Supramolecular Assemblies with Symmetrical Octahedral Structures – Synthesis, Characterization, and Electrochemical Properties



Functional nanosized cage complexes with an octahedral framework have been synthesized by the facile self-assembly reactions of six 90° PdII-containing compounds {[Pd(dppf)(OTf)2] or [Pd(PPh3)(OTf)2], dppf = 1,1′-bis(diphenylphosphanyl)ferrocene, OTf = trifluoromethylsulfonate} and four 120° functional tritopic ligands [2,4,6-tri(4-pyridyl)-1,3,5-triazine] in acetone. Diffusion-ordered NMR spectroscopy (DOSY) and AFM images clarify the formation of 3–4 nm nanoparticles. These highly symmetrical cage complexes are discrete, face-directed, functional nanoparticles with symmetrical octahedral structures. The self-assembled functional cage complexes exhibit interesting electrochemical activities, and thus will potentially be useful in the catalysis of redox reactions, the encapsulation of sizeable guest molecules and the control of organic synthetic reactions.