Dihydro‐<scp>1<i>H</i></scp>‐Pyrazoles as Donor Blocks in Donor–Acceptor Chromophores for Electro‐Optics: A <scp>DFT</scp> Study of Hyperpolaizability and Electronic Excitations

ABSTRACT A diverse set of promising donors for donor–acceptor chromophores based on dihydro‐1 H ‐pyrazole (pyrazoline) for use in electro‐optics was investigated using DFT at M06‐2X/aug‐cc‐pVDZ level of theory. These calculations showed that it is possible to achieve a molecular hyperpolarizability of up to 1700*10 −30 esu (up to three times higher compared to conventional diethylaniline donors) for a simple tricyanofuran‐based acceptor by carefully tuning the donor structure. It was shown that the molecular hyperpolarizability is mainly affected by the substituents in the aryl rings in positions 3 and 1 of the pyrazoline cycle, while the substituents of the aryl ring in position 5 and the pyrazoline ring itself can be varied without significant effects on the hyperpolarizability. For one of the compounds, a detailed study of the lowest energy electronic excitation was performed using the TD‐DFT, confirming the role of the pyrazoline ring as a secondary donor.