Differentiable Formation of Chiroptical Lanthanide Heterometallic Ln(n)Ln'(4-n)(L-6) (n=0-4) Tetrahedra with C-2-Symmetrical Bis(tridentate) Ligands

Construction of lanthanide heterometallic complex is important for engineering multifunction molecular containers. However, it remains a challenge because of the similar ionic radii of lanthanides. Herein we attempt to prepare chiral lanthanide heterometallic tetrahedra. Upon crystallization with a mixture of [Eu2L3] and [Ln(2)L(3)] (Ln=Gd, Tb and Dy) helicates, a mixture of heterometallic Eu(n)Ln'(4-n)(L-6) (n=0-4) tetrahedra was prepared. Selective formation of heterometallic tetrahedron was observed as MS deconvolution results deviated from statistical results. The formation of heterometallic tetrahedron was found to be sensitive to ionic radii as well as the ratio of the two helicates used in the crystallization.