Neutron diffraction of tri(3,5-tert-butylphenyl)methane at 20 K reveals an intermolecular C-H···H-C distance of only 1.566(5) Å, which is the shortest reported to date. The compound crystallizes as a C-symmetric dimer in an unusual head-to-head fashion. Quantum chemical computations of the solid state at the HSE-3c level of theory reproduce the structure and the close contact well (1.555 Å at 0 K) and emphasize the significance of packing effects; the gas-phase dimer structure at the same level shows a 1.634 Å C-H···H-C distance. Intermolecular London dispersion interactions between contacting tert-butyl substituents surrounding the central contact deliver the decisive energetic contributions to enable this remarkable bonding situation.

The formation of a bis(μ-oxido)dicopper complex with the ligand 2-(diethylaminoethyl)-6-phenylpyridine (PPN) and its subsequent hydroxylation of the pendant phenyl group (studied earlier by Holland et al., Angew. Chem. Int. Ed.- 1999, 38, 1139-1142) has been reinvestigated to gain a better understanding of such systems in view of the development of new synthetic applications. To this end, we prepared a simple copper imine complex system that also affords selective o-hydroxylation of aromatic aldehydes by using dioxygen as the oxidant: Applying the ligand N'-benzylidene-N,N-diethylethylenediamine (BDED), salicylaldehyde was prepared in good yields and we show that this reaction also occurs through an intermediate bis-μ-oxido copper complex. The underlying reaction mechanism for the PPN-supported complex was studied at the BLYP-D/TZVP level of density functional theory and the results for representative stationary points along reaction paths of the BDED-supported complex reveal a closely related mechanistic scenario. The results demonstrate a new facile synthetic way to introduce OH groups into aromatic aldehydes.

Double perovskites are promising candidates for less toxic and highly stable metal halide perovskites, but their optoelectronic performances still lag behind those of the lead halide counterpart, due to the indirect nature of the bandgap and the strong electron–phonon coupling. Reducing the dimensionality of Cs2AgBiBr6 down to a 2D layered form is strategic in order to tune the band gap from indirect to direct and provides new insights into the structure–property relationships of double perovskites. Herein, we report on a series of monolayer 2D hybrid double perovskites of formula (RA)4AgBiBr8, where RA represents different primary ammonium large cations with alkyl- and aryl-based functionalities. An in-depth experimental characterization of structure, film morphology, and optical properties of these perovskites is carried out. Interestingly, the variation of the ammonium cation and the interplanar distance between adjacent inorganic monolayers has peculiar effects on the film-forming ability and light emission properties of the perovskites. Experiments have been combined with DFT calculations in order to understand the possible origin of the different emissive features. Our study provides a toolbox for future rational developments of 2D double perovskites, with the aim of narrowing the gap with lead halide perovskite optoelectronic properties.

The long-known, ubiquitously present, and always attractive London dispersion (LD) interaction was probed with hexaphenylethane (HPE) derivatives. A series of all-meta hydrocarbyl [Me, i Pr, t Bu, Cy, Ph, 1-adamantyl (Ad)]-substituted triphenylmethyl (TPM) derivatives [TPM–H, TPM–OH, (TPM–O)2, TPM•] was synthesized en route, and several derivatives were characterized by single-crystal X-ray diffraction (SC-XRD). Multiple dimeric head-to-head SC-XRD structures feature an excellent geometric fit between the meta-substituents; this is particularly true for the sterically most demanding t Bu and Ad substituents. NMR spectra of the i Pr-, t Bu-, and Cy-derived trityl radicals were obtained and reveal, together with EPR and UV–Vis spectroscopic data, that the effects of all-meta alkyl substitution on the electronic properties of the trityl scaffold are marginal. Therefore, we concluded that the most important factor for HPE stability arises from LD interactions. Beyond all-meta t Bu-HPE we also identified the hitherto unreported all-meta Ad-HPE. An intricate mathematical analysis of the temperature-dependent dissociation constants allowed us to extract ΔG d 298(exptl) = 0.3(5) kcal mol–1 from NMR experiments for all-meta t Bu-HPE, in good agreement with previous experimental values and B3LYP-D3­(BJ)/def2-TZVPP­(C-PCM) computations. These computations show a stabilizing trend with substituent size in line with all-meta Ad-HPE (ΔG d 298(exptl) = 2.1(6) kcal mol–1) being more stable than its t Bu congener. That is, large, rigid, and symmetric hydrocarbon moieties act as excellent dispersion energy donors. Provided a good geometric fit, they are able to stabilize labile molecules such as HPE via strong intramolecular LD interactions, even in solution.

Multi-state photoswitchable compounds are highly attractive for application in data storage or multi-responsive materials. Herein, a trisazobenzene macrocycle is presented, which can be switched selectively into three individual states.