Stimulating intra- and intermolecular charge transfer and nonlinear optical response for biphenalenyl biradicaloid dimer under an external electric field

Abstract

An interesting biphenalenyl biradicaloid (IDPL) dimer consisting of both-middle superimposed phenalenyls and both-end nonsuperimposed phenalenyls has been synthesized, and has attracted intensive research interest due to its intra- and intermolecular interactions and semiconductive characteristics. It is significant that under regulation of the external electric field the directional charge transfer (CT) can produce attractive properties. In the present work, the structure and electronic properties of the IDPL dimer under an external electric field (along the horizontal Fx or the vertical Fz directions) are explored, and the following properties determined: (i) as the horizontal Fx increases, the intramolecular CT becomes larger, which induces the intermolecular CT of the IDPL dimer. (ii) In contrast, as the vertical Fz increases, the large intermolecular CT gives rise to the intramolecular CT of the IDPL dimer. (iii) More importantly, the external electric field effectively regulates and controls the first hyperpolarizability (βtot) of the IDPL dimer. Compared with the vertical Fz, the horizontal Fx induces a larger first hyperpolarizability (βtot = 5.48 × 105 a.u.). Furthermore, the application of a uniform external electric field (Fx,y,z) to the IDPL dimer was investigated to define the external electric field direction of the material application. The βtot values were increased with increasing of the uniform Fx,y,z. Our study provides an effective strategy for developing high-performance NLO materials by tuning the external electric field, and could be of significance for application in switch devices.

Single-Crystal Investigation, Hirshfeld Surface Analysis, and DFT Study of Third-Order NLO Properties of Unsymmetrical Acyl Thiourea Derivatives

“…From Table S2, it can be seen that the changes in average amplitudes of the BTCC compound are very small (almost negligible), so the default field amplitude applied by Gaussian is considered reliable here. The FF method has been widely used in recent years for its ability to provide reproducible results of higher-order polarizabilities for several classes of compounds. − This method was also found to consist of other NLO calculation methods like TD-SOS, etc …”

Facially Polarized Molecule for Alkalides and Superalkalides with Considerable Nonlinear Optical Response

“…The first hyperpolarizability density and the natural transition orbital maps were also plotted by the Multiwfn. M06‐2X not only exhibits good performance for calculating electronic structures, but also broadly used to calculate electric properties,,, i.e . dipole moment, polarizability, hyperpolarizabilities.…”

Effect of external electric field on hexadiene homolog C6H6(SiF2)3

“…(2) For substances with clusters or ring structures, such as carbon nanotubes and so on, the molecular structure and electronic structure can be regulated to achieve the researches and developments of new functional materials. [5][6][7][8][9] In 2017, Tian et al 6 found that external electric field can regulate the electronic structure of carbon nanotubes. In 2018, Gao et al 7 found that the external electric field can effectively regulated the first hyperpolarizability of Interesting Biphenalenyl Biradicaloid (IDPL) dimer.…”

“…[5][6][7][8][9] In 2017, Tian et al 6 found that external electric field can regulate the electronic structure of carbon nanotubes. In 2018, Gao et al 7 found that the external electric field can effectively regulated the first hyperpolarizability of Interesting Biphenalenyl Biradicaloid (IDPL) dimer. This research can be used to further develop nonlinear (NLO) materials, which is of great significance for the application of switching devices.…”

“…In 2016, Aragonès et al 4 proposed that external electric field can catalyze (polar) Diels‐Alder reaction. (2) For substances with clusters or ring structures, such as carbon nanotubes and so on, the molecular structure and electronic structure can be regulated to achieve the researches and developments of new functional materials 5–9 . In 2017, Tian et al 6 found that external electric field can regulate the electronic structure of carbon nanotubes.…”