Enhancement of Second-Order Nonlinear Optical Properties of Centrosymmetric Ferrocenyl Borasiloxane by a Broken-Symmetry Approach

Abstract

A new eight-membered centrosymmetric ferrocenyl borasiloxane FcBSi (1) and its pyridine adduct FcBSiPy (2) were synthesized and spectroscopically characterized. Further, the compound FcBSi (1) is confirmed by single-crystal X-ray diffraction studies, which crystallizes the triclinic crystal system in the centrosymmetric space group P1̅ with an eight-membered ring (B 2 O 4 Si 2 ) configuration. Both the compounds FcBSi (1) and FcBSiPy (2) exhibit a negative solvatochromism in nonpolar to polar solvents because the dipole interactions between solvent and solute molecules make high ground-state dipole moments. The time-dependent density functional theory (DFT) calculations further support the same trend with the experimental results. Second-order nonlinear optical (NLO) properties of FcBSi (1) and its four coordinated pyridine adduct FcBSiPy (2) were studied by the Kurtz and Perry powder technique. The enhanced second harmonic generation efficiency (1.88 times) and ground-state dipole moment in 2 were achieved by breaking the symmetry through the formation of four coordinated boron pyridine adduct in the solid state. Further, optical and NLO properties were supported by DFT, which revealed enhanced polarizability (α 0 ), hyperpolarizability (β 0 ), and dipole moment (μ tot ) in FcBSiPy (2).

A Multi‐Scale Approach for Modeling the Optical Response of Molecular Materials Inside Cavities

“…[1,2] Such materials are made by growing scaffold-like crystalline structures formed by metallic ions and organic molecules. Some envisioned optical applications of molecular materials are enhancement of: luminescence, [3] second harmonic generation, [4] Raman scattering, [5] infrared sensing, [6][7][8] and photon upconversion. [9] To fully realize their potential, the spectacular advances in fabrication techniques need to be matched by accurate and computationally efficient theoretical models.…”

“…[ 1,2 ] Such materials are made by growing scaffold‐like crystalline structures formed by metallic ions and organic molecules. Some envisioned optical applications of molecular materials are enhancement of: luminescence, [ 3 ] second harmonic generation, [ 4 ] Raman scattering, [ 5 ] infrared sensing, [ 6–8 ] and photon upconversion. [ 9 ]…”

AIE‐Active Ferrocene Appended Linear (D‐π‐A) Aromatic Ester Chromophores: Structural, Theoretical and Effect on Phenyl Ring on Luminescence and Nonlinear Optical Properties

“…In this state, the presence of water molecules surrounded by THF solution acted as a barrier, effectively blocking the non‐radiative pathway and thereby enhancing the fluorescence intensity. These morphological alterations were related to the AIE phenomenon, which was brought by the addition of water molecules, restricting the intramolecular rotation (RIR) in the solution [25] . It is significant to note that the distribution was uniform across the solution in the non‐aggregate state and that a substantial portion of the excitation experienced non‐radiative decay in the surrounding solvent.…”

Benzo‐bisimidazole based nanosheets having porphyrin like internal core with high second order nonlinear optical response: A theoretical perspective

“…In spite of experimental work; several theoretical studies were also performed to demonstrate the NLO phenomenon by enhancing the first and second order hyperpolarizability. [29][30][31][32] Jiang et al have performed theoretical study to designed a coupled porphyrin chromophores of large first static hyperpolarizability by joining the promising building blocks. 33 Feng Long Gu et al 34 designed and synthesized hexaphyrins with mislinked pyrrole units.…”

“…For instance, Xinliang Feng et al 28 explore the nonlinear optical switching in regioregular porphyrin based covalent organic framework. In spite of experimental work; several theoretical studies were also performed to demonstrate the NLO phenomenon by enhancing the first and second order hyperpolarizability 29–32 . Jiang et al have performed theoretical study to designed a coupled porphyrin chromophores of large first static hyperpolarizability by joining the promising building blocks 33 .…”