Highly Accurate Synthesis of Quasi‐sub‐nanoparticles by Dendron‐assembled Supramolecular Templates

Abstract

AbstractQuasi‐sub‐nanomaterials (1–3 nm) have been predicted to exhibit unique properties originating from the gray structures considered both bulk solids and molecules, while their synthesis is extremely difficult. The present study describes a new template synthesis method for quasi‐sub‐nanosized materials using a combination of coordination chemistry and polymer chemistry. Utilizing self‐assembly of guest basic phenylazomethine dendron units onto host acidic core units with six tritylium cations, the dendron‐assembled supramolecules were constructed easily and quantitatively without costly techniques. This huge supramolecular capsule accumulating multiple acidic rhodium salts in its basic ligands enabled a precise synthesis of rhodium particles via formation of multinuclear complexes. The obtained particles (Rh84, ≈1.5 nm) have particle sizes within 1–3 nm range and were larger than conventional sub‐nanoparticles (Rh14, ≈0.85 nm), therefore the precise template synthesis of quasi‐sub‐nanoparticles was successfully demonstrated.