TY - JOUR

T1 - Dihydro-1H-Pyrazoles as Donor Blocks in Donor–Acceptor Chromophores for Electro-Optics: A DFT Study of Hyperpolaizability and Electronic Excitations

AU - Ishchenko, Roman

AU - Shelkovnikov, Vladimir

PY - 2024/11/4

Y1 - 2024/11/4

N2 - A diverse set of promising donors for donor–acceptor chromophores based on dihydro-1H-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.

AB - A diverse set of promising donors for donor–acceptor chromophores based on dihydro-1H-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.

KW - DFT calculations

KW - donor–acceptor chromophores

KW - electonic excitations

KW - pyrazolines

UR - https://www.scopus.com/record/display.uri?eid=2-s2.0-85208461669&origin=inward&txGid=be345f0ca8c87f281d50a67fc2b9e63d

UR - https://www.mendeley.com/catalogue/12ca0389-cd16-38a4-81c1-edecccfa960b/

U2 - 10.1002/qua.27511

DO - 10.1002/qua.27511

M3 - Article

VL - 124

JO - International Journal of Quantum Chemistry

JF - International Journal of Quantum Chemistry

SN - 0020-7608

IS - 21

ER -