Synthesis of novel nonlinear optical chromophores with enhanced electro-optic activity by introducing suitable isolation groups into the donor and bridge

Liu, Fenggang; Chen, Shujie; Mo, Songmin; Qin, Gangzhi; Yu, Canwen; Zhang, Weijun; Shi, Wen‐Jing; Chen, Peiling; Xu, Huajun; Fu, Mingkai

doi:10.1039/c9tc01658a

Cited by 39 publications

(13 citation statements)

References 45 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Similar to many NIR dipolar polyenes, merocyanines, and cyanines, the meso -substituted oxazolyl thiother groups provide the sulfur’s π-accepting interaction with the conjugated structures of new push–pull heptamethines. − Herein, the primary π-accepting orbital of sulfur is associated with its low-lying sigma antibonding orbital, enabling negative hyperconjugation from the linked carbon p π orbital to the antibonding orbital σ* S–C of the sulfur–carbon bond. The NMR spectra showed that two olefinic protons H b and H c neighboring the sulfur atom in new heptamethine chromophores experience significant deshielding of chemical shifts (0.37–0.53 ppm) compared to the corresponding protons in meso -chloro-substituted chromophores (Table S1).…”

Section: Resultsand Discussionmentioning

confidence: 99%

Critical Role of Non-classical Intermolecular Hydrogen Bonding in Affecting the π–π Stacking and Nonlinear Optical Properties of Tricyanofuran-Based Push–Pull Heptamethines

Zhang

Zou

et al. 2021

Chem. Mater.

View full text Add to dashboard Cite

Currently, there is immense interest in the chemistry of push–pull heptamethines containing a strong acceptor of 2-dicyanomethylidene-3-cyano-4,5,5-trimethyl-2,5-dihydrofuran (TCF). This class of compounds is important as second-order nonlinear optical (NLO) chromophores for electro-optic (EO) applications. The crystal packing of TCF-based NLO chromophores is generally dominated by intermolecular π–π stacking and non-classical C–H···N(cyano) hydrogen bonding interactions, considerably limiting the bulk NLO properties of chromophores in solid films. In this paper, we report a series of TCF-based push–pull heptamethines bearing the substituent of 4,5-diphenyl-oxazol-2-ylsulfanyl group at the central position of the π-conjugated bridge. Crystallographic studies show a very uncommon crystal packing mode of one-dimensional chain structure with vanished C–H···N(cyano) contacts and negligible π–π stacking. Such reduced intermolecular interactions and fine-tuned bond length alternation lead to NLO performance breakthrough of these chromophores in poled polymeric films, including much better EO coefficients up to 465% in improvement, higher polar order, and larger molecular hyperpolarizabilities (up to 4,135 × 10–30 esu at 1304 nm), over the results from the simple chloro-substituted heptamethines. Our study indicates that the interplay of steric effect, non-classical C–H···N hydrogen bonding, and intermolecular π–π stacking is critically important in optimizing the supramolecular assembly and NLO properties of TCF-based heptamethines for photonic applications.

show abstract

Section: Resultsand Discussionmentioning

confidence: 99%

Critical Role of Non-classical Intermolecular Hydrogen Bonding in Affecting the π–π Stacking and Nonlinear Optical Properties of Tricyanofuran-Based Push–Pull Heptamethines

Zhang

Zou

et al. 2021

Chem. Mater.

View full text Add to dashboard Cite

show abstract

“…The latter threshold can be overcome by switching to more recent nonlinear materials. New organic materials have been shown to work under much higher temperatures 46,47 . Also, recent barium titanate (BTO) plasmonic modulators have shown great potential for high-power applications with demonstrated high-temperature stability beyond 250 °C 48 .…”

Section: Methodsmentioning

confidence: 99%

Compact and ultra-efficient broadband plasmonic terahertz field detector

et al. 2019

View full text Add to dashboard Cite

Terahertz sources and detectors have enabled numerous new applications from medical to communications. Yet, most efficient terahertz detection schemes rely on complex free-space optics and typically require high-power lasers as local oscillators. Here, we demonstrate a fiber-coupled, monolithic plasmonic terahertz field detector on a silicon-photonics platform featuring a detection bandwidth of 2.5 THz with a 65 dB dynamical range. The terahertz wave is measured through its nonlinear mixing with an optical probe pulse with an average power of only 63 nW. The high efficiency of the scheme relies on the extreme confinement of the terahertz field to a small volume of 10−8(λTHz/2)3. Additionally, on-chip guided plasmonic probe beams sample the terahertz signal efficiently in this volume. The approach results in an extremely short interaction length of only 5 μm, which eliminates the need for phase matching and shows the highest conversion efficiency per unit length up to date.

show abstract

“…[34][35][36] In past a decade, EO performance has been improved via strategies such as siteisolation, self-assembly, chromophore blending, and charge blocking layers (CBLs) to enhance the r N hcos 3 yi value of bulk materials. 26,28,31,33,[37][38][39][40][41][42][43][44][45][46][47][48][49] Recent work 50,51 has also shown substantial increases in hyperpolarizability due to theoryguided design, after years of little increase in b of reported chromophores.…”

Section: Introductionmentioning

confidence: 99%

Design and synthesis of chromophores with enhanced electro-optic activities in both bulk and plasmonic–organic hybrid devices

Elder

Johnson

et al. 2022

Mater. Horiz.

Self Cite

View full text Add to dashboard Cite

show abstract

Synthesis of novel nonlinear optical chromophores with enhanced electro-optic activity by introducing suitable isolation groups into the donor and bridge

Abstract: Four nonlinear optical chromophores A–D functionalized with different isolation groups on both the donor and bridge sections of the chromophores have been synthesized and systematically investigated.

Cited by 39 publications

References 45 publications

Critical Role of Non-classical Intermolecular Hydrogen Bonding in Affecting the π–π Stacking and Nonlinear Optical Properties of Tricyanofuran-Based Push–Pull Heptamethines

Critical Role of Non-classical Intermolecular Hydrogen Bonding in Affecting the π–π Stacking and Nonlinear Optical Properties of Tricyanofuran-Based Push–Pull Heptamethines

Compact and ultra-efficient broadband plasmonic terahertz field detector

Design and synthesis of chromophores with enhanced electro-optic activities in both bulk and plasmonic–organic hybrid devices

Contact Info

Product

Resources

About