Anhydrous H[BH (CN) ] crystallizes from acidic aqueous solutions of the dicyanodihydridoborate anion. The formation of H[BH (CN) ] is surprising as the protonation of nitriles requires strongly acidic and anhydrous conditions but it can be rationalized based on theoretical data. In contrast, [BX(CN) ] (X=H, F) gives the expected oxonium salts (H O)[BX(CN) ] while (H O)[BF (CN) ]/H[BF (CN) ] is unstable. H[BH (CN) ] forms chains via N-H⋅⋅⋅N bonds in the solid state and melts at 54 °C. Solutions of H[BH (CN) ] in the room-temperature ionic liquid [EMIm][BH (CN) ] contain the [(NC)H BCN-H⋅⋅⋅NCBH (CN)] anion and are unusually stable, which enabled the study of selected spectroscopic and physical properties. [(NC)H BCN-H⋅⋅⋅NCBH (CN)] slowly gives H and [(NC)H BCN-BH(CN) ] . The latter compound is a source of the free Lewis acid BH(CN) , as shown by the generation of [BHF(CN) ] and BH(CN) ⋅py.

Controlling the nanoscale morphology in assemblies of π‐conjugated molecules is key to developing supramolecular functional materials. Here, we report an unsymmetrically substituted amphiphilic PtII complex 1 that shows unique self‐assembly behavior in nonpolar media, providing two competing anti‐cooperative and cooperative pathways with distinct molecular arrangement (long‐ vs. medium‐slipped, respectively) and nanoscale morphology (discs vs. fibers, respectively). With a thermodynamic model, we unravel the competition between the anti‐cooperative and cooperative pathways: buffering of monomers into small‐sized, anti‐cooperative species affects the formation of elongated assemblies, which might open up new strategies for pathway control in self‐assembly. Our findings reveal that side‐chain immiscibility is an efficient method to control anti‐cooperative assemblies and pathway complexity in general.

Carba-closo-dodecaborate anions with two functional groups have been synthesized via a simple two-step procedure starting from monoamino-functionalized {closo-1-CB11 } clusters. Iodination at the antipodal boron atom provided access to [1-H2 N-12-I-closo-1-CB11 H10 ](-) (1 a) and [2-H2 N-12-I-closo-1-CB11 H10 ](-) (2 a), which have been transformed into the anions [1-H2 N-12-RCC-closo-1-CB11 H10 ](-) (R=H (1 b), Ph (1 c), Et3 Si (1 d)) and [2-H2 N-12-RCC-closo-1-CB11 H10 ](-) (R=H (2 b), Ph (2 c), Et3 Si (2 d)) by microwave-assisted Kumada-type cross-coupling reactions. The syntheses of the inner salts 1-Me3 N-12-RCC-closo-1-CB11 H10 (R=H (1 e), Et3 Si (1 f)) and 2-Me3 N-12-RCC-closo-1-CB11 H10 (R=H (2 e), Et3 Si (2 f)) are the first examples for a further derivatization of the new anions. All {closo-1-CB11 } clusters have been characterized by multinuclear NMR and vibrational spectroscopy as well as by mass spectrometry. The crystal structures of Cs1 a, [Et4 N]2 a, K1 b, [Et4 N]1 c, [Et4 N]2 c, 1 e, and [Et4 N][1-H2 N-2-F-12-I-closo-1-CB11 H9 ]⋅0.5 H2 O ([Et4 N]4 a⋅0.5 H2 O) have been determined. Experimental spectroscopic data and especially spectroscopic data and bond properties derived from DFT calculations provide some information on the importance of inductive and resonance-type effects for the transfer of electronic effects through the {closo-1-CB11 } cage.

A gold(I)-catalysed direct thioetherification reaction between allylic alcohols and thiols is presented. The reaction is generally highly regioselective (SN2′). This dehydrative allylation procedure is very mild and atom economical, producing only water as the by-product and avoiding any unnecessary waste/steps associated with installing a leaving or activating group on the substrate. Computational studies are presented to gain insight into the mechanism of the reaction. Calculations indicate that the regioselectivity is under equilibrium control and is ultimately dictated by the thermodynamic stability of the products.

Understanding the relationship between molecular design and packing modes constitutes one of the major challenges in self‐assembly and is essential for the preparation of functional materials. Herein, we have achieved high precision control over the supramolecular packing of amphiphilic PtII complexes by systematic variation of the hydrophilic side‐chain length. A novel approach of general applicability based on complementary X‐ray diffraction and solid‐state NMR spectroscopy has allowed us to establish a clear correlation between molecular features and supramolecular ordering. Systematically increasing the side‐chain length gradually increases the steric demand and reduces the extent of aromatic interactions, thereby inducing a gradual shift in the molecular packing from parallel to a long‐slipped organization. Notably, our findings highlight the necessity of advanced solid‐state NMR techniques to gain structural information for supramolecular systems where single‐crystal growth is not possible. Our work further demonstrates a new molecular design strategy to modulate aromatic interaction strengths and packing arrangements that could be useful for the engineering of functional materials based on PtII and aromatic molecules.