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

We present here the coordination self-assembly of a new heteroleptic (bpyPd) 4 L 1 L 2 2 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(NO 3 ) 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.