Relativistic electronic structure of cadmium(II) multidecker phthalocyanine compounds

Abstract Cadmium phthalocyanines (Pc) give rise to multilayered compounds, which may have potential application in material science. The Cd(II) single macrocycle ( 1 ) ( C 4 v ), double decker [CdPc 2 ] ( 2 ) ( D 4 ), triple decker [Cd 2 Pc 3 ] ( 3 ) ( D 4 h ) and quadruple decker [Cd 3 Pc 4 ] ( 4 ) ( D 4 d ), are already characterized experimentally. The electronic structures of the multidecker compounds were compared against the single macrocycle ( 1 ) which is used as benchmark. Relativistic electronic structure were carried out via DFT calculations using the two components ZORA Hamiltonian including both scalar and spin–orbit effects. Double point groups were used to take into account the inclusion of the spin–orbit coupling, and their group correlation is shown. The calculations show that the quadruple decker is the most reactive and behaves like a one-dimensional molecular metal.