A Heterotetranuclear Zinc(II)-Cerium(IV) Salamo Complex Possessing Deca- and Dodeca-Coordinated Cerium(IV) Atoms: Synthesis, Structure, and Photophysical Properties

A heterotetranuclear zinc(II)-cerium(IV) complex [(ZnL) 2 Ce(OAc) 2 ][Ce(NO 3 ) 6 ] · Py (H 2 L = 6,6′-methoxy-2,2′-[1,2-ethylenedioxybis(nitrilomethylidyne)]diphenol and Py = pyridine) is successfully prepared by a one-pot reaction of a Salamo-type ligand H 2 L with Zn(OAc) 2 ·2H 2 O, Ce(NO 3 ) 3 -6H 2 O, and an auxiliary ligand Py. The Zn n -Ce IV complex consists of one dicationic [(ZnL) 2 Ce(OAc) 2 ] 2+ unit with a deca-coordinated Ce IV atom, one [Ce(NO 3 )6] 2− dianionic unit with a dodeca-coordinated Ce IV atom, and one uncoordinated Py molecule. Interestingly, the two Ce IV atoms are positive tetravalent, which may probably be due to the oxidation of trivalent Ce m atoms during the reaction. Moreover, the photophysical properties of the Zn n -Ce IV complex are studied.