A novel bichromophore based on julolidine chromophores with enhanced transferring efficiency from hyperpolarizability <i>β</i> to electro-optic activity

He, Ying; Chen, Lu; Zhang, Hua; Chen, Zhuo; Huo, Fuyang; Li, Bing; Zhen, Zhen; Liu, Xinhou; Bo, Shuhui

doi:10.1039/c7tc04928e

Cited by 23 publications

(5 citation statements)

References 33 publications

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“…The formed complexes of highly polarizable FP-TCF-based anionic cyanines with a cationic polyelectrolyte have enabled an efficient translation of the optimal molecular third-order NLO properties of cyanines into macroscopic properties, leading to one of the largest third-order susceptibilities of 1.6 × 10 –10 esu and excellent figure of merit (FOM) for all-optical signal processing. Given the synergistic efforts in the study of organic second- and third-order nonlinear optics from molecule to the material level, − it seems natural to assume that the FP-TCF acceptor can be exploited as a new acceptor for synthesizing and optimizing the performance of push–pull heptamethines for EO applications.…”

Section: Introductionmentioning

confidence: 99%

Efficient, Stable, and Scalable Push–Pull Heptamethines for Electro-Optics

Zhang

Zou

et al. 2022

Chem. Mater.

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Currently, there is increasing interest in the use of push–pull heptamethine chromophores containing the 2-dicyanomethylidene-3-cyano-4,5,5-trimethyl-2,5-dihydrofuran (TCF) electron acceptor for electro-optic (EO) applications. Compared with the benchmark push–pull tetraenes with a stronger trifluoromethyl-substituted TCF acceptor (CF3-TCF), the TCF-based push–pull heptamethines showed lower EO activities; however, they have better chemical and thermal stability and higher synthetic efficacy. Herein we report the facile synthesis and analysis of structure–property relationship of dipolar heptamethines containing a strong electron acceptor, bis(4-fluorophenyl)-substituted TCF (FP-TCF). The FP-TCF acceptor was synthesized through two consecutive multiple steps, one-pot reactions to achieve a good overall yield of 50%, which is higher than that of making CF3-TCF. The reduced π–π stacking and fine-tuned bond-length alternation boost the nonlinear optical activities of FP-TCF-based heptamethines in plasmon-coupled EO polymer waveguides, leading to larger EO coefficients (up to 205%) over those of the TCF-based chromophores. More importantly, we demonstrate for the first time an ultralarge molecular first hyperpolarizability of 8437 × 10–30 esu at 1304 nm for M1a-FP-ON, which exceeds the results of two best-performing but synthetically demanding push–pull tetraene chromophores. The results mark an important milestone in developing highly efficient push–pull polymethines with good stability and synthetic scalability for photonic applications.

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Section: Introductionmentioning

confidence: 99%

Efficient, Stable, and Scalable Push–Pull Heptamethines for Electro-Optics

Zhang

Zou

et al. 2022

Chem. Mater.

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“…The complex structure 359 was also synthesized by means of Wittig reaction, formylation, and condensation reaction steps with TCF (Scheme ) . In that work, however, formation of compound 358 via Cu(I)‐catalyzed reaction preceded the condensation reaction with TCF.…”

Section: Reactions From Julolidinesmentioning

confidence: 99%

Synthesis and Derivatization of Julolidine: A Powerful Heterocyclic Structure

Varejão

Fernandes

2019

Eur J Org Chem

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Julolidines constitute a class of N‐heterocycle compounds which have in common the 2,3,6,7‐tetrahydro‐1H,5H‐benzo[1,2]quinolizine ring. Due mainly to its fluorescence properties, such structures have shown potential application in a range of scientific and technological areas and have attracted attention of a great variety of research groups. For example, julolidines have been used for detection of ions and volatile compounds in environmental and biological samples, to the construction of dye‐sensitized solar cells, photoconductive materials and as fluorescent sensors for bioimaging. This review summarizes the strategies reported to the synthesis of the julolidine ring and the principal modifications for obtaining more complex julolidine derivatives with improved fluorescence properties of these compounds. In this context, aldol condensation, olefination, imine synthesis, and cross‐coupling reactions have been extensively explored and discussed. Examples of applications, which illustrate the great potential of such structures, will also be briefly presented.

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“…A variety of dendritic structure have been explored to develop high performance second-order NLO materials so far, including dendrimers, − dendronized polymers, − hyperbranched polymers (HBPs), − and dendronized hyperbranched polymers (DHPs). − Furthermore, it has been manifested that rational regulation of the topological structure for a dendritic NLO material is highly necessary to maximize the final NLO effects. , For example, we demonstrated that by simply changing the dendrimer structure from “cone-like” to “global-like”, the corresponding d 33 values can be remarkably improved from 194 to 246 pm/V based on the same azo-chromophores . Further introducing the azo-chromophores into an intelligent X-shaped Janus structure, the resulting dendrimers, even with a relatively low generation, can surprisingly produce the largest d 33 value up to 299 pm/V for azo-chromophores due to the achievement of highly ordered noncentrosymmetric arrangement during the poling process .…”

Section: Introductionmentioning

confidence: 99%

A Correlation Study between Dendritic Structure and Macroscopic Nonlinearity for Second-Order Nonlinear Optical Materials

Zang

Liu

et al. 2020

Macromolecules

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To study the effect of dendritic structure on the macroscopic nonlinearities, four types of dendritic nonlinear optical (NLO) materials containing the same isophorone-bridged chromophores are prepared, including AB 2 -type dendrimer (D1), AB 2 -type hyperbranched polymer (HBP, HP1), "A 3 +B 2 "-type HBP (HP2), and "A 3 +AB 2 "-type HBP (HP3). The detailed 1 H NMR spectra analysis manifests that through suitable end-capping modifications, HP1 exhibits a relatively perfect dendritic structure like dendrimer with the degree of branching close to 1 while both HP2 and HP3 still contain a lot of linear structural defects. As a result, the measured second-harmonic generation (SHG) coefficients (d 33 ) of D1 and HP1 can be up to 71.3 and 77.6 pm/ V, respectively, both of which are much larger than those of HP2 (32.2 pm/V) and HP3 (55.4 pm/V). Our results strongly suggest that AB 2 -type self-polymerization with suitable end-capping modifications is a feasible methodology to achieve large NLO effects, while simultaneously maintaining merits of facile one-pot synthesis and high thermal stability of NLO effects. In addition, the higher d 33 value for HP3 than HP2 could be due to the optimization of dendritic structure derived from the particular "A 3 +AB 2 "-type polymerization, providing a new way to design hyperbranched NLO polymers.

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A novel bichromophore based on julolidine chromophores with enhanced transferring efficiency from hyperpolarizability β to electro-optic activity

Abstract: Novel bichromophores YL3 based on julolidine donor chromophores were synthesized via a Cu(i) catalyzed click-reaction and systematically characterized in this paper.

Cited by 23 publications

References 33 publications

Efficient, Stable, and Scalable Push–Pull Heptamethines for Electro-Optics

Efficient, Stable, and Scalable Push–Pull Heptamethines for Electro-Optics

Synthesis and Derivatization of Julolidine: A Powerful Heterocyclic Structure

A Correlation Study between Dendritic Structure and Macroscopic Nonlinearity for Second-Order Nonlinear Optical Materials

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