A versatile and rapid access to various chain lengths of ethylene-bridged BODIPY motifs was discovered. Corresponding oligomers comprising up to eight monomeric units were studied with respect to their microstructures by photophysical, X-ray crystallographic, and computational means. The investigation of three different dipyrrin cores revealed a crucial dependence on the substitution pattern of the core, whereas the nature of the meso-periphery is less critical. The impact of substituent effects on the conformational space was investigated by Monte Carlo simulations and a set of DFT methods (B3LYP, PBEh-3c, TPSS/PWPB95), including dispersion effects. Cryptopyrrole-derived oligo-BODIPYs are characterized by a tight intramolecular arrangement triggering a dominant J-type excitonic coupling with red-shifts up to 45 nm, exceptionally small line widths of the absorption and emission event (up to 286 cm), outstandingly high attenuation coefficients (up to 1 042 000 M cm), and quantum yields of up to unity.

Several pnictogen dihalide complexes of the type (WCA‐IDipp)EX2 (E=P, As, Sb; X=Cl, Br) that bear an anionic N‐heterocyclic carbene ligand with a weakly coordinating borate moiety (WCA‐IDipp, WCA=B(C6F5)3, IDipp=1,3‐bis(2,6‐diisopropylphenyl)imidazolin‐2‐ylidene) were prepared by salt metathesis reactions between the respective pnictogen trihalides EX3 and the lithium salt (WCA‐IDipp)Li⋅toluene. Two‐electron reduction of the dihalides (WCA‐IDipp)EX2 with 1,3‐bis(trimethylsilyl)‐1,4‐dihydropyrazine or elemental magnesium afforded the dipnictenes (WCA‐IDipp)2E2, which display typical element‐element double bonds as observed in diaryldiphosphenes, ‐arsenes and ‐stibenes. To provide an insight into the factors contributing to the structural stability of the pnictogen dihalide and dipnictene compounds, quantum chemical calculations were performed at the domain‐based local pair natural orbital coupled‐cluster (DLPNO‐CCSD(T)) level. A local energy decomposition (LED) analysis of the interaction between the carbene and the pnictogen dihalide or dipnictene moiety demonstrates that London dispersion is an essential factor for the stabilization of these compounds.

Several group 16 adducts of the type [(WCA-IDipp)E]Li(solv.) that bear an anionic N-heterocyclic carbene ligand with a weakly coordinating borate moiety (WCA-IDipp, WCA = B(C6F5)3, IDipp = 1,3-bis(2,6-diisopropylphenyl)imidazolin-2-ylidene, E =...

A modular approach afforded heteroleptic arsaphosphene species supported by neutral and anionic N-heterocyclic carbenes.

A series of neutral iridium(I) complexes of the general type [(WCA−NHC)]IrL(COD)] (COD=1,5‐cyclooctadiene; L=phosphine, pyridine), bearing anionic N‐heterocyclic carbenes (WCA−NHC) with a weakly coordinating anionic (WCA) borate moiety, were prepared by addition of phosphines and pyridine to [(WCA−NHC)]Ir(COD)], in which the available coordination site is stabilized by intramolecular metal‐arene interaction (π‐face donation). The solvent and substrate scope of the neutral complexes as catalysts for H/D exchange was investigated, revealing their suitability for promoting efficient deuteration in nonpolar solvents such as cyclohexane.