A diamagnetic complex, {(cis-indigo-N,N)(2-)(Cp*Ir-III)} (1), in which deprotonated cis-indigo dianions coordinate an iridium center through two nitrogen atoms was obtained. By employment of the ability of the iridium center in 1 to coordinate an additional ligand, the complex [(Bu4N+)2{[Sn-II(Pc3-)](cis-indigo-N,N)Cp2-*Ir-III}(-)(2)0.5(H(2)Indigo)2.5C(6)H(4)C(l2) (2), which has two functional ligands coordinating an Ir-III center, was obtained. This complex has a magnetic moment of 1.71 B at 300 K, in accordance with an S = 1/2 spin state. The spin density is mainly delocalized over the Pc3- macrocycle and partially on (cis-indigo-N,N)(2-). Due to an effective pi-pi interaction, a thermally activated charge transfer from [Sn-II(Pc3-)](-) to (cis-indigo-N,N)(2-) is observed, with an estimated Gibbs energy (-Delta G degrees) of 9.27 +/- 0.18 kJ/mol. The deprotonation of indigo associated with the coordination of Ir-III by the indigo releases H+ ions, which protonate noncoordinating indigo molecules to produce leuco cis-indigo (H(2)Indigo). One H(2)indigo links two (cis-indigo-N,N)(2) dianions in 2 to produce strong N-HO=C and O-HO=C hydrogen-bonding interactions.