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We use different halido ligands to tune metal-metal interactions, nucleation pathways and hetero-seeded growth in supramolecular copolymerizations.

The self-assembly of discrete molecular entities into functional nanomaterials has become a major research area in the past decades. The library of investigated compounds has diversified significantly, while the field as a whole has matured. The incorporation of metal ions in the molecular design of the (supra-)molecular building blocks greatly expands the potential applications, while also offering a promising approach to control molecular recognition and attractive and/or repulsive intermolecular binding events. Hence, supramolecular polymerization of metal-containing monomers has emerged as a major research focus in the field. In this perspective article, we highlight recent significant advances in supramolecular polymerization of metal-containing monomers and discuss their implications for future research. Additionally, we also outline some major challenges that metallosupramolecular chemists (will) have to face to produce metallosupramolecular polymers (MSPs) with advanced applications and functionalities., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

We report on the synthesis of the first examples of 1,3-azaborinine derived oxindole systems, the BN-isosteres of the important compound class of the oxindoles. Hydroboration of terminal aryl acetylenes with FmesBH2, followed by treatment with 2 equiv. of a glycine ester derived isonitrile gave a small series of 1,3-azaborinine derived oxindoles. The new BN-oxindoles show interesting photophysical behavior.

In recent years, the development of sophisticated analytical tools, kinetic models and sample preparation methods has significantly advanced the field of supramolecular polymerization, where the competition of kinetic vs. thermodynamic processes has become commonplace for a wide range of building blocks. Typically, the kinetic pathways are identified in thermally controlled assembly experiments before they ultimately evolve to the thermodynamic minimum. However, there might be cases where the identification and thus the assessment of the influence of kinetic aggregates is not trivial, making the analysis of the self-assembly processes a hard task. Herein, we demonstrate that "hidden" kinetic pathways can have drastic consequences on supramolecular polymerization processes, to the point that they can even overrule thermodynamic implications. To this end, we analyzed in detail the supramolecular polymerization of a chiral Pd II complex 1 that forms two competing aggregates ( Agg I and Agg II ) of which kinetic Agg II is formed through a "hidden" pathway, i.e. this pathway is not accessible by common thermal polymerization protocols. The hidden pathway exhibits two consecutive steps: first, Agg II is formed in a cooperative process, which subsequently evolves to clustered superstructures driven by rapid kinetics. At standard conditions, Agg II displays an extraordinary kinetic stability (>6 months), which could be correlated to its cooperative mechanism suppressing nucleation of thermodynamic Agg I . Furthermore, the fast kinetics of cluster formation sequester monomers from the equilibria in solution and prevents the system from relaxing into the thermodynamic minimum, thus highlighting the key implications of hidden pathways in governing supramolecular polymerization processes., (This journal is © The Royal Society of Chemistry 2020.)