Structures of the neutral and positively charged forms of the 4,4′,4″-tris( N , N -phenyl-3-methylphenylamino)triphenylamine (m-MTDATA) molecule and its dimer, and charge localization in the corresponding cationic species

The structures of the 4,4′,4″-tris(N,N-phenyl-3-methylphenylamino)triphenylamine (m-MTDATA) molecule and its dimer in their neutral and positively charged forms were studied by performing quantum-chemical calculations at the Hartree−Fock (HF) and density functional theory (DFT) levels of theory using several exchange-correlation functionals (PBE, PBE0, BHANDHLYP, and M06-HF) with different percentages of HF exchange. It was found that there are at least four possible isomeric structures of m-MTDATA with different (planar or perpendicular) arrangements of the peripheral diphenylamino groups. The charge localization in the monomeric and dimeric cationic species was also determined. The results indicated that the charge on the dimeric cation is localized on the central region or on the side fragment of the cationic part of the dimer, depending on the dimer structure. DFT calculations showed a tendency to overestimate the charge delocalization over the molecule, irrespective of the percentage of HF exchange applied.