Donor–acceptor organo-imido polyoxometalates: high transparency, high activity redox-active NLO chromophores

Al-Yasari, Ahmed; Steerteghem, Nick Van; Moll, Hani El; Clays, Koen; Fielden, John

doi:10.1039/c6dt00115g

Cited by 35 publications

(29 citation statements)

References 67 publications

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“…They are also essential for photodynamic therapy, biological imaging, and the protection of human eyes and optical sensors (by NLO materials with optical limiting effects) from high intensity LASER beams [3,4]. NLO effects arise from the interaction of an applied optical field (usually LASER) with the electronic field created by the oscillation of electrons in a NLO material, generating a new optical field that is altered in frequency, amplitude, phase, or any other physical property [5][6][7].…”

Section: Introductionmentioning

confidence: 99%

Concomitant Effects of Transition Metal Chelation and Solvent Polarity on the First Molecular Hyperpolarizability of 4-Methoxyacetophenone Thiosemicarbazone: A DFT Study

Nkungli

Ghogomu

2016

Journal of Theoretical Chemistry

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Nonlinear optical (NLO) properties of organic and metal-organic materials are of considerable interest to emerging optoelectronic and photonic technologies. Much work has been carried out on the former materials but the latter ones have received less attention till date. Herein, a density functional theory (DFT) study on the combined effects of transition metal chelation and solvent polarity on the first hyperpolarizability ( tot ) of 4-methoxyacetophenone thiosemicarbazone (MAPTSC) is reported. MAPTSC exhibits a tautomeric form with higher optical nonlinearity rendering its NLO response in polar solvents potentially switchable. Our results have revealed significant modifications of the first hyperpolarizability of MAPTSC upon complexation with different transition metal chlorides in the presence of solvents with varying dielectric constants. Therefore, its second-order NLO response is highly tunable by the synergy of transition metal chelation and solvent polarity. MAPTSC and its Zn(II) and Pt(II) chloride complexes are promising NLO materials because their gas-phase tot values are larger than those of the prototype push-pull molecules, paranitroaniline (PNA) and urea, by factors of about 1. 40-1.76 and 19.57-37.24, respectively; these factors greatly increase in polar solvent medium. Moreover, they possess high optical transparencies in the visible region of the electromagnetic spectrum which mitigate transparency/nonlinearity trade-offs, thereby increasing the likelihood of broad band NLO response.

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Section: Introductionmentioning

confidence: 99%

Concomitant Effects of Transition Metal Chelation and Solvent Polarity on the First Molecular Hyperpolarizability of 4-Methoxyacetophenone Thiosemicarbazone: A DFT Study

Nkungli

Ghogomu

2016

Journal of Theoretical Chemistry

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“…It is a potential new class of NLO materials with much better transparency/non-linearity trade-offs and reversible electrochemistry than related organic systems. 95…”

Section: Organoimido Derivatives Of Poms: Synthesis and Applicationsmentioning

confidence: 99%

“…Dalton TransactionsFielden et al have proved that polyoxometalates (POMs) can be outstanding redox active acceptors for high-performance second-order nonlinear optical (NLO) chromophores. It is a potential new class of NLO materials with much better transparency/non-linearity trade-offs and reversible electrochemistry than related organic systems 95. In2017, Diego Venegas-Yazigi et al reported the synthesis, electrochemical and photophysical properties of the first Re organometallic hybrid POM [ n Bu 4 N][Mo 6 O 18 NC 6 H 4 -CH 2 -N 3 C 2 H 2 -Re-phen(CO) 3 ] (Scheme 13).…”

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confidence: 99%

Insights into organic–inorganic hybrid molecular materials: organoimido functionalized polyoxomolybdates

2022

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“…The authors attribute the large response to a modulation of the conjugation along the polymer backbone. Al-Yasari et al have characterized donoracceptor organo-imido polyoxometalates with static first hyperpolarizabilities that exceed those of comparable compounds [76]. And Coe et al have investigated the second-order nonlinear optical response of Helquat dyes with large static first hyperpolarizabilities [77].…”

Section: B Post-tfl Experimental Researchmentioning

confidence: 99%

Physics of the fundamental limits of nonlinear optics: a theoretical perspective [Invited]

Lytel¹

2016

J. Opt. Soc. Am. B

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The theory of the fundamental limits (TFL) of nonlinear optics is a powerful tool for experimentalists seeking to create molecules and materials with large responses, and for theorists who are seeking to understand how the basic elements of quantum theory delineate the boundaries within which these searches should be conducted. On a practical level, the TFL provides a metric for measuring the performance or 'goodness' of new molecules, relative to what is possible. Explorations of large sets of structures within the theory provide insight into new design rules for creating more active molecules. This article is a review of the TFL, starting with a history of its development and its first use to discover that all molecules as of the year 2000 fell a factor of 30 below the limits, and continuing to the present day where the theory continues to provide research opportunities and challenges. The review focuses on off-resonant nonlinear optics in order to sharply focus on the key elements of the TFL, but pointers are provided to the literature for near-and on-resonance applications.

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Donor–acceptor organo-imido polyoxometalates: high transparency, high activity redox-active NLO chromophores

Cited by 35 publications

References 67 publications

Concomitant Effects of Transition Metal Chelation and Solvent Polarity on the First Molecular Hyperpolarizability of 4-Methoxyacetophenone Thiosemicarbazone: A DFT Study

Concomitant Effects of Transition Metal Chelation and Solvent Polarity on the First Molecular Hyperpolarizability of 4-Methoxyacetophenone Thiosemicarbazone: A DFT Study

Insights into organic–inorganic hybrid molecular materials: organoimido functionalized polyoxomolybdates

Physics of the fundamental limits of nonlinear optics: a theoretical perspective [Invited]

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