Reduction of terbium(III) double-decker phthalocyanine, (TbPc2)-Pc-III (1), by sodium fluorenone ketyl in the presence of bis(triphenylphosphoranylidene)ammonium cations yields one-electron-reduced (PPN+){Tb-III(Pc2-)(2)}(-)center dot 2.5C(6)H(4)Cl(2) (2) containing the dianionic Pc2- macrocycles, whereas a stronger NaCpCo(CO)(2) reductant in the presence of an excess of cryptand yields two-electron-reduced {Cryptand(Na+)}(2){(Pc2-)Tb-III(Pc center dot 3-)}(2-) (3) containing the Pc center dot 3- radical trianionic macrocycle. Isolated pairs of the Tb-III(Pc2-)(2)}(-) anions are formed in 2, whereas compound 3 has unique 3D packing of the macrocycles with weak pi-orbitals overlapping in all three directions. This is the first example of the two-electron-reduced lanthanide double-decker containing Pc center dot 3- radical trianion studied in solid state. Compound 2 manifests single-ion magnet (SIM) behavior with a large effective spin-reversal energy barrier of U-eff = 538 cm(-1) in comparison with previously studied (Bu4N+){Tb-III(Pc2-)(2)}(-) (U-eff = 230 cm(-1)). Thus, changes in cation size and shape affect the molecular packing of {Tb-III(Pc2-)(2)}(-) and increase the spin-reversal energy barrier. At the same time, two-electron-reduced species 3 containing Tb-III and Pc center dot 3- show no signs of SIM such as hysteresis loop at 1.9 K, and no peaks are observed on the temperature dependencies of in-phase (chi') and out-of-phase (chi '') signals. In contrast to EPR silent 2, both compounds 1 and 3 manifest broad signals from paramagnetic Tb-III ions. Narrower signals attributed to Pc center dot 3- are of high intensity only in 3. In addition to the absorption bands of Pc in the UV and visible spectral range, compound 3 manifests the lowest energy absorption band in solid-state spectra even in the near IR range at 4700 cm(-1) (2130 nm), whereas such bands are not observed in the spectrum of 2. These data show that the reduction of the Pc macrocycles in the lanthanide double-deckers leads to the appearance of new very low-energy new transitions associated with Pc center dot 3- whose energy is the lowest among known reduced metal phthalocyanines.