Catechols occupy a unique role in the structural, bio-, and geochemistry of silicon. Although a wealth of knowledge exists on their hypercoordinate complexes, the structure of tetracoordinate bis­(catecholato)­silane, Si­(catH)2 1, has been enigmatic since its first report in 1951. Indeed, the claim of a planar-tetracoordinated silicon in 1 triggered a prominent debate, which is unsettled to this day. Herewith, we present a comprehensive structural study on 1 and derivatives in the gas phase by electron diffraction, in a neon matrix by IR spectroscopy, in solution by diffusion NMR spectroscopy, and in the solid-state by X-ray diffraction and MAS NMR spectroscopy, complemented by high-level quantum-chemical computations. The compound exhibits unprecedented phase adaptation. In the gas phase, the monomeric bis­(catecholato)­silane is tetrahedral, but in the condensed phase, it is metastable toward oligomerization up to a degree controllable by the type of catechol, temperature, and concentration. For the first time, spectroscopic evidence is obtained for a rapid Si–O σ-bond metathesis reaction. Hence, this study sorts out a long-lasting debate and confirms dynamic covalent features for our Earth’s crust’s most abundant chemical bond.

N‐Heteropolycycles are among the most promising candidates for applications in organic devices. For this purpose, a profound understanding of the low‐energy electronic absorbance and emission characteristics is of crucial importance. Herein, we report high‐resolution absorbance and fluorescence spectra of pentacene (PEN) and 6,13‐diazapentacene (DAP) in solid neon obtained using the matrix‐isolation technique. Accompanying DFT calculations allow the assignment of specific vibrationally resolved signals to corresponding modes. Furthermore, we present for the first time evidence for the formation of van der Waals dimers of both substances. These dimers exhibit significantly different optical characteristics resulting from the change of electronic properties evoked by the incorporation of sp2 nitrogen into the molecular backbone.

N‐Heteropolycycles are attractive as materials in organic electronic devices. However, a detailed understanding of the low‐energy electronic excitation characteristics of these species is still lacking. In this work, the matrix isolation technique is applied to obtain high‐resolution absorbance spectra for a series of tetracene and core‐substituted N‐analogues. The experimental electronic excitation spectra obtained for matrix‐isolated molecules are then analysed with the help of quantum‐chemical calculations. Additional lower energy excitation bands in the spectrum of the core‐substituted N‐derivatives of tetracene could be explained in terms of intensity borrowing from dipole‐forbidden transitions due to Herzberg–Teller vibronic coupling. In the case of tetracene, evidence for the additional formation of London dimers (J aggregates) is found at higher tetracene concentrations in the matrix.

Amide-substituted diynes were cyclized in the presence of ac ationic gold catalyst and an external nucleophile leadingt o1 -indenones and 1-iminoindenones. The electron-donating features of the nitrogen atom enable the formation of ar eactive ketenei miniumi on, which can be trapped by either diphenyl sulfoxide or anthranil as nucleophiles in as ubsequent oxidations tep, providings ubstituted inden-1-on-3-carboxamides.Scheme1.Dual activationofd iynes andfurtherreactions.Scheme2.Formation of ak etene iminiumi on.Scheme3.Initiale xperiment.

The bonding between two neutral aromatic compounds, especially small ones, has been controversially debated in the last decades, and terms like “π‐stacking” had to be revised. Surprisingly, despite of many experimental and computational work, there is still no clear consensus about the structure of and the bonding in the pyridine dimer. In this work, for different isomeric forms of the pyridine dimer, the structures and bonding were elucidated by combining high‐resolution matrix‐isolation spectroscopic results with quantum‐chemical calculations. High‐resolution IR spectra of Ne matrices at 4 K containing pyridine were recorded for different concentrations and upon annealing to 10 and 12 K, relying on three isotopologues of pyridine. The spectra show the presence of hydrogen‐bonded, T‐shaped, and stacked forms of weakly‐bound pyridine dimers. Among these, the hydrogen‐bonded isomer is identified as the lowest‐energy form. The results provide for the first time conclusive information about the interaction between two pyridine dimers.