A formal gold-for-chromium transmetalation allowed the gold carbenoid species [Cy3 PAuCAr2 ]NTf2 (11) (Ar=pMeOC6 H4 -) to be obtained in crystalline form. The structure in the solid state suggests that there is only little back donation of electron density from gold to the carbene center of 11 and hence very modest AuC double-bond character; rather, it is the organic ligand framework that is r...

A new hexaazatriphenylene (HAT) derivative formed by the fusion of three HAT units has been prepared and its electronic and molecular structures have been fully characterized by optical and vibrational Raman spectroscopy, electrochemistry, solid-state UV and inverse photoemission spectroscopy (UPS and IPES), and by quantum-chemical calculations. A comparative HAT versus tri-HAT study was perfor...

In the title compound, C(20)H(18)N(2)O, the pyrazole ring adopts a planar conformation. The C-N bond lengths in the pyrazole ring are shorter than a standard C-N single bond (1.443 Å), but longer than a standard double bond (1.269 Å), indicating electron delocalization. The propenal group assumes an extended conformation. Inter-molecular C-H⋯O hydrogen bonds connect mol-ecules into cyclic centr...

Photo-induced charge transfer at molecular heterojunctions has gained particular interest due to the development of organic solar cells (OSC) based on blends of electron donating and accepting materials. While charge transfer between donor and acceptor molecules can be described by Marcus theory, additional carrier delocalization and coherent propagation might play the dominant role. Here, we d...

Crystalline solids self-assembled from anionic and cationic porphyrins provide a new class of multifunctional optoelectronic micro- and nanomaterials. A 1 : 1 combination of zinc(II) tetra(4-sulfonatophenyl)porphyrin (ZnTPPS) and tin(IV) tetra(N-methyl-4-pyridiniumyl)porphyrin (SnTNMePyP) gives porphyrin nanosheets with high aspect ratios and varying thickness. The room temperature preparation ...

The influence of several substituents on the ring-opening elementary step of cyclobutene-like systems is analyzed computationally in detail. We focus on trans-1,2-disiloxycyclobutene-like molecules. Electronic effects (hyperconjugation and π delocalization) and geometrical constraints are decoupled and allow for an instructive analysis. It is found that the energy difference between closed and ...

The asymmetric unit of title salt co-crystal, [K(C9H11N2S2)(C12H24O6)], comprises a K(+) cation, an (-)S2CN(Et)py anion and a 18-crown-6 mol-ecule. Substantial delocalization of π-electron density is evident in the di-thio-carbamate anion, as indicated by the equivalent C-S bond lengths. The K(+) cation sits within an O6S2 donor set lying 0.7506 (6) Å out of the least-squares plane through the ...

Radical stabilization energies (RSEs) for a wide variety of nitrogen-centered radicals and their protonated counterparts have been calculated at G3(MP2)-RAD and G3B3 level. The calculated RSE values can be rationalized through the combined effects of resonance delocalization of the unpaired spin, electron donation through adjacent alkyl groups or lone pairs, and through inductive electron donat...

Halogen bonds are shown to possess the same characteristics as hydrogen bonds: charge transfer, resonance assistance and cooperativity. This follows from the computational analyses of the structure and bonding in N-halo-base pairs and quartets. The objective was to achieve an understanding of the nature of resonance-assisted halogen bonds (RAXB): how they resemble or differ from the better unde...

Stability of the π-π stacking interactions in the Ben||substituted-coronene and HFBen||substituted-coronene complexes was studied using the computational quantum chemistry methods (where Ben and HFBen are benzene and hexaflourobenzene, || denotes π-π stacking interaction, substituted-coronene is coronene molecule which substituted with four X groups, and X= NH2, CH3, OH, H, F, CF3, CN and NO). ...