Structure–property relationship of carborane–embedded cationiciridium(III) complexes was investigated in this work, especially with donor-acceptor-type ligands. Firstly, an efficient synthetic approach for the new donor-acceptor-type ligands (2 and 4 ) was developed. By using these ligands, novel iridium(III) complexesII and IV were prepared. Complex IV shows about 92 nm red-shift in solution (ФP = 0