Novel Third-Order Nonlinear Optical Materials with Craig-Möbius Aromaticity

Abstract

Electron delocalization in aromatic materials significantly impacts their third-order nonlinear optics (NLO). Despite organometallic complexes with Craig-Möbius aromaticity attracting great attention for their unusual physicochemical properties, their third-order NLO have been little studied to date. Herein, 12 Craig-Möbius aromatic organometallics with a stable structure similar to osmapentalyne, namely, carbolong complexes, are screened by DFT. They exhibit high third-order NLO responses because of the d and p electron delocalization in the organometallic ring. Furthermore, electron–hole distribution analyses draw a conclusion that extending the conjugated plane will increase the π-conjugation system to enhance the local excitation in the plane, and the introduction of typical aromatic ligands can result in the organometallic ring-to-ligand charge transfer (RLCT), which are effective methods to improve the third-order NLO response. This study opens a new window in the application of Craig-Möbius aromatic complexes and provides a new approach for third-order NLO materials design.

Bucket Effect to Improve Third‐Order Nonlinear Optical Response on Metal‐Heteroaromatic Compounds

“…[ 6‐7 ] Previous studies have illustrated the profound influence of intermolecular packing of crystal structures, solvent effect, [ 8 ] and the interpenetrated structures [ 9 ] on third‐order NLO effects. Furthermore, the π‐conjugated systems of both organometallic rings [ 10 ] and ligands [ 11‐12 ] also effectively promote the NLO effects, which have been verified in former research. Clarifying the structural property relationships between aromaticity and third‐order NLO responses is beneficial for the development of effective NLO materials.…”

“…The smaller the NICS(1) ZZ value is, the larger the corresponding γ tends to be, which is consistent with previous reports. [ 10 ]…”

“…In the previous theoretical research, the carbolong compounds with Craig‐Möbius aromaticity exhibited a good third‐order NLO response. [ 10,24 ] Both the expansion of conjugated planarization and the introduction of typical aromatic ligands can further improve the third‐order NLO response. Simultaneously, the alkenes (C=C) have been verified that they have a better conjugation ability and higher charge transfer efficiency than alkynes (C ≡ C) in experiments.…”

Celebrating the 10th Anniversary of the Youth Innovation Promotion Association, Chinese Academy of Sciences: Emerging Young Scientists in Physical Chemistry

“…The Letter by Lu et al 39 discusses the polymer translocation times in polymer processing. The Letter by Wang et al 40 first theoretically investigates the 12 Craig−Mobius aromatic organometallics with high third-order nonlinear optical properties. The Letter by Cheng et al 41 identifies candidate structures for the important nonlinear optical material Sr 2 Be 2 B 2 O 7 (SBBO) by employing the highthroughput crystal-structure prediction method coupled with Rietveld refinements.…”

“…discusses the polymer translocation times in polymer processing. The Letter by Wang et al . first theoretically investigates the 12 Craig–Möbius aromatic organometallics with high third-order nonlinear optical properties.…”