Zirconium(IV) Metallocavitands As Blue-Emitting Materials

A series of zirconium-carboxylate metallocavitands with the general formula [(CpZr)3(μ-κ2,O′,O″CR)3(μ3-O)­(μ2-OH)3]Cl (Cp = cyclopentadienyl; R = C5H4N (5), C6H7N (6), C18H14N (7), and C18H12N (8)) were synthesized in moderate to high yields (40–83%) by reacting the corresponding carboxylic acids 1–4 with Cp2ZrCl2 in a self-assembly procedure at room temperature. The metallocavitands were characterized using 1H and 13C NMR spectroscopy and by single-crystal X-ray diffraction. Complexes 7 and 8 exhibit efficient photoluminescence properties in solution. The photoluminescence peak of 7 was observed at 464 nm and that of 8 at 422 nm with respective quantum yields in solution of 87 and 65%.