AbstractBy changing the chemical composition of phthalocyanine molecules, the electrical properties of the ensemble in the solid state can be influenced directly. This is shown for phthalocyaninatomanganese (PcMn) as compared with purely divalent central metals and for complexes in which the ligand system has been modified by either electron‐withdrawing heteroatoms such as N instead of CH leading to tetrapyridotetraazaporphyrinatozinc (TPyTAPZn) or substituents such as F instead of H leading to hexadecafluorophthalocyaninatozinc (F16PcZn). The accessibility of additional oxidation states of Mn or the stabilisation of frontier orbital states by the ligand leads to a lower ionisation potential and interactions with impurities or dopant molecules are changed. A change in the observed majority carrier (n‐type behaviour) is seen even under UHV conditions. Measurements of the thermoelectric power and electrical conductivity are presented of the pure films and after exposure to oxidising ambient. During film growth either island growth or a growth following the Stranski‐Krastanov mechanism was observed. The comparison of the temperature dependence of thermopower and electrical conductivity leads to a discussion of the type of majority carriers, their generation as well as their transportation. For the materials investigated in this study the band model fails to explain the observed properties and a localised transport mechanism has to be considered. A transport in localised states close to the Fermi edge is discussed for TPyTAPZn and F1