The computed fluoride ion affinity (FIA) is a valuable descriptor to assess the Lewis acidity of a compound. Despite its widespread use, the varying accuracy of applied computational models hampers the broad comparability of literature data. Herein, we evaluate the performance of selected methods (like DLPNO-CCSD(T)) in FIA computations against CCSD(T)/CBS data and guide for the choice of suitable density functionals that allow the treatment of larger Lewis acids. Based on the benchmarked methods, we computed an extensive set of gas-phase and solvation corrected FIA, that is covering group 13-16 elements featuring moderate to strong electron-withdrawing substituents (190 entries). It permits an unbiased comparison of FIA over a significant fraction of the periodic table, serves as a source of reference for future synthetic or theoretical studies, and allows to derive some simple design principles for strong fluoride ion acceptors. Finally, the manuscript includes a tutorial section for the computation of FIA with and without the consideration of solvation.

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Ziegler‐Natta (ZN) based co‐polymerization processes for the production of linear low‐density polyethylene (LLDPE) generally give rise to a non‐uniform incorporation distribution of the comonomer. It has been shown that lowering the titanation temperature during catalyst synthesis can increase the evenness of this distribution. However, polymerization process parameters also affect the resulting incorporation distribution. To investigate these factors, a ZN system using a variety of comonomer‐types, at various ‐concentrations and polymerization temperatures is studied. The molecular properties of the polymer samples obtained are analyzed by high‐temperature size‐exclusion chromatography (HT‐SEC). It is shown that a more uniform incorporation distribution of the comonomer can be achieved by lowering either the polymerization temperature or the comonomer concentration, and that lowering both increases the effect.

Gold-catalyzed cyclization of 1,5-diynesw ith ketones as reagents and solvent provides diversely substituted vinyl ethers under mild conditions. The regioselectivity of such gold-catalyzed cyclizations is usually controlled by the scaffold of the diyne. Herein, we report the first solvent-controlled switchingo fr egioselectivity from a6 -endo-dig-to 5endo-dig-cyclization in these transformations,p roviding fulvene derivatives. With respectt ot he functional-group toler-ance, aryl fluorides, chlorides, bromides,and ethers are tolerated. Furthermore, the mechanism and selectivity are put to scrutinyb ye xperimental studies and at hermodynamic analysis of the product. Additionally,6 -(vinyloxy)fulvenesa re a hitherto unknown class of compounds. Theirr eactivity is briefly evaluated, to give insights into their potential applications.[ + + ] Crystallographic investigation;T heoreticali nvestigation Supporting information and the ORCID identification number(s) for the author(s) of this article can be found under: https://doi.

Previously it was demonstrated that triptycene end-capping can be used as ac rystal engineering strategy to directt he packing of quinoxalinophenanthrophenazines (QPPs) towards cofacially stacked p dimers with large molecular overlap resulting in high charge transfer integrals. Remarkably,t his packing motif wasf ormed under different crystallization conditions and with av ariety of derivatives bearing additional functional groups or aromatic substitu-ents. Benzothienobenzothiophene(BTBT) and its derivatives are knowna ss ome of the best performing compounds for organic field-effect transistors. Here, the triptycene end-capping concepti si ntroducedt ot his class of compounds and polymorphic crystal structures are investigated to evaluate the potentialo ft riptycene end-caps as synthons forc rystal engineering.