Structures and electronic states of paramagnetic species in Al–NTCDA co-deposit films

Structures and electronic states of paramagnetic species in co-deposit film composed of 1,4,5,8-naphthalene-tetracarboxylic-dianhydride (NTCDA) and aluminum (Al) have been investigated by means of hybrid density functional theory (DFT) calculations to determine the species in detail. Al–NTCDA 1:1 complex, 1:3 Al3–NTCDA complex and an Al metal bridged dimer Al–(NTCDA)2 were examined as paramagnetic species of Al–NTCDA complexes. The simulated electron paramagnetic resonance (EPR) spectra of the 1:3 complex and the dimer were in reasonable agreement with experiment reported previously by Tachikawa et al. [Tachikawa et al., J. Phys. Chem. B 109 (2005) 3139]. It was found that the contribution from the 1:1 complex to the EPR spectra was very small. From the comparison with theoretical and experimental UV and EPR spectra, it was found that several paramagnetic and diamagnetic species exist in the co-deposit film of Al/NTCDA. The structures and electronic states were discussed on the basis of theoretical results.