Effect of One- and Two-Electron Reduction of Terbium(III) Double-Decker Phthalocyanine on Single-Ion Magnet Behavior and NIR Absorption.

Reduction of terbium(III) double-decker phthalocyanine, TbPc (1), by sodium fluorenone ketyl in the presence of bis(triphenylphosphoranylidene)ammonium cations yields one-electron-reduced (PPN){Tb(Pc)}·2.5CHCl (2) containing the dianionic Pc macrocycles, whereas a stronger NaCpCo(CO) reductant in the presence of an excess of cryptand yields two-electron-reduced {Cryptand(Na)}{(Pc)Tb(Pc)} (3) containing the Pc radical trianionic macrocycle. Isolated pairs of the {Tb(Pc)} anions are formed in 2, whereas compound 3 has unique 3D packing of the macrocycles with weak π-orbitals overlapping in all three directions.