Synthetic approaches to iridium complexes of metal phthalocyanines (Pc) and fullerene anions have been developed to give three types of complexes. The compound{(Cp*IrIIII2)SnIIPc(2−)}·2C6H4Cl2 (1) (Cp* is pentamethylcyclopentadienyl) is the first crystalline complex of a metal phthalocyanine in which an iridium(III) atom is bonded to the central tin(II) atom of Pc via a Sn–Ir bond length of 2.58 Å. In (TBA+)(C60•–){(Cp*IrIIII2)SnIIPc(2−)}·0.5C6H14 (2), the {(Cp*IrIIII2)SnIIPc(2−)} units cocrystallize with (TBA+)(C60•–) to form double chains of C60•– anions and closely packed chains of {(Cp*IrIIII2)SnIIPc(2−)}. Interactions between the fullerene and phthalocyanine subsystems are realized through π–π stacking of the Cp* groups of {(Cp*IrIIII2)SnIIPc(2−)} and the C60•– pentagons. Furthermore, the spins of the C60•– are strongly antiferromagnetically coupled in the chains with an exchange interaction J/kB = −31 K. Anionic (TBA+){(Cp*IrIICl)(η2-C60–)}·1.34C6H4Cl2 (3) and (TBA+){(Cp*IrIII)(η2-C60–)}·1.3C6H4Cl2·0.2C6H14 (4) are the first transition metal complexes containing η2-bonded C60– anions, with the Cp*IrIICl and Cp*IrIII units η2-coordinated to the 6–6 bonds of C60–. Magnetic measurements indicate diamagnetism of the {(Cp*IrIICl)(η2-C60–)} and {(Cp*IrIII)(η2-C60–)} anions due to the formation of a coordination bond between two initially paramagnetic Cp*IrIICl or Cp*IrIII groups and C60•– units. DFT calculations support a diamagnetic singlet ground state of 4, in which the singlet–triplet energy gap is greater than 0.8 eV. DFT calculations also indicate that the C60 molecules are negatively charged.