In Situ Tandem Synthesis of Charged Boron‐Oxo Clusters into Highly Ordered Architectures

Abstract

Abstract The controlled assembly of multiple cationic and anionic clusters into well‐defined architectures remains one of the major challenges in chemistry. In this work, a series of charged boron‐oxo cluster‐based structures, named BOC‐n ( n  = 1–8) have been successfully synthesized using an in situ tandem strategy. Through the comprehensive combination of the dynamic covalent chemistry and coordination interactions, porphyrin‐like cationic metal boron‐oxo clusters ([Cu(II)B 8 O 8 Qi 8 ] 2+ in BOC‐1 and [Cu(II) 2 B 10 O 12 (Qi) 8 ] 2+ in BOC‐2 to 8 ; Qi = quinoline) have been developed. These cationic clusters further exhibit versatile dynamic properties and maintain directional control through metrically matched π─π stacking and C─H···π interactions during assembly, enabling the formation of highly ordered architectures with diverse incoming ligands and various guest anions. Notably, BOC‐2 can reversibly respond to guest molecules through electrostatic interaction to facilitate anion exchange. Furthermore, the modulation of axial ligands and guest anions influence their optical third‐order nonlinear properties.