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Download fileTuning of Second-Order Nonlinear Optical Properties Based on [2.2]Paracyclophanes Isomer: the Relative Configuration and Polarizable Environment
journal contribution
posted on 19.09.2020, 13:29 authored by Jin-Ting Ye, Jing-Hai Liu, Qiang Zhang, Yong-Qing Qiu, Li-Hui WangThrough-space
charge transfer provides more flexibilities and possibilities
to regulate the properties of organic optoelectronic materials, biotechnology,
photochemistry, and so on, by changing spatially the aromatic packing
configuration. In this study, a series of [2.2]pCp-based cis (pseudogeminal)
and trans (pseudopara) molecules are designed to explore the effect
of isomers on the activities quantified by the second-order nonlinear
optical (NLO) properties from density functional theory calculations.
The results show that the first hyperpolarizability (βtot) of the trans isomer is larger than that corresponding to cis ones,
especially for cis/trans-TPA-TRZ systems.
Moreover, the designed molecule trans-TPA-TRZ shows remarkably large βtot value up to 39.7 ×
10–30 esu, which demonstrates that the activity
of a material depends not only on the intrinsic property of the acceptor
or donor itself but also on their combination, intramolecular conformation,
and conjugate packing mode. Interestingly, visualization of the full
hyperpolarizability tensor, termed the unit sphere representation,
has been used to provide insight and intuition into the relationship
between the hyper-Rayleigh scattering response coefficient and molecular
structure. Furthermore, the influence of the solid-state environment
on the NLO coefficient is substantial, particularly for the trans-TPA-TRZ molecule, whch increases further
to 84.2 × 10–30 esu according to the polarizable
continuum model and optimally tuned range-separated hybrid functional.
Our work provides rich insight into designing and developing high-performance
second-order NLO materials by tuning the relative configuration and
polarizable environment of the [2.2]pCp-based through-space π-extended
conjugated systems and might be of potential application in optoelectronics.
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Keywords
results showTPA-TRZ systemsβ tot valueTPA-TRZ moleculeinsightwhch increasesRelative Configurationtrans isomertheory calculationsSecond-Order Nonlinear Optical Prop...polarizable environmentmolecule transconfigurationPolarizable Environment Through-spa...NLO coefficientresponse coefficientoptoelectronic materialspCp-basedhyperpolarizability tensorintramolecular conformationpolarizable continuum modelNLO materialsunit sphere representationcis ones