Shape Complementary Coordination Self-Assembly of a Redox-Active Heteroleptic Complex

We present here the coordination self-assembly of a new heteroleptic (bpyPd)(4)(LL22)-L-1 coordination complex (1) from one novel pyridinium-functionalized bis-2,4,6-tris(pyridin-3-yl)-1,3,5-triazine (bis-3-TPT, L-1) macrocyclic ligand, two separate 3-TPT (L-2) ligands, and four cis-blocking bpyPd(NO3)(2) (bpy = 2,2'-bipyridine). While homoleptic self-assemblies with either L-1 or L-2 gave dynamic mixtures of products, a single thermodynamic heteroleptic complex was obtained driven by the shape complementarity of building blocks. Moreover, the redox-active nature of the heteroleptic assembly facilitates the highly efficient catalytic aerobic photo-oxidation of aromatic secondary alcohols under mild conditions.