeration and highly soluble in nonpolar organic solvents.     

Carbon-carbon and carbon-nitrogen coupling reactions catalyzed by palladium nanoparticles derived from a palladium substituted Keggin-type polyoxometalate

Palladium 15-20 nm particles stabilized by a Keggin-type polyoxometalate were prepared by reduction of K(5)PPdW(11)O(39) with H(2). The nanoparticles were shown to be effective catalysts for Suzuki-, Heck-, and Stille-type carbon-carbon coupling and carbon-nitrogen coupling reactions of bromoarenes in aqueous media. Chloroarenes were also reactive in reaction media without solvent. [reaction: see text]