Formation of a Pd₁₆ Molecular Basket Architecture of Reduced Symmetry and Angular Deviation in a Fluorenone Scaffold to Govern the Host–Guest Chemistry of Pd₆ Trifacial Tubes

The employment of flexible ligands with significant conformational freedom in coordination-driven self-assembly enables the formation of unique and intricate structures. In this study, the self-assembly of such a fluorenone-appended ligand (<b>L1</b>) with a sterically demanding acceptor, [Pd-(tmed)-(ONO₂)₂] (<b>M1</b>), generated a new and unique molecular basket architecture, (<b>M1</b>) <b>₁₆</b> (<b>L1</b>) <b>₈</b> (<b>B</b>), featuring a large hollow cavity. <b>B</b> possesses an unusual twisted architecture of low symmetry, consisting of 16 Pd-(II) centers arranged as four tetrahedra connected by eight flexible ligands, representing a structurally complex system reminiscent of biological architectures. Designing such entropically disfavored, large architectures of reduced symmetry is challenging but desirable, since they can act as ideal models to study complicated natural systems. The host-guest property of supramolecular hosts is governed by the confined cavities and noncovalent interactions, which are dictated by the angular disposition of ligand coordination sites. To explore this, the fluorenone scaffold was used to synthesize two other tetradentate ligands (<b>L2</b> and <b>L3</b>) that differed in the spatial distributions of their coordination vectors. The self-assembly of these ligands with [Pd-(en)-(ONO₂)₂] (<b>M2</b>) resulted in the formation of water-soluble (<b>M2</b>) <b>₆</b> (<b>L1</b>/<b>L2</b>/<b>L3</b>) <b>₃</b> trifacial tubes of different geometries with varying internal cavity dimensions. These angular variations further altered the orientation of the fluorenone carbonyl groups within the cavities, thereby modulating their guest binding abilities and highlighting the importance of tailoring supramolecular hosts for specific guest binding.