RESUMEN
Quantum interference (QI) effects offer unique opportunities to modulate charge transport through single molecules. In recent years, several transmission selection rules have been developed to determine constructive and destructive QIs in an intuitive and simple manner, although some of these rules fail for cross-conjugated systems. In this work, we evaluate the performance of distinct transmission rules on a broad series of anthracene and fluorene derivatives with distinctive structural features including linear-, broken-, and cross-conjugation, heteroatoms, and five-membered rings as such species affords a predictive challenge for the qualitative selection rules for QI effects. The electron transport properties and local transmission plots are first evaluated by combining DFT and the nonequilibrium Green function method allowing for an equal-footing comparison of the conductance of the different polycyclic compounds. Our findings are in line with experimental observations on the influence of the type of conjugation and the connectivity to the metallic electrodes on the transport properties. Thus, cross-conjugated systems exhibit reduced conductance values as compared to the linear-conjugated ones, although the transmission is enhanced in the meta-connected junctions. Remarkably, our study reveals that aromatic cores exhibit generally larger zero-bias conductance for a given connectivity, in contrast to the negative aromaticity-conductance relationship found in literature.
RESUMEN
Inverse sandwich complexes of Yb and Sm stabilized by a bulky ß-diketiminate (BDI) ligand have been prepared: (BDI)Ln(η6,η6-C6H6)Ln(BDI); Ln=lanthanide. Coordinated benzene ligands can be neutral, di-anionic or, often controversially discussed, even tetra-anionic. The formal charge on benzene is correlated to assignment of the metal oxidation state which generally poses a problem. Herein, we take advantage of the structural similarities found when comparing CaII with YbII, and SrII with SmII complexes. In this work, we found an excellent overlap of the Ca/Yb inverse sandwich structures but a striking difference for the Sr/Sm pair. The much shorter Sm-N and Sm-C6H6 distances are strong evidence for a SmIII-benzene-4-SmIII assignment. This was further supported by NMR spectroscopy, magnetic susceptibility, reactivity and comprehensive computational investigation.
RESUMEN
The synthesis and characterization of a homologous series of T-shaped {MNO}10 nitrosyl complexes of the form [M(PR3)2(NO)]+ (M = Pd, Pt; R = tBu, Ad) are reported. These diamagnetic nitrosyls are obtained from monovalent or zerovalent precursors by treatment with NO and NO+, respectively, and are notable for distinctly bent M-NO angles of â¼123° in the solid state. Adoption of this coordination mode in solution is also supported by the analysis of isotopically enriched samples by 15N NMR spectroscopy. Effective oxidation states of M0/NO+ are calculated, and metal-nitrosyl bonding has been interrogated using DFT-based energy decomposition analysis techniques. While a linear nitrosyl coordination mode was found to be electronically preferred, the M-NO and P-M-P angles are inversely correlated to the extent that binding in this manner is prevented by steric repulsion between the bulky ancillary phosphine ligands.
RESUMEN
Spectroscopic and computational examination of a homologous series of rhodium(I) pybox carbonyl complexes has revealed a correlation between the conformation of the flanking aryl-substituted oxazoline donors and the carbonyl stretching frequency. This relationship is also observed experimentally for octahedral rhodium(III) and ruthenium(II) variants and cannot be explained through the classical, Dewar-Chatt-Duncanson, interpretation of metal-carbonyl bonding. Instead, these findings are reconciled by local changes in the magnitude of the electric field that is projected along the metal-carbonyl vector: the internal Stark effect.