Unraveling the role of superalkalis in modulating the static and dynamic hyperpolarizabilities of emerging calix[4]arenes

Khalida Khalil; Shahnaz; Ralf Ludwig; Ammar M. Tighezza; Khurshid Ayub; Tariq Mahmood; Mazhar Amjad Gilani

doi:10.1039/D3CP04825J

Unraveling the role of superalkalis in modulating the static and dynamic hyperpolarizabilities of emerging calix[4]arenes†

Khalida Khalil,^a Shahnaz,^b Ralf Ludwig,

^cde Ammar M. Tighezza,^f Khurshid Ayub,

^g Tariq Mahmood

^gh and Mazhar Amjad Gilani

*^a

Author affiliations

* Corresponding authors

^a Department of Chemistry, COMSATS University Islamabad, Lahore Campus, Lahore 54600, Pakistan
E-mail: mazhargilani@cuilahore.edu.pk

^b Department of Chemistry, Lahore College for Women University, Lahore, Pakistan

^c University of Rostock, Institute of Chemistry, Physical and Theoretical Chemistry, Albert-Einstein-Straße 27, Rostock 18059, Germany

^d University of Rostock, Faculty of Interdisciplinary Research, Department Science and Technology of Life, Light and Matter, Rostock 18059, Germany

^e Leibniz Institute for Catalysis, Rostock 18059, Germany

^f Department of Chemistry, College of Science, King Saud University, P.O. Box 2455, Riyadh 11451, Saudi Arabia

^g Department of Chemistry, COMSATS University Islamabad, Abbottabad Campus, Abbottabad 22060, Pakistan

^h Department of Chemistry, College of Science, University of Bahrain, Sakhir P. O. Box 32038, Bahrain

Abstract

Calixarenes, as novel organic materials, can play a pivotal role in the development of high-performance nonlinear optical materials due to the ease of design and fabrication. In this study, DFT simulations were employed to investigate the geometric, electronic, and NLO responses of calix[4]arene doped with Li₃O, Na₃O, and K₃O superalkalis. The computed values of the vertical ionization energies and interaction energies indicate the chemical and thermodynamic stabilities of the targeted M₃O@calix[4]arene complexes. The corresponding energy gaps (2.01 to 3.49 eV) are notably reduced, indicating the semiconductor nature of the materials. Surprisingly, the M₃O@calix[4]arene complexes exhibit transparency in the UV/visible range as the absorption peaks are shifted in the near infrared (NIR) region. The highest values of 5.9 × 10⁵ a.u. and 2.3 × 10⁸ a.u. for the respective first and second hyperpolarizabilities are observed for Na₃O@calix[4]arene. Furthermore, the Na₃O@calix[4]arene complex exhibits maximum values of 2.3 × 10⁵ a.u. for second harmonic generation (SHG) and (K₃O@calix[4]arene) 2.3 × 10⁶ a.u. for the electro-optical Pockels effect (EOPE) at 1064 nm. Similarly, approximations are made for the dynamic second hyperpolarizability coefficients (EOKE and EFISHG) at different wavelengths. Notably, the Na₃O@calix[4]arene complex demonstrates the highest quadratic nonlinear refractive index (n₂) of 9.5 × 10⁻¹⁵ cm² W⁻¹ at 1064 nm. This research paves the way for the development of stable calix[4]arenes doped with superalkalis, leading to an improved nonlinear optical (NLO) response.

Physical Chemistry Chemical Physics

Unraveling the role of superalkalis in modulating the static and dynamic hyperpolarizabilities of emerging calix[4]arenes†

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