Charge transfer in thin films of donor–acceptor complexes studied by infrared spectroscopy

The degree of charge transfer in thin films of organic charge transfer (CT)-complexes, which are deposited via thermal evaporation, is examined via infrared-spectroscopy. We demonstrate a linear relationship between the shift in the excitation energy of the CN-stretching mode of CT-complexes with the acceptor 7,7,8,8-tetracyanoquinodimethane (TCNQ) and the charge transfer. The measured correlation corresponds very well with DFT calculations. For Na-TCNQ we observe a splitting in the peak of the CN-stretching mode, which can be explained by the coupling of two modes and was confirmed by the calculations. In CT-complexes with partial charge transfer the appearance of an electronic excitation is demonstrated.

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► Linear relation between charge transfer and energy of the TCNQ CN-stretching mode.
► Splitting of CN-stretching mode in fully charged complexes due to mode coupling.
► Energy absorption band due to electronic excitation of partially charged complexes.